CN102677465A - Modified tussah silk fabric with functionalized nanometer chitosan and nanometer titanium dioxide - Google Patents
Modified tussah silk fabric with functionalized nanometer chitosan and nanometer titanium dioxide Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 38
- 239000004744 fabric Substances 0.000 title claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 64
- 239000004408 titanium dioxide Substances 0.000 title 1
- 239000004753 textile Substances 0.000 claims abstract description 101
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 35
- 239000000835 fiber Substances 0.000 claims description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims description 13
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- -1 poly Chemical compound 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000000845 anti-microbial effect Effects 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000004043 dyeing Methods 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 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 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 230000037303 wrinkles Effects 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 7
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- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
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- 230000001580 bacterial effect Effects 0.000 abstract 1
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- 229920000742 Cotton Polymers 0.000 description 6
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- 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 description 5
- 239000000980 acid dye Substances 0.000 description 5
- 239000001488 sodium phosphate Substances 0.000 description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 150000004040 pyrrolidinones Chemical class 0.000 description 4
- 238000004045 reactive dyeing Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 102000004169 proteins and genes Human genes 0.000 description 3
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- 238000009941 weaving Methods 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- QQLILYBIARWEIF-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)CCO QQLILYBIARWEIF-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
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- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
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- 238000005213 imbibition Methods 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
本发明涉及一种功能化纳米壳聚糖和纳米二氧化钛改性的柞蚕丝织物，依次通过由柞蚕长丝织造柞蚕丝织物、制备整理液和进行柞蚕丝织物整理的步骤而得，解决了现有纺织材料改性技术中的无法有效改善柞蚕丝织物的对环境损害、易皱、不抗菌、易缩以及染色性差、舒适性和功能差等技术问题，改善和提高了柞蚕丝织物的抗皱、柔软、抗菌、防缩、自清洁、抗紫外线、染料的吸附效率等综合性能，且具备制备成本低、工艺简单、环保、易实现等有益技术效果。The invention relates to a tussah silk fabric modified by functionalized nano-chitosan and nano-titanium dioxide. The textile material modification technology cannot effectively improve the technical problems of tussah silk fabrics such as environmental damage, easy to wrinkle, non-bacterial, easy to shrink, poor dyeability, poor comfort and function, and improve and enhance the anti-wrinkle and softness of tussah silk fabrics. , antibacterial, anti-shrinkage, self-cleaning, anti-ultraviolet, dye adsorption efficiency and other comprehensive properties, and has beneficial technical effects such as low preparation cost, simple process, environmental protection, and easy realization.
Description
Technical field
The invention belongs to textile material modification technology field, relate in particular to functionalized nano tussah silk textiles finishing technique field, particularly relate to a kind of functionalized nano shitosan and nano-titanium dioxide modified tussah silk textiles.
Background technology
Along with the continuous enhancing of domestic and international environmental protection consciousness, exploitation textiles formaldehyde-free durable crease-proof finishing agent becomes development trend.Formaldehydeless finishing agent of having developed such as epoxy resin, double hydroxyethyl sulfone, polybasic carboxylic acid and soluble polyurethane etc.; In application, obtained certain effect; But all exist certain shortcoming such as ageing low, strength damage big, be prone to yellowing; Particularly these finishing agents all are chemical syntheses, and some also has hypotoxicity.
Environmental fabric finishing agent is safe, nontoxic and excellent biological compatibility with it, and is noticeable gradually in recent years, and it is put in order COTTON FABRIC with natural materials such as protein, chitin, shitosan etc.The Along with people's growth in the living standard; The consumer not only considers the quality index of textiles and takes performance now; More consider environmental protection indexs such as harm, hope that textiles has more functions to the human body beneficial health, as have skin care, antibiotic, preserve moisture, uvioresistant etc.Though these environmental finishing agent raw materials are green, safe in utilization, simple use still exists the not enough problem of poor, the wrinkle resistant durability of anchor effect, and can not fully satisfy these required functions of health of people simultaneously.
According to U.S. Patent number US6239710, under 150 ℃ to 280 ℃ temperature,, with an organic solvent prepare finishing agent, but finishing effect is undesirable and comparatively serious to environmental nuisance at heated in water solution silk.A kind of environment-friendly type weaving protein fibre dressing liquid is disclosed at european patent number EP145683; Though reached higher environmental protection index; But the height of preparation cost, the complicacy of technology causes in actual industrial production preparation, being difficult to routine and uses on a large scale and use.
At present, in the textile material field, cotton fiber is a kind of senior native cellulose fibre, is considered to " green fiber ".Its COTTON FABRIC quality is plentiful abundant, soft hand feeling, and good sucting wet air permeability and good wearing comfort always receive people's favor, and market and development prospect are widely at home and abroad arranged.In various fabrics, textile clothes are one of most popular consumer goods of back to nature, but COTTON FABRIC is wrinkling serious in dress, after washing, need flatiron could recover original outward appearance.For a long time, the anti-wrinkle shrink-proof finishing agent great majority that use are the formolation compound, in arrangement processing and wearing process, can discharge ecological environment and the extremely harmful formaldehyde of human body.
And useless silk is as the main discarded object of Silk Industry, and shitosan is the second largest regenerated resources of nature as the discarded object of materials such as shrimp, crab, is only second to cotton fiber, but is not all effectively utilized.
Simultaneously, we know that tussah silk is the principal item of tussah, belongs to natural protein fibre, and its single fiber is thick, good springiness, fabric is plentiful, water imbibition is strong, and acid-fast alkali-proof, wearing comfort are high, have rough, magnificent appearance style.But compare with other fibers, still there are some weakness in tussah silk on wearability, especially at aspects such as water stain, yellowing, wrinkle.Along with the development of synthetic fiber processing industry, easy wrinkle, the yielding defective of silk tussah fibre goods highlight more, have become a great problem of domestic and international silk circle of puzzlement.Therefore, overcome its weakness, have great importance for the quality and the functionalization that improve tussah silk through modification technology.
The appearance of nano material is for the modification of tussah silk provides a new approach.Nano titanium oxide is colourless particulate, and particle diameter is little, and is nontoxic, tasteless, has physics, the chemical property such as optics, electricity, chemistry, catalysis of a series of excellences, anti-aging at macromolecular material, improve and existingly on heat endurance and the mechanical property use widely.Aspect the exploitation new textile material, nano titanium oxide can be given fibrous material with functions such as uvioresistant, infrared ray, wear-resisting, antistatic, antibiotic, automatically cleanings, is with a wide range of applications.
Shitosan comes from shellfish shells such as shrimp, crab, its aboundresources.As the unique alkaline polysaccharide of nature, shitosan has characteristics such as excellent biological compatibility, avirulence and biodegradability, can be used for coloration of textile materials such as cotton, hair, silk at field of textiles and increase deeply, improves the anti-microbial property of textiles etc.But because the macromolecular chain of shitosan is longer, though some molecule can get between fiber under certain condition, most surfaces attached to silk fiber influence the feel of fiber etc.Shitosan is processed macromolecule organic nano particulate; The attribute such as antibiotic, the crease-resistant and raising dyeability that not only can keep the natural macromolecular material of shitosan itself; And can bring into play the characteristic of its nano material, thus absorption property improves greatly, and anti-microbial property strengthens.
The present invention prepares nano titanium oxide and Nano chitosan distillate; Again silk tussah fibre is handled; Utilize the effect such as small size and bigger serface of nano material; Realize the functional modification of silk tussah fibre, thereby improve the performances such as dyeability, wrinkle resistance anti-microbial property and uvioresistant of tussah silk textiles.
Summary of the invention
The object of the invention provides a kind of functionalized nano shitosan and nano-titanium dioxide modified tussah silk textiles; The step preparation of weaving tussah silk textiles, prepare dressing liquid and carrying out tussah silk textiles arrangement through the tussah long filament successively gets; Solved in the existing textile material modification technology can't effectively improve tussah silk textiles to environmental nuisance, be prone to wrinkle, not antibiotic, be prone to contract and the technical barrier of comfortable function difference such as dyeability difference; Crease-resistant, soft, antibiotic, shrinkproof, automatically cleaning, the uvioresistant of tussah silk textiles, the comprehensive comfort properties such as adsorption efficiency of dyestuff have greatly been improved; And preparation cost is low, environmental protection and preparation technology are simple and easy to useful advantages such as realization; The pre-treatment of weaving through the tussah long filament has realized tussah long filament high cleaning, highly soft; Applicable to the requirement of the comfort property of high-grade textile material, improved the extra added value of product, the innovation degree is higher.
For realizing above-mentioned purpose, the present invention realizes through following technical scheme:
A kind of functionalized nano shitosan of the present invention and nano-titanium dioxide modified tussah silk textiles; It is characterized in that said functionalized nano shitosan and nano-titanium dioxide modified tussah silk textiles are weaved tussah silk textiles, prepare dressing liquid and carried out the step preparation of tussah silk textiles arrangement and got by the tussah long filament successively; Wherein:
One, the tussah silk long fiber is weaved tussah silk textiles: the tussah long filament that the uniformity of selecting for use is higher is washed removal of impurities, carries out the shredding combing again, carries out textile then; Wherein, Said washing is that 32～34 ℃, concentration are to keep 24～27min in the 7.6g/L soda ash water for the first tussah long filament that the said uniformity of selecting for use is higher soaks in temperature fully; Soak into fully in temperature is 27～29 ℃ low temperature distillation water again and keep 22～24 min, taking out the tussah long filament then is that 26～28 ℃ of low temperature carry out the low temperature indirect dewatered drying in temperature; Said shredding combing be before shredding the higher tussah filament surface of the said uniformity of selecting for use evenly a small amount of temperature of spraying be that 32 ℃, concentration are that every premium on currency contains 0.006 cationic surfactant solution; Again through opener shredding and combing machine for fur combing; Further remove impurity, and break into the tussah long filament that crimpness is arranged of 79～82mm; Said textile is the tussah silk textiles that the above-mentioned tussah long filament that crimpness is arranged of breaking into 79～82mm is prepared into, and the said tussah silk textiles that is prepared into is the tussah silk bondedfibre fabric that the tussah silk knitted fabric that is woven into or the tussah silk woven fabric that is woven into or water sting;
Two, preparation dressing liquid: with concentration is that the chitosan solution of 0.01～10g/L adds evenly to mix in the acid solution that concentration is 10～80g/L and obtains the homogeneous mixed liquor, and wherein, the acid in the said acid solution is BTCA, citric acid or maleic anhydride; In above-mentioned homogeneous mixed liquor, add then in the ortho phosphorous acid sodium solution that concentration is 10～60g/L after the full and uniform dissolving; Add 0.075 ~ 0.085g polyvinylpyrrolidone again; After abundant dispersed with stirring is even; In the said well-beaten while; Dropwise adding the sodium tripolyphosphate solution that concentration is 20g/L and dropwise add concentration with 28～30 droplets/minute with 15/min is 0.01～10g/L nanometer titanium dioxide titanium solution, dropwise add sodium tripolyphosphate solution and nanometer titanium dioxide titanium solution after, obtain nano titanium oxide and Nano chitosan finishing functions liquid after powerful again the stirring; Wherein said nano titanium oxide is nanometer anatase titania or rutile type nano titanic oxide; The ortho phosphorous acid sodium solution that above-mentioned concentration is the chitosan solution of 0.01～10g/L, acid solution that concentration is 10～80g/L, concentration is 10～60g/L, sodium tripolyphosphate solution, the concentration that concentration is 20g/L are that the volume ratio of 0.01～10g/L nanometer titanium dioxide titanium solution is 7～9:10～13:9～12:11～14:7～9;
Three, carry out tussah silk textiles and put in order, the tussah silk textiles that is prepared into described in the step 1 is immersed in the said nano titanium oxide and Nano chitosan finishing functions liquid in the step 2, dip time is 36～38min, and two soak two rolls, and pressure is 0.9kg/cm
2, liquid carrying rate is 70～90%, is preliminary drying 5min in 80 ℃ the convection oven in temperature; Stagnate 1 min; Being preliminary drying 5min in 80 ℃ the convection oven in temperature again, is to bake 3min under 165～168 ℃ in temperature then, and washing to neutral back promptly gets after temperature is 27～29 ℃ low temperature drying.
As an optimal way, the said low temperature indirect dewatered drying in the step 1 is in rolling the drying drum that speed is 118 commentaries on classics/min, to wrap up the tussah long filament through science fabric, and the tussah long filament is not directly contacted with cylinder, and bowl temperature remains on 26 ℃ always.
As an optimal way; Step 2 said concentration extremely is that the particle diameter of Nano sol of 0.01～10g/L nanometer titanium dioxide titanium solution is less than 100nm; In said nano titanium oxide and the Nano chitosan finishing functions liquid, the particle diameter that mixes Nano sol of Nano chitosan and nano titanium oxide is less than 100nm.
As an optimal way, BTCA described in the step 2 is the crosslinking agent of environment-friendly type, makes between shitosan and silk tussah fibre and forms covalent bond, and it is crease-resistant wrinkle resistant to give tussah silk textiles simultaneously.
As an optimal way, the fiber surface that step 3 is carried out the tussah silk textiles after the tussah silk textiles arrangement has layer of even Nano chitosan and nano titanium oxide.
As an optimal way, the tussah silk textiles that step 3 is carried out after the tussah silk textiles arrangement is the antimicrobial form tussah silk textiles.
As an optimal way, the tussah silk textiles that step 3 is carried out after the tussah silk textiles arrangement is an easy dyeing type tussah silk textiles.
More crucial is: in above-mentioned optimal way; Said low temperature indirect dewatered drying in the step 1 is to be through science fabric parcel tussah long filament in 118 rev/mins the drying drum rolling speed; The tussah long filament is not directly contacted with cylinder, and bowl temperature remains on 26 ℃ always; Said concentration in the step 2 is that the particle diameter of Nano sol of 0.01～10g/L nanometer titanium dioxide titanium solution is less than 100nm; In said nano titanium oxide and the Nano chitosan finishing functions liquid, the particle diameter that mixes Nano sol of Nano chitosan and nano titanium oxide is less than 100nm; BTCA described in the step 2 is the crosslinking agent of environment-friendly type, makes between shitosan and silk tussah fibre and forms covalent bond, and it is crease-resistant wrinkle resistant to give tussah silk textiles simultaneously; The fiber surface that step 3 is carried out the tussah silk textiles after the tussah silk textiles arrangement has layer of even Nano chitosan and nano titanium oxide; Functionalized nano shitosan that obtains and nano-titanium dioxide modified tussah silk textiles; More outstanding on the adsorption efficiency performance of crease-resistant, soft, antibiotic, shrinkproof, the automatically cleaning of tussah silk textiles, uvioresistant, dyestuff, be more than three times of adsorption efficiency performance indications of crease-resistant under other situation, soft, antibiotic, shrinkproof, automatically cleaning, uvioresistant, dyestuff.
The principle of technical scheme of the present invention is: because rutile type nano titanic oxide has anti-ultraviolet function, nanometer anatase titania has photocatalysis, antibiotic, automatically cleaning and anti-ultraviolet effect.The big molecule of shitosan has a large amount of amino; Being used for tussah silk modification processing can make its textiles have a large amount of positive charges in dye bath; Reduce on the fiber with negative electrical charge, overcome in the dyeing course on the fiber negative electrical charge to ACID DYES and the anionic Coulomb repulsion of REACTIVE DYES, thereby dye on the promotion dyestuff; Have dyeing and increase dark effect, the anti-microbial property of the fiber that also strengthens simultaneously.Crosslinking agent BTCA, citric acid and maleic anhydride can produce crosslinked action with silk tussah fibre and shitosan, can improve the wrinkle resistance of tussah silk textiles, strengthen shitosan etc. simultaneously in the set at fiber surface.Because the carboxyl in the crosslinking agent is electronegative, dosage of crosslinking agent is too much, and the negative charge amount of fiber surface is increased, thereby influences the action effect of dyestuff and shitosan, so need suitably its consumption of control.Therefore, adopt the combination dressing liquid of nano titanium oxide and Nano chitosan, can improve tussah silk textiles wrinkle, be prone to contract and shortcoming such as dyeability is relatively poor, realize antibiotic, the anti-ultraviolet function of tussah silk textiles simultaneously.
Compared with prior art, advantage of the present invention is:
1, utilizes the small-size effect of nano material, make in its hole that embeds fiber, realize the functionalization filling; Utilize the Large ratio surface effect of nano material, thereby have many activated centres, have high activity, improve the adsorption efficiency of dyestuff.
2, the good characteristic of comprehensive utilization nano titanium oxide and Nano chitosan gives tussah silk textiles many excellent properties simultaneously.Can make fabric have anti-ultraviolet function when using rutile type nano titanic oxide, nanometer anatase titania has photocatalysis, can give antibacterial fabric, automatically cleaning and anti-ultraviolet function.Amido is rich on the surface of Nano chitosan, is applied on the silk tussah fibre, can reduce on the fiber with negative electrical charge, promote to dye on the dyestuff, thereby improve dyeability.
3, green crosslinking agent BTCA, citric acid and maleic anhydride; And the adding of catalyst inferior sodium phosphate, can impel amido and hydroxyl, the amido generation cross-linking reaction of fiber in the chitosan molecule, improve the set of shitosan at fiber surface.
4, enrich in the nano titanium oxide, the shitosan source that are used for the tussah silk finishing functions, and cost is lower, and the preparation technology of Nano chitosan is simple, easy to be realized, therefore, but this method has suitability for industrialized production and the high characteristics of application surcharge.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.
Embodiment 1:
A kind of functionalized nano shitosan and nano-titanium dioxide modified tussah silk textiles; It is characterized in that said functionalized nano shitosan and nano-titanium dioxide modified tussah silk textiles are weaved tussah silk textiles, prepare dressing liquid and carried out the step preparation of tussah silk textiles arrangement and got by the tussah long filament successively; Wherein:
One, the tussah silk long fiber is weaved tussah silk textiles: the tussah long filament that the uniformity of selecting for use is higher is washed removal of impurities, carries out the shredding combing again, carries out textile then; Wherein, Said washing is that 32～34 ℃, concentration are to keep 24～27 min in the 7.6g/L soda ash water for the first tussah long filament that the said uniformity of selecting for use is higher soaks in temperature fully; Soak into fully in temperature is 27～29 ℃ low temperature distillation water again and keep 22～24 min, taking out the tussah long filament then is that 26～28 ℃ of low temperature carry out the low temperature indirect dewatered drying in temperature; Said shredding combing be before shredding the higher tussah filament surface of the said uniformity of selecting for use evenly a small amount of temperature of spraying be that 32 ℃, concentration are that every premium on currency contains 0.006 cationic surfactant solution; Again through opener shredding and combing machine for fur combing; Further remove impurity, and break into the tussah long filament that crimpness is arranged of 79～82mm; Said textile is the tussah silk textiles that the above-mentioned tussah long filament that crimpness is arranged of breaking into 79～82mm is prepared into, and the said tussah silk textiles that is prepared into is the tussah silk bondedfibre fabric that the tussah silk knitted fabric that is woven into or the tussah silk woven fabric that is woven into or water sting;
Two, preparation dressing liquid: with concentration is that the chitosan solution of 0.01～10g/L adds evenly to mix in the acid solution that concentration is 10～80g/L and obtains the homogeneous mixed liquor, and wherein, the acid in the said acid solution is BTCA, citric acid or maleic anhydride; In above-mentioned homogeneous mixed liquor, add then in the ortho phosphorous acid sodium solution that concentration is 10～60g/L after the full and uniform dissolving; Add 0.075 ~ 0.085g polyvinylpyrrolidone again; After abundant dispersed with stirring is even; In the said well-beaten while; Dropwise adding the sodium tripolyphosphate solution that concentration is 20g/L and dropwise add concentration with 28～30/min with 15/min is 0.01～10g/L nanometer titanium dioxide titanium solution, dropwise add sodium tripolyphosphate solution and nanometer titanium dioxide titanium solution after, obtain nano titanium oxide and Nano chitosan finishing functions liquid after powerful again the stirring; Wherein said nano titanium oxide is nanometer anatase titania or rutile type nano titanic oxide; The ortho phosphorous acid sodium solution that above-mentioned concentration is the chitosan solution of 0.01～10g/L, acid solution that concentration is 10～80g/L, concentration is 10～60g/L, sodium tripolyphosphate solution, the concentration that concentration is 20g/L are that the volume ratio of 0.01～10g/L nanometer titanium dioxide titanium solution is 7～9:10～13:9～12:11～14:7～9;
Three, carrying out tussah silk textiles puts in order, the tussah silk textiles that is prepared into described in the step 1 is immersed in the said nano titanium oxide and Nano chitosan finishing functions liquid in the step 2; Dip time is 36～38min, and two soak two rolls, and pressure is 0.9 kilogram/square centimeter; Liquid carrying rate is 70～90%; In temperature is preliminary drying 5min in 80 ℃ the convection oven, stagnates 1 min, is preliminary drying 5min in 80 ℃ the convection oven in temperature again; Be to bake 3min under 165～168 ℃ in temperature then, washing to neutral back promptly gets after temperature is 27～29 ℃ low temperature drying.
Wherein, the said low temperature indirect dewatered drying in the step 1 be roll speed be in 118 rev/mins the drying drum through science fabric parcel tussah long filament, the tussah long filament is not directly contacted with cylinder, bowl temperature remains on 26 ℃ always; Step 2 said concentration extremely is that the particle diameter of Nano sol of 0.01～10g/L nanometer titanium dioxide titanium solution is less than 100nm; In said nano titanium oxide and the Nano chitosan finishing functions liquid, the particle diameter that mixes Nano sol of Nano chitosan and nano titanium oxide is less than 100nm; BTCA described in the step 2 is the crosslinking agent of environment-friendly type, makes between shitosan and silk tussah fibre and forms covalent bond, and it is crease-resistant wrinkle resistant to give tussah silk textiles simultaneously; The fiber surface that step 3 is carried out the tussah silk textiles after the tussah silk textiles arrangement has layer of even Nano chitosan and nano titanium oxide.
Embodiment 2:
1, under the room temperature, the 5g/L shitosan is added after 10g/L BTCA and 10g/L inferior sodium phosphate fully dissolve, add an amount of polyethylene of dispersing agent pyrrolidones again; After abundant dispersed with stirring is even; The powerful sodium tripolyphosphate solution that dropwise adds 20g/L down that stirs is processed the Nano chitosan dispersion liquid, adds the 10g/L amido silicon oil again; The 5g/L nanometer anatase titania obtains nano-TiO after powerful the stirring
2Disperse dressing liquid with Nano chitosan;
2, tussah silk textiles is immersed in the above dressing liquid, dip time is 10min, and two soak two rolls, and liquid carrying rate is 90%, 80 ℃ of preliminary drying 5min, and 165 ℃ bake 3min, washes back 80 ℃ of oven dry.253 ° of the nano-material modified functionalization tussah silk textiles creasy recovery angles that makes to the bacteriostasis rate of Escherichia coli and staphylococcus aureus more than 95%, improve more than 1 to the color depth value K/S value of ACID DYES and reactive dyeing.
Embodiment 3:
1, under the room temperature; The 5g/L shitosan is added after the 50g/L BTCA fully dissolves with the 50g/L inferior sodium phosphate, an amount of polyethylene of dispersing agent pyrrolidones, fully dispersed with stirring even after; Stir the sodium tripolyphosphate solution that dropwise adds 20g/L; Add the 10g/L amido silicon oil again, the 5g/L nanometer anatase titania obtains nano-TiO after powerful the stirring
2Disperse dressing liquid with Nano chitosan;
2, tussah silk textiles is immersed in the above dressing liquid, dip time is 10min, and two soak two rolls, and liquid carrying rate is 90%, 80 ℃ of preliminary drying 5min, and 165 ℃ bake 3min, washes back 80 ℃ of oven dry.253 ° of Nano chitosan that makes and nano-titanium dioxide modified functionalization tussah silk textiles creasy recovery angles reach 100% to the bacteriostasis rate of Escherichia coli and staphylococcus aureus, improve more than 1 to the color depth value K/S value of ACID DYES and reactive dyeing.
Embodiment 4:
1, under the room temperature; The 5g/L shitosan is added after the 30g/L BTCA fully dissolves with the 20g/L inferior sodium phosphate, an amount of polyethylene of dispersing agent pyrrolidones, fully dispersed with stirring even after; Stir the sodium tripolyphosphate solution that dropwise adds 20g/L; Add the 10g/L amido silicon oil again, the 5g/L rutile type nano titanic oxide obtains nano TiO 2 after powerful the stirring and Nano chitosan disperses dressing liquid;
2, tussah silk textiles is immersed in the above dressing liquid, dip time is 10min, and two soak two rolls, and liquid carrying rate is 90%, 80 ℃ of preliminary drying 5min, and 165 ℃ bake 3min, washes back 80 ℃ of oven dry.241 ° of the nano-material modified functionalization tussah silk textiles creasy recovery angles that makes; Bacteriostasis rate to Escherichia coli and staphylococcus aureus reaches more than 95%; Tussah silk textiles reaches good ultraviolet protection property; To the UV-preventing rate more than 95%, improve more than 2 to the color depth value K/S value of ACID DYES and reactive dyeing.
Embodiment 5:
1, under the room temperature; The 5g/L shitosan is added after the 60g/L maleic anhydride fully dissolves with the 50g/L inferior sodium phosphate, an amount of polyethylene of dispersing agent pyrrolidones, fully dispersed with stirring even after; Stir the sodium tripolyphosphate solution that dropwise adds 20g/L; Add the 10g/L amido silicon oil again, the 5g/L rutile type nano titanic oxide obtains nano TiO 2 after powerful the stirring and Nano chitosan disperses dressing liquid;
2, tussah silk textiles is immersed in the above dressing liquid, dip time is 10min, and two soak two rolls, and liquid carrying rate is 90%, 80 ℃ of preliminary drying 5min, and 165 ℃ bake 3min, washes back 80 ℃ of oven dry.249 ° of the nano-material modified functionalization tussah silk textiles creasy recovery angles that makes reach more than 95% the bacteriostasis rate of Escherichia coli and staphylococcus aureus, improve more than 1 to the color depth value K/S value of ACID DYES and reactive dyeing.
The present invention is not limited to above-mentioned specific embodiment, is not deviating under spirit of the present invention and the nature thereof, and those of ordinary skill in the art can make various corresponding changes and distortion according to the present invention.These corresponding changes and distortion all should belong within the protection domain of accompanying claims of the present invention.
Claims (7)
1. a functionalized nano shitosan and nano-titanium dioxide modified tussah silk textiles; It is characterized in that said functionalized nano shitosan and nano-titanium dioxide modified tussah silk textiles are weaved tussah silk textiles, prepare dressing liquid and carried out the step preparation of tussah silk textiles arrangement and got by the tussah long filament successively; Wherein:
(1) the tussah silk long fiber is weaved tussah silk textiles: the tussah long filament that the uniformity of selecting for use is higher is washed removal of impurities, carries out the shredding combing again, carries out textile then; Wherein, Said washing is that 32～34 ℃, concentration are to keep 24～27 minutes in the 7.6g/L soda ash water for the first tussah long filament that the said uniformity of selecting for use is higher soaks in temperature fully; Soak into fully in temperature is 27～29 ℃ low temperature distillation water again and keep 22～24min, taking out the tussah long filament then is that 26～28 ℃ of low temperature carry out the low temperature indirect dewatered drying in temperature; Said shredding combing be before shredding the higher tussah filament surface of the said uniformity of selecting for use evenly a small amount of temperature of spraying be that 32 ℃, concentration are that every premium on currency contains 0.006 cationic surfactant solution; Again through opener shredding and combing machine for fur combing; Further remove impurity, and break into the tussah long filament that crimpness is arranged of 79～82mm; Said textile is the tussah silk textiles that the above-mentioned tussah long filament that crimpness is arranged of breaking into 79～82mm is prepared into, and the said tussah silk textiles that is prepared into is the tussah silk bondedfibre fabric that the tussah silk knitted fabric that is woven into or the tussah silk woven fabric that is woven into or water sting;
(2) preparation dressing liquid: with concentration is that the chitosan solution of 0.01～10g/L adds evenly to mix in the acid solution that concentration is 10～80g/L and obtains the homogeneous mixed liquor; Wherein, the acid in the said acid solution is BTCA, citric acid, poly, maleic anhydride or tartaric acid; In above-mentioned homogeneous mixed liquor, add then in the ortho phosphorous acid sodium solution that concentration is 10～60g/L after the full and uniform dissolving; Add 0.075 ~ 0.085g polyvinylpyrrolidone again; After abundant dispersed with stirring is even; In the said well-beaten while; Dropwise adding the sodium tripolyphosphate solution that concentration is 20g/L and dropwise add concentration with 28～30/min with 15 droplets/minute is 0.01～10g/L nanometer titanium dioxide titanium solution, dropwise add sodium tripolyphosphate solution and nanometer titanium dioxide titanium solution after, obtain nano titanium oxide and Nano chitosan finishing functions liquid after powerful again the stirring; Wherein said nano titanium oxide is nanometer anatase titania or rutile type nano titanic oxide; The ortho phosphorous acid sodium solution that above-mentioned concentration is the chitosan solution of 0.01～10g/L, acid solution that concentration is 10～80g/L, concentration is 10～60g/L, sodium tripolyphosphate solution, the concentration that concentration is 20g/L are that the volume ratio of 0.01～10g/L nanometer titanium dioxide titanium solution is 7～9:10～13:9～12:11～14:7～9;
(3) carry out the tussah silk textiles arrangement: the tussah silk textiles that is prepared into described in the step (1) is immersed in the said nano titanium oxide and Nano chitosan finishing functions liquid in the step (2); Dip time is 36～38min; Two soak two rolls, and pressure is 0.9kg/m
2, liquid carrying rate is 70～90%, is preliminary drying 5min in 80 ℃ the convection oven in temperature; Stagnate 1 min; Being preliminary drying 5min in 80 ℃ the convection oven in temperature again, is to bake 3min under 165～168 ℃ in temperature then, and washing to neutral back promptly gets after temperature is 27～29 ℃ low temperature drying.
2. functionalized nano shitosan according to claim 1 and nano-titanium dioxide modified tussah silk textiles; It is characterized in that; Said low temperature indirect dewatered drying in the step (1) is through science fabric parcel tussah long filament in rolling the drying drum that speed is 118 commentaries on classics/min; The tussah long filament is not directly contacted with cylinder, and bowl temperature remains on 26 ℃ always.
3. functionalized nano shitosan according to claim 1 and nano-titanium dioxide modified tussah silk textiles; It is characterized in that; Said concentration in the step (2) is that the particle diameter of Nano sol of 0.01～10g/L nanometer titanium dioxide titanium solution is less than 100nm; In said nano titanium oxide and the Nano chitosan finishing functions liquid, the particle diameter that mixes Nano sol of Nano chitosan and nano titanium oxide is less than 100nm.
4. functionalized nano shitosan according to claim 1 and nano-titanium dioxide modified tussah silk textiles; It is characterized in that; Organic acids such as BTCA described in the step (2) are the crosslinking agent of environment-friendly type; Make between shitosan and silk tussah fibre and form covalent bond, improve the crease-resistant crease resistance of tussah silk textiles simultaneously.
5. functionalized nano shitosan according to claim 1 and nano-titanium dioxide modified tussah silk textiles; It is characterized in that the fiber surface that step (3) is carried out the tussah silk textiles after the tussah silk textiles arrangement has layer of even Nano chitosan and nano titanium oxide.
6. functionalized nano shitosan according to claim 1 and nano-titanium dioxide modified tussah silk textiles is characterized in that, the tussah silk textiles that step (3) is carried out after the tussah silk textiles arrangement is the antimicrobial form tussah silk textiles.
7. according to claim 1 or 7 described functionalized nano shitosan and nano-titanium dioxide modified tussah silk textiles, it is characterized in that the tussah silk textiles that step (3) is carried out after the tussah silk textiles arrangement is an easy dyeing type tussah silk textiles.
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