CN102268823A - Method for improving dye depth of cellulose fiber fabrics by using chitosan - Google Patents
Method for improving dye depth of cellulose fiber fabrics by using chitosan Download PDFInfo
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- CN102268823A CN102268823A CN 201110230522 CN201110230522A CN102268823A CN 102268823 A CN102268823 A CN 102268823A CN 201110230522 CN201110230522 CN 201110230522 CN 201110230522 A CN201110230522 A CN 201110230522A CN 102268823 A CN102268823 A CN 102268823A
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- shitosan
- fiber fabric
- cellulose base
- base fiber
- dye
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- 239000004744 fabric Substances 0.000 title claims abstract description 78
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920001661 Chitosan Polymers 0.000 title abstract description 8
- 239000000975 dye Substances 0.000 claims abstract description 50
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000129 anionic group Chemical group 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 38
- 229920002678 cellulose Polymers 0.000 claims description 38
- 239000001913 cellulose Substances 0.000 claims description 38
- 238000004043 dyeing Methods 0.000 claims description 38
- 239000002585 base Substances 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 229920000742 Cotton Polymers 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000344 soap Substances 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 229920000297 Rayon Polymers 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 238000004061 bleaching Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000000985 reactive dye Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 239000000982 direct dye Substances 0.000 claims description 5
- 239000000984 vat dye Substances 0.000 claims description 4
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 claims description 2
- 239000000980 acid dye Substances 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000010446 mirabilite Substances 0.000 description 6
- 230000037303 wrinkles Effects 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention relates to a method for improving the dye depth of cellulose fiber fabrics by using chitosan. In the method, a polycarboxylic acid solution is used as a solvent and a cross-linking agent of chitosan and epoxy chloropropane is used as a cross-linking agent, and chitosan is covalently grafted to the surface of the cellulose fiber fabrics through padding, preliminary drying and baking at a high temperature. The combining strength of chitosan and the cellulose fiber fabrics is increased greatly, the electrostatic repulsion between the cellulose fiber fabrics and anionic dyes is reduced, the dye-uptake of dyes and the color depth of the fabrics are improved obviously, and the crease resistance of the cellulose fiber fabrics processed by using the method is improved obviously.
Description
Technical field
The invention belongs to field of textiles, be specifically related to a kind of method that improves the cellulose base fiber fabric dye level with shitosan.
Background technology
When cellulose base fiber fabric contacts with the aqueous solution, because the ionization of some group in the cellulose macromolecule can make negative electrical charge on the fabric face band; Anionic dye is also electronegative in the aqueous solution, during dyeing, can have bigger electrostatic repulsion between dyestuff and the fiber, makes the dye-uptake of dyestuff reduce.Adopt mostly at present in dyeing course, to add the electro kinetic potential that a large amount of neutral electrolytes reduce fiber surface, reduce dyestuff and interfibrous electrostatic repulsion, improve dye-uptake.But electrolytically add the increase that affiliation causes the dyeing cost, make that simultaneously electrolytical concentration increases in the dyeing waste-water, increased the weight of the difficulty of wastewater treatment.
Many in recent years researchers adopt cation modifier that cellulose fibre is carried out modification and handle, on cellulose fibre, introduce amino, amido, make cellulose fibre in dye bath, be electropositive, allow the electrostatic repulsion between itself and the anionic dye reduce, strengthen the adsorption capacity of cellulose fibre, improve the dye-uptake and the degree of fixation of dyestuff anionic dye.
Shitosan is a kind of natural polycationic compounds, has closely similar structure with cellulose fibre, is easy to be adsorbed by cellulose.Under acid condition, the amino of shitosan can be positively charged in conjunction with H+, and it is put on the cellulose fibre, can reduce fiber surface with negative electrical charge, thereby the fiber surface negative electrical charge is to the anionic electrostatic repulsion of coloring matter in the minimizing dyeing course, improves the dyestuff dye-uptake.Zhou Wenchang [Zhou Wenchang, Wang Nanfang. [J] textile technology progress is inquired in the application of shitosan in cotton fabric dyeing process, 2006, ] and Li Lianju [Li Lianju (6): 33-35., Zhang Jianli. the shitosan impregnation process is to influence [J] printing and dyeing of cotton fabric by utilizing reactive dye dyeing, 2006, (22): 1-3.] adopt the mode of padding and flooding respectively, put shitosan in order surface of cotton fabric, improve the dye-uptake of dyestuff and the color depth of fabric.This dual mode mainly is to utilize the physical absorption between shitosan and the cellulose fibre to make shitosan attached to the cellulose base fiber fabric surface, and both are not in conjunction with firm, and in dyeing course subsequently, shitosan comes off from fabric easily, influences final effect.Peng Yonggang [Peng Yonggang, Ji Junling, Tao Yongxin, Deng. dyeability research [J] printing and dyeing of chitosan graft oxidation COTTON FABRIC, 2011 (8): 12-14,32.] with the cellulose fibre selective oxidation, make 2, the 3-dialdehyde cellulose, utilize then on the shitosan-schiff base reaction between NH2 and the aldehyde radical, shitosan is covalently bound on the cellulose fibre, significantly improved the fastness that combines between shitosan and the cellulose fibre, but in the oxidizing process of cellulose fibre, cause the damage of fibre strength easily.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method that improves the cellulose base fiber fabric dye level with shitosan, significantly improve the fastness that combines between shitosan and the cellulose fibre by this method, the chitin modified cellulose base fiber fabric that obtains obviously strengthens the adsorption capacity of dyestuff, and the dye-uptake of dyestuff and the color depth of fabric obviously improve.
The technical scheme that realizes above-mentioned purpose is: with solvent and the crosslinking agent of polybasic carboxylic acid solution as shitosan, epoxychloropropane is as crosslinking agent, by pad, preliminary drying, high temperature bake, to the cellulose base fiber fabric surface, select for use anionic dye to carry out normal dyeing then the shitosan covalence graft.
The invention provides a kind of method, may further comprise the steps with shitosan raising cellulose base fiber fabric dye level:
(1) be the NaOH solution of 10-30% with immersing mass fraction under the cellulose base fiber fabric room temperature of destarch, boiling-off, bleaching, after soaking 10-20min, wash 3-5 time, in being the glacial acetic acid of 5%-10%, mass fraction soaks 30-45min again, be washed to neutrality at last, 80-85 ℃ of oven dry makes alkali pretreatment of fiber cellulose fiber fabric;
(2) shitosan is dissolved in the polybasic carboxylic acid solution that mass fraction is 5%-10%, treat that it dissolves fully after, add crosslinking agent, make the shitosan dressing liquid;
(3) will pad the shitosan dressing liquid through the pretreated cellulose base fiber fabric of alkali, two soak two rolls pick-up 70%-100%, padding mass fraction again is 5%-20%NaOH solution, and two soak two rolls pick-up 80%-100%, after the 80-85 ℃ of oven dry, high temperature bakes 1-3min, washes 3-5 time then, removes the not shitosan of covalent cross-linking, after the 80-85 ℃ of oven dry, select for use the anionic dyestuff to carry out normal dyeing, dyeing gets final product through washing, soap, drying after finishing.
As shown from the above technical solution: the present invention at first adopts alkali lye that fabric is carried out activation processing, utilizes the expanded effect of alkali to cellulose fibre, improves the accessibility and the reactivity of fiber; Polybasic carboxylic acid is the solvent of shitosan, can be used as crosslinking agent again, under appropriate condition can with cellulose, shitosan generation esterification, and the free carboxyl group of polybasic carboxylic acid also can form salt type bond with the reaction of amino in the shitosan; The crosslinking agent epoxychloropropane can be crosslinked with hydroxyl, the hydroxyl on the shitosan, amino on the cellulose macromolecule under the high-temperature alkaline condition, realizes the covalent cross-linking of shitosan and cellulose fibre.
As preferably, its molecular weight of shitosan is 1.1-2.5 * 10
5, deacetylation is 75-95%.
As preferably, the polybasic carboxylic acid described in the step (2) is one or both in citric acid, the tartaric acid.The solubility of shitosan in citric acid, tartaric acid solution is better.
As preferably, the cellulose base fiber fabric described in the step (1) is cotton, fiber crops, viscose fabric or both intertextures.
As preferably, the concentration of shitosan in polybasic carboxylic acid solution described in the step (2) is 0.25g/L-1.25g/L.Chitosan concentration is too high, and solution viscosity is too high, influences subsequent treatment.
As preferably, the crosslinking agent described in the step (2) is an epoxychloropropane, and concentration is 0.01-0.05mol/L in polybasic carboxylic acid solution.Epoxychloropropane concentration is too high, can cause the shitosan self-crosslinking, reduces the amount of shitosan and cellulose graft.
As preferably, the baking temperature described in the step (3) is 140-160 ℃.
As preferably, the anionic dyestuff described in the step (3) is REACTIVE DYES, direct dyes, ACID DYES or soluble vat dye.
The present invention is with the method advantage that shitosan improves the cellulose base fiber fabric dye level:
(1) polybasic carboxylic acid is the solvent of shitosan, is again the crosslinking agent between shitosan and the cellulose fibre, helps shitosan fixing on cellulose base fiber fabric.
(2) epoxychloropropane both can with the hydroxyl reaction on the cellulose macromolecule, again can with hydroxyl on the shitosan, amino reaction, after high temperature baked, shitosan was covalently bonded to the cellulose base fiber fabric surface, prevented that in the dyeing course, shitosan comes off from fabric face.
(3) cellulose base fiber fabric of modification of the present invention significantly strengthens the absorption property of anionic dye, has improved the dye-uptake of dyestuff and the color depth of fabric, can reduce the consumption of neutral electrolyte in the dyeing course.
(4) wrinkle resistance of the cellulose base fiber fabric of modification of the present invention obviously improves.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be understood that these embodiment just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1
The alkali preliminary treatment: 2g is immersed mass fraction under the COTTON FABRIC room temperature of destarch, boiling-off, bleaching be 20% NaOH solution, after soaking 20min, wash 3 times, in 10% glacial acetic acid, soak 30min again, be washed to neutrality, 80 ℃ of oven dry make alkali preliminary treatment COTTON FABRIC;
It is in 5% the citric acid solution that the 0.025g shitosan is dissolved in the 100mL mass fraction, treat that it dissolves fully after, add the 0.001moL epoxychloropropane, make the shitosan dressing liquid;
To pad the shitosan dressing liquid through the pretreated COTTON FABRIC of alkali, two soak two rolls, pick-up 70%, and padding mass fraction again is 5%NaOH solution, two soak two rolls, after 100%, 85 ℃ of oven dry of pick-up, 140 ℃ bake 3min, wash then 3 times, remove the not shitosan of covalent cross-linking, after 85 ℃ of oven dry, select for use REACTIVE DYES to carry out normal dyeing.
Comparative example 1:
It is in 1% the acetum that the 0.025g shitosan is dissolved in the 100mL mass fraction, makes the shitosan dressing liquid; To pad the shitosan dressing liquid through the COTTON FABRIC of alkali preliminary treatment (processing procedure is with embodiment 1) then, two soak two rolls, and after 70%, 85 ℃ of oven dry of pick-up, 140 ℃ bake 3min, washes then 3 times, after 85 ℃ of oven dry, selects for use REACTIVE DYES to carry out normal dyeing.The dyeing prescription that embodiment 1 and comparative example 1 use:
REACTIVE DYES 3RS/% (o.w.f) 2
Glauber salt/gL
-150
Sodium carbonate/gL
-120
Bath raio 1: 50
Room temperature goes into to dye, and adds glauber salt behind the 15min, slowly is warming up to 60 ℃, continuous dye add sodium carbonate fixation 30min behind the 15min after, take out sample, use cold wash, soap boiling (soap flakes 2g/L, soda ash 2g/L, 95 ℃, 10min, bath raio 1: 30), washing is dried.
Embodiment 2
The alkali preliminary treatment: 2g is immersed mass fraction under the viscose fabric room temperature of destarch, boiling-off, bleaching be 10% NaOH solution, after soaking 10min, wash 4 times, in 5% glacial acetic acid, soak 45min again, be washed to neutrality, 85 ℃ of oven dry make alkali preliminary treatment viscose fabric;
It is in 10% the tartaric acid solution that the 0.05g shitosan is dissolved in the 100mL mass fraction, treat that it dissolves fully after, add the 0.002moL epoxychloropropane, make the shitosan dressing liquid;
To pad the shitosan dressing liquid through the pretreated viscose fabric of alkali, two soak two rolls, pick-up 80%, and padding mass fraction again is 10%NaOH solution, two soak two rolls, after 80%, 80 ℃ of oven dry of pick-up, 150 ℃ bake 2min, wash then 4 times, remove the not shitosan of covalent cross-linking, after 80 ℃ of oven dry, select for use direct dyes to carry out normal dyeing.
Comparative example 2
It is in 1% the acetum that the 0.05g shitosan is dissolved in the 100mL mass fraction, makes the shitosan dressing liquid; To pad the shitosan dressing liquid through the viscose fabric of alkali preliminary treatment (processing method is with embodiment 2), two soak two rolls, and after 80%, 80 ℃ of oven dry of pick-up, 150 ℃ bake 2min, wash then 4 times, after 80 ℃ of oven dry, select for use direct dyes to carry out normal dyeing.
The dyeing prescription that embodiment 2 and Comparative Examples 2 are used:
Direct dyes are Congo red/% (o.w.f) 2
Glauber salt/gL
-150
Bath raio 1: 50
Room temperature goes into to dye, and adds glauber salt behind the 15min, slowly is warming up to 50 ℃, behind the insulation 30min, takes out sample, uses cold wash, soap boiling (soap flakes 2g/L, soda ash 2g/L, 95 ℃, 10min, bath raio 1: 30), washing, oven dry.
Embodiment 3
The alkali preliminary treatment: 2g is immersed mass fraction under the linen room temperature of destarch, boiling-off, bleaching be 30% NaOH solution, after soaking 20min, wash 5 times, in 8% glacial acetic acid, soak 35min again, be washed to neutrality, 85 ℃ of oven dry make alkali preliminary treatment linen;
It is in 8% citric acid, the tartaric acid mixed solution (citric acid and tartaric mol ratio are 3: 1) that the 0.125g shitosan is dissolved in the 100mL mass fraction, treat that it dissolves fully after, add the 0.005moL epoxychloropropane, make the shitosan dressing liquid;
To pad the shitosan dressing liquid through the pretreated linen of alkali, two soak two rolls pick-up 100%, padding mass fraction again is 20%NaOH solution, and two soak two rolls pick-up 90%, after 85 ℃ of oven dry, 160 ℃ bake 1min, wash then 5 times, remove the not shitosan of covalent cross-linking, after 85 ℃ of oven dry, select for use soluble vat dye to carry out normal dyeing, dyeing gets final product through washing, soap, drying after finishing.
Comparative example 3
It is to make the shitosan dressing liquid in 1% the acetum that the 0.125g shitosan is dissolved in the 100mL mass fraction, to pad the shitosan dressing liquid through the linen of alkali preliminary treatment (processing method is with embodiment 3), two soak two rolls, after 100%, 85 ℃ of oven dry of pick-up, 160 ℃ bake 1min, wash then 5 times, after 85 ℃ of oven dry, select for use soluble vat dye to carry out normal dyeing, dyeing gets final product through washing, soap, drying after finishing.
The dyeing prescription that embodiment 3 and Comparative Examples 3 are used:
Anthrasol Blue IBC/% (o.w.f) 2
Glauber salt/gL
-130
Bath raio 1: 50
Room temperature goes into to dye, and adds glauber salt behind the 15min, slowly is warming up to 40 ℃, behind the insulation 30min, take out sample, immerse in the colour developing liquid (97.7% sulfuric acid concentration is 20mL/L), behind the 10min, take out sample, use cold wash, soap boiling (soap flakes 2g/L, soda ash 2g/L, 95 ℃, 10min; bath raio 1: 30), washing, oven dry.
Embodiment 4
The alkali preliminary treatment: 2g is immersed mass fraction under sticking/cotton (35/65) fabric room temperature of destarch, boiling-off, bleaching be 20% NaOH solution, after soaking 15min, wash 3 times, in 5% glacial acetic acid, soak 45min again, be washed to neutrality, 85 ℃ of oven dry make the alkali preliminary treatment and glue/COTTON FABRIC;
It is in 6% citric acid, the tartaric acid mixed solution (citric acid and tartaric mol ratio are 4: 1) that the 0.1g shitosan is dissolved in the 100mL mass fraction, treat that it dissolves fully after, add the 0.004moL epoxychloropropane, make the shitosan dressing liquid;
Will through alkali pretreated sticking/COTTON FABRIC pads the shitosan dressing liquid, two soak two rolls pick-up 90%, padding mass fraction again is 15%NaOH solution, and two soak two rolls pick-up 100%, after 80 ℃ of oven dry, 150 ℃ bake 3min, wash then 4 times, remove the not shitosan of covalent cross-linking, after 80 ℃ of oven dry, select acid dyeing for use, dyeing gets final product through washing, soap, drying after finishing.
Comparative example 4
It is to make the shitosan dressing liquid in 1% the acetum that the 0.1g shitosan is dissolved in the 100mL mass fraction, to pad the shitosan dressing liquid through the sticking/COTTON FABRIC of alkali preliminary treatment (processing method is with embodiment 4), two soak two rolls, after 90%, 80 ℃ of oven dry of pick-up, 150 ℃ bake 3min, wash then 4 times, after 80 ℃ of oven dry, select acid dyeing for use, dyeing gets final product through washing, soap, drying after finishing.
The dyeing prescription that embodiment 4 and Comparative Examples 4 are used:
Acid Orange II/% (o.w.f) 2
Ammonium sulfate/% (o.w.f) 8
Bath raio 1: 50
After preparing dye liquor by above-mentioned prescription, dye bath is warming up to 40 ℃, fabric is dropped into begin dyeing in the dye bath.Dye bath is warming up to 100 ℃ gradually with the speed of 2 ℃/min, dyes 60min at 100 ℃, takes out sample after dyeing finishes, and uses cold wash, oven dry.
Embodiment 5
The mensuration of dye uptake:, calculate dye-uptake with following formula with the absorbance of 722S spectrophotometer at maximum absorption wave strong point mensuration dye liquor:
Dye-uptake/%=(1-I/I
0) * 100
In the formula: I is dyeing back raffinate absorbance; I
0Be dye liquor initial concentration absorbance.
The mensuration of color depth (K/S value): with DYED FABRICS folding twice (four layers), adopt Datacolor SF60OX computer color measurement and color match instrument to measure the K/S value of DYED FABRICS at λ max place, each sample is surveyed and is averaged for four times.
The mensuration of anti-crease property: the anti-crease property of fabric is pressed GB/T3819-1997 " textiles anti-crease property " standard testing.
Measure embodiment 1～4, comparative example 1～4 and handle dye-uptake, color depth, the wrinkle resistance of fabric by top method without shitosan, shown in result such as the table 1, table 2:
The Color of table 1 shitosan finish fabric
Can find out that from table 1 cellulose base fiber fabric is after the shitosan arrangement, dye-uptake, K/S value obviously increase, and only rely on physical bond in the comparative example 1～4 between fabric and the shitosan, and in dyeing course subsequently, shitosan easily comes off from fabric; And the polybasic carboxylic acid that embodiments of the invention 1-4 uses be the solvent of shitosan is the covalent cross-linking that crosslinking agent, epoxychloropropane also can be realized shitosan and cellulose fibre simultaneously, makes the color depth of the dye-uptake of final dyestuff and fabric much larger than Comparative Examples.
Table 2 shitosan finish fabric wrinkle resistance and the not contrast of finish fabric
As can be seen from Table 2, after cellulose base fiber fabric pads chitosan solution, wrinkle resistance increases to some extent, this is because shitosan is a kind of natural high polymer, form a skim at the cellulose fibre surface energy, but owing to only rely on physical absorption to combine between shitosan and the cellulose fibre, so that wrinkle resistance increases is not obvious.And polybasic carboxylic acid that embodiments of the invention 1-4 uses and epoxychloropropane all can be used as the crosslinking agent between shitosan and the cellulose fibre, after high temperature bakes, between shitosan and cellulose fibre, form covalent cross-linking, increased the elasticity of fiber, improve the ability that fabric is replied from deformation, made the wrinkle resistance of fabric obviously improve.
With above-mentioned foundation desirable embodiment of the present invention is enlightenment, and by above-mentioned description, the related work personnel can carry out various change and modification fully in the scope that does not depart from this invention technological thought.The technical scope of this invention is not limited to the content on the specification, must determine its technical scope according to the claim scope.
Claims (9)
1. method that improves the cellulose base fiber fabric dye level with shitosan, it is characterized in that: with solvent and the crosslinking agent of polybasic carboxylic acid solution as shitosan, epoxychloropropane is as crosslinking agent, by pad, preliminary drying, high temperature bake, to the cellulose base fiber fabric surface, select for use anionic dye to carry out normal dyeing then the shitosan covalence graft.
2. claim 1 is described improves the method for cellulose base fiber fabric dye level with shitosan, may further comprise the steps:
(1) will immerse mass fraction under the cellulose base fiber fabric room temperature of destarch, boiling-off, bleaching is the NaOH solution of 10-30%, after soaking 10-20min, wash 3-5 time, in being the glacial acetic acid of 5%-10%, mass fraction soaks 30-45min again, be washed to neutrality at last, 80-85 ℃ of oven dry makes alkali pretreatment of fiber cellulose fiber fabric;
(2) shitosan is dissolved in the polybasic carboxylic acid solution that mass fraction is 5%-10%, treat that it dissolves fully after, add crosslinking agent, make the shitosan dressing liquid;
(3) will pad the shitosan dressing liquid through the pretreated cellulose base fiber fabric of alkali, two soak two rolls pick-up 70%-100%, padding mass fraction again is 5%-20%NaOH solution, and two soak two rolls pick-up 80%-100%, after the 80-85 ℃ of oven dry, high temperature bakes 1-3min, washes 3-5 time then, removes the not shitosan of covalent cross-linking, after the 80-85 ℃ of oven dry, select for use the anionic dyestuff to carry out normal dyeing, dyeing gets final product through washing, soap, drying after finishing.
3. claim 1 is described improves the method for cellulose base fiber fabric dye level with shitosan, and it is characterized in that: its molecular weight of used shitosan is 1.1-2.5 * 10
5, deacetylation is 75-95%.
4. claim 1 is described improves the method for cellulose base fiber fabric dye level with shitosan, and it is characterized in that: polybasic carboxylic acid is one or both in citric acid, the tartaric acid.
5. claim 2 is described improves the method for cellulose base fiber fabric dye level with shitosan, and it is characterized in that: cellulose base fiber fabric is cotton, fiber crops, viscose fabric or both intertextures.
6. claim 2 is described improves the method for cellulose base fiber fabric dye level with shitosan, and it is characterized in that: the concentration of shitosan in polybasic carboxylic acid solution is 0.25g/L-1.25g/L.
7. claim 2 is described improves the method for cellulose base fiber fabric dye level with shitosan, and it is characterized in that: crosslinking agent is an epoxychloropropane, and concentration is 0.01-0.05mol/L in polybasic carboxylic acid solution.
8. claim 2 is described improves the method for cellulose base fiber fabric dye level with shitosan, and it is characterized in that: baking temperature is 140-160 ℃.
9. claim 2 is described improves the method for cellulose base fiber fabric dye level with shitosan, and it is characterized in that: the anionic dyestuff is REACTIVE DYES, direct dyes, ACID DYES or soluble vat dye.
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