CN103147281B - Super-hydrophobic fabric preparation method and super-hydrophobic functional fabric - Google Patents

Super-hydrophobic fabric preparation method and super-hydrophobic functional fabric Download PDF

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Publication number
CN103147281B
CN103147281B CN201310074491.XA CN201310074491A CN103147281B CN 103147281 B CN103147281 B CN 103147281B CN 201310074491 A CN201310074491 A CN 201310074491A CN 103147281 B CN103147281 B CN 103147281B
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fabric
super
preparation
titanium dioxide
hydrophobic
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CN103147281A (en
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袁志好
孟祥君
袁翔
孙巍
郭翠
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TIANJIN WEINENG NEW MATERIALS CO Ltd
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TIANJIN WEINENG NEW MATERIALS CO Ltd
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Abstract

The invention relates to a super-hydrophobic fabric preparation method and a super-hydrophobic functional fabric. The preparation method comprises the following steps: I. preparing stable silicic acid and titanium dioxide mixed sol; II. applying the mixed sol obtained in step I onto a clean fabric through steps of soaking, membrane brushing and drying, and firmly bonding nanoscale silicon dioxide and titanium dioxide particles on the fiber surface of the fabric; and III. modifying the surfaces of the silicon dioxide and titanium dioxide particles, obtained in step II, with organosilane through the steps of soaking and drying, so as to realize the super-hydrophobic property, wherein the organosilane at least comprises hexadecyltrimethoxysilane. The invention provides a preparation method of super-hydrophobic fabric with stronger adhesive force and environment friendliness, and the super-hydrophobic fabric obtained by adopting the preparation method has the functions of ultraviolet irradiation resistance and washing resistance.

Description

A kind of preparation method of superhydrophobic fabric and super hydrophobic functional fabric
Technical field
The present invention relates to the preparation method of fabric in a kind of field of light chemical industry and corresponding fabric, particularly relate to a kind of preparation method and super hydrophobic functional fabric of superhydrophobic fabric.
Background technology
The animals and plants of occurring in nature have a lot of peculiar phenomenon, and super hydrophobic surface is wherein a kind of.Vegeto-animal super hydrophobic surface is that the rough surface structure of being wrapped up by wax causes.Wax can make surface have lower surface energy, thus increases contact angle, and coarse surface texture also can increase this hydrophobic effect further.Because super hydrophobic surface has the properties such as waterproof, anti-pollution, automatically cleaning, people are thus enjoyed to pay close attention to.
In prior art, the technology preparing super hydrophobic surface mainly can be divided into following a few class: the etching method on silicon materials surface, sol-gal process, chemical vapour deposition technique, mechanical stretching method, polymerisation membrane formation process, template, Electrospinning Method, electrochemical deposition method, and corroding metal method etc.The common feature of these methods is that the surface of preparation has lower surface energy, has again larger roughness simultaneously, thus causes it to have super-hydrophobic characteristic.But above-mentioned prior art also also exists the shortcomings such as equipment complexity, cost intensive, preparation condition harshness, unstable properties.
Summary of the invention
The object of the invention is to propose that a kind of technique is simple, cost is lower, utilize eco-friendly material to prepare the method with ultra-hydrophobicity fabric, make fabric have uvioresistant and irradiate and wash durability.
For achieving the above object, the invention provides a kind of preparation method of superhydrophobic fabric, described preparation method comprises the steps: step one, prepares stable silicic acid and titanium dioxide mixed sols: under constant agitation, be dropwise add butyl titanate in the acid solution of 1 ~ 3 to PH, solution becomes muddy gradually, dirty solution is put into the water bath heating of 70 ~ 90 ° of C until become translucent TiO 2 sol, in colloidal sol, the content of titanium dioxide controls between 5 ~ 25g/L; By concentration be the sodium silicate solution of 10 ~ 25g/L and above-mentioned preparation TiO 2 sol under agitation by volume ratio be the ratio mixing of 0.2 ~ 5, the PH regulating mixed liquor with acid is 7 ~ 9, obtains silicic acid and titanium dioxide mixed sols; Step 2, the mixed sols of gained in step one is applied on the clean fabric after via washed with de-ionized water by the step of immersion ~ brush film ~ oven dry, nano level silica and titanium dioxide granule in the fiber surface strong bonded of fabric; Step 3, the silica passing through the step gained in step 2 soaking ~ dry and titanium dioxide granule finishing organosilan, realize ultra-hydrophobicity; Described organosilan at least comprises hexadecyl trimethoxy silane.
Preferably, in described step 2, first soak 5 ~ 30min by the mixed sols of the gained in step one of the fabric after washed with de-ionized water, then take out and dry 5 ~ 30min at 60 ~ 100 ° of C temperature; Repeat aforesaid operations at least one times, finally dry 4 ~ 6h at 60 ~ 100 ° of C.
Preferably, in described step 3, the fabric obtained in step 2 being immersed in volume fraction is 6 ~ 12h in the hexadecyl trimethoxy silane ethanolic solution of 2 ~ 4%, and then dry 6 ~ 12h at 60 ~ 100 ° of C temperature, obtains the fabric with floride-free super-hydrophobic function.
Preferably, in described step one, the acid being used for regulating mixed liquor PH is nitric acid, hydrochloric acid or sulfuric acid.
Another object of the present invention is to provide a kind of super hydrophobic functional fabric, described fabric is obtained by above-mentioned preparation method.
Based on technique scheme, advantage of the present invention is:
The invention provides the stronger and preparation method of eco-friendly superhydrophobic fabric of a kind of adhesive force, namely by super hydrophobic functional fabric that preparation method of the present invention obtains, be not only a kind of floride-free super-hydrophobic function fabric, and, there is the function of ultraviolet radiation resisting and wash fast function; Meanwhile, the present invention selects sodium metasilicate as raw material in fabric processing procedure, greatly reduces production cost, makes application of the present invention stronger.
Accompanying drawing explanation
Accompanying drawing described herein is used to provide a further understanding of the present invention, and form a application's part, schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the SEM photo of the super hydrophobic functional fabric face prepared by the present invention;
Fig. 2-1 is the droplet morphology on the super hydrophobic functional fabric prepared by the present invention;
Fig. 2-2 is top views of Fig. 2-1;
Fig. 2-3 is the liquid-drop contact angles on the super hydrophobic functional fabric prepared by the present invention;
Fig. 3 is the ultraviolet radiation resisting performance schematic diagram of the super hydrophobic functional fabric prepared by the present invention;
Fig. 4 is the washing durability schematic diagram of the super hydrophobic functional fabric prepared by the present invention.
Detailed description of the invention
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
The preparation method of a kind of superhydrophobic fabric provided by the invention, operation principle of the present invention is: the bionic principle utilizing " lotus leaf effect ", first carries out surface treatment to fabric, makes nano particle evenly firmly be combined in fabric face, make its surface roughening; Again the long chain silane of low-surface-energy is applied on fabric, prepares floride-free super-hydrophobic uvioresistant and irradiate water-wash resistance fabric.
Preparation method of the present invention mainly comprises at least three steps, that is: prepare silica and titanium dioxide mixed sols, be applied on fabric by mixed sols and form nano-scale particle and the nano-scale particle finishing organosilan at fabric, concrete technical scheme refers to following embodiment.
Embodiment 1:
Dropwise added by 17mL butyl titanate in the nitric acid of the 0.1mol/L of 200mL, and constantly stir, solution becomes muddy gradually; Dirty solution is put into constant temperature water bath, heating water bath 3 ~ 4h under 85 ° of C, white precipitate gradually becomes translucent colloidal sol, and in colloidal sol, the content of titanium dioxide is 20g/L.
7.52g sodium metasilicate is added in 400ml deionized water, prepare sodium silicate solution, and with by above-mentioned TiO 2 sol by volume ratio be 0.6 ratio under agitation mix, then sulfuric acid and hydrochloric acid etc. can certainly be used with nitric acid adjustment PH=9(), obtain milky silicic acid and titanium dioxide mixed sols.
COTTON FABRIC is immersed in mixing water colloidal sol after 10min, dries 15min at 80 ° of C, repeat aforesaid operations 2 times, finally dry 6h at 80 ° of C.The COTTON FABRIC of above-mentioned process being immersed in volume fraction is 12h in 4% hexadecyl trimethoxy silane ethanolic solution, dries 12h, obtain floride-free super-hydrophobic function fabric under 80 ° of C.
Another object of the present invention is to provide a kind of super hydrophobic functional fabric, described fabric is obtained by above-mentioned preparation method.Described fabric can be the various fabric such as cotton fiber, polyster fibre.In the present embodiment, employing be cotton fiber.
The SEM photo of the super hydrophobic functional fabric face that said method shown in Fig. 1 obtains; Liquid in the form of this super hydrophobic functional fabric face and contact angle values as shown in Fig. 2-1, Fig. 2-2 and Fig. 2-3.
From in above-mentioned test accompanying drawing, the cotton fiber surface coverage of the present invention particle of size at 50 ~ 500nm, forms certain roughness.Obtain good super-hydrophobic effect after being modified further by organosilan, contact angle reaches 159.2 °, and can hinder and refuse methylene blue drop.
Fig. 3 and Fig. 4 is ultraviolet radiation resisting performance and the washing durability of prepared super hydrophobic functional fabric.
As seen from the figure, super hydrophobic functional fabric of the present invention still can keep the contact angle of water more than 140 ° at Ultraviolet radiation 6h; Clean 10 times in washing machine, and after each cleaning 30min, still can keep the contact angle of water more than 155 °.
To sum up, use the super hydrophobic functional fabric that preparation method of the present invention obtains, compared with other superhydrophobic fabrics of the prior art, mainly have the following advantages:
(1) the super hydrophobic functional fabric that prepared by the inventive method has the function of ultraviolet radiation resisting.It still can keep the contact angle of water more than 140 ° after more than Ultraviolet radiation 6h, irradiates 40 days, still can keep the contact angle of water more than 150 ° under natural sunshine.
(2) the super hydrophobic functional fabric that prepared by the inventive method has wash fast function.Washing machine cleans more than 10 times, cleans 30min at every turn, still can keep the contact angle of water more than 155 °.
(3), after the fabric that super hydrophobic functional fabric of the present invention is obtained has ultraviolet radiation resisting and wash fast function, the long-time irradiation of strong sunshine can be adapted to, also can resist washing away for a long time of rainwater, more can adapt to severe natural environment.And can waterproof and dustproof, automatically cleaning, save a large amount of clean and repair the expense of cost, manpower and time, decrease the pollution of washing agent to environment.
(4) the present invention has selected and has carried out surface treatment without silicon fluoride, and this organosilan good biocompatibility, can not cause the allergic reaction of skin, and can not welding (as Ozone in Atmosphere layer etc.).
(5) the floride-free super-hydrophobic function fabric prepared of the present invention, high-grade fabric, home decoration, outdoor tent and various waterproof cloth can be widely used in, there are opposing adverse circumstances, durable for a long time, super-hydrophobic effect keeps permanent effect, there is wide market application foreground.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the field are to be understood that: still can modify to the specific embodiment of the present invention or carry out equivalent replacement to portion of techniques feature; And not departing from the spirit of technical solution of the present invention, it all should be encompassed in the middle of the technical scheme scope of request of the present invention protection.

Claims (3)

1. a preparation method for superhydrophobic fabric, is characterized in that: described preparation method comprises the steps:
Step one, prepare stable silicic acid and titanium dioxide mixed sols: under constant agitation, be in the acid solution of 1 ~ 3, dropwise add the butyl titanate solution that concentration is 50 ~ 100mL/L to pH, solution becomes muddy gradually, dirty solution is put into the water bath heating of 70 ~ 90 DEG C until become translucent TiO 2 sol, in colloidal sol, the content of titanium dioxide controls between 5 ~ 25g/L;
By concentration be the sodium silicate solution of 10 ~ 25g/L and above-mentioned preparation TiO 2 sol under agitation by volume ratio be the ratio mixing of 0.2 ~ 5, the pH regulating mixed liquor with acid is 7 ~ 9, obtains silicic acid and titanium dioxide mixed sols;
Step 2, the mixed sols of gained in step one is applied on clean fabric by the step of immersion ~ brush film ~ oven dry, be specially and first soak 5 ~ 30min by the mixed sols of the gained in step one of the fabric after washed with de-ionized water, then take out and dry at 60 ~ 100 DEG C of temperature; Repeat aforesaid operations at least one times, finally dry 4 ~ 6h, finally nano level silica and titanium dioxide granule in the fiber surface strong bonded of fabric at 60 ~ 100 DEG C;
Step 3, the silica passing through the step gained in step 2 soaking ~ dry and titanium dioxide granule finishing organosilan, realize ultra-hydrophobicity; Described organosilan at least comprises hexadecyl trimethoxy silane.
2. the preparation method of superhydrophobic fabric according to claim 1, it is characterized in that: in described step 3, the fabric obtained in step 2 being immersed in volume fraction is 6 ~ 12h in the hexadecyl trimethoxy silane ethanolic solution of 2 ~ 4%, then dry 6 ~ 12h at 60 ~ 100 DEG C of temperature, obtains the fabric with floride-free super-hydrophobic function.
3. a super hydrophobic functional fabric, is characterized in that: described fabric is obtained by the preparation method described in above-mentioned any one claim.
CN201310074491.XA 2013-03-08 2013-03-08 Super-hydrophobic fabric preparation method and super-hydrophobic functional fabric Expired - Fee Related CN103147281B (en)

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CN103726302B (en) * 2013-12-06 2016-01-20 南京工业大学 Preparation method of multifunctional super-hydrophobic hybrid material
CN103806262B (en) * 2014-01-28 2016-08-17 东华大学 A kind of preparation method of automatically cleaning wool fabric
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CN104088148A (en) * 2014-07-13 2014-10-08 成都市绿科华通科技有限公司 Surface-modified functional yak hair/wool fabric
CN104088147A (en) * 2014-07-13 2014-10-08 成都市绿科华通科技有限公司 Functional woolen fabric with super-hydrophobicity
CN104372608B (en) * 2014-11-12 2020-10-23 江南大学 Method for preparing super-hydrophobic fabric through sol-gel electrochemical deposition
CN104745019B (en) * 2015-03-31 2017-08-25 华南理工大学 A kind of preparation method of automatically cleaning characteristic nano silicon/titania modified PVDF super-hydrophobic composite films
CN104746336B (en) * 2015-04-01 2017-03-01 江南大学 A kind of method for sorting of the chinlon hydrophobic fabric based on butyl titanate
CN105316932A (en) * 2015-11-30 2016-02-10 无锡新德印染制品有限公司 Preparation method of fabric with super-hydrophobic function
CN106884316A (en) * 2017-01-18 2017-06-23 雅戈尔服装控股有限公司 A kind of preparation method of photocatalyst-type floride-free super-hydrophobic automatically cleaning textile
CN107385984B (en) * 2017-07-31 2019-10-18 华南理工大学 A kind of waterproof paper and preparation method thereof
CN108251903A (en) * 2018-03-08 2018-07-06 唐卫兵 A kind of preparation method of the cellulose nano-fibrous spinning solution of super-hydrophobicity
CN108330558A (en) * 2018-03-08 2018-07-27 唐卫兵 A kind of preparation method of the hydrophobic fibre element chitosan nano fiber spinning solution of antibacterial functions
CN109736075A (en) * 2018-12-28 2019-05-10 杭州蓝色倾情服饰有限公司 Uvioresistant fabrics and preparation method thereof
CN111379163A (en) * 2018-12-29 2020-07-07 江苏唐工纺实业有限公司 Based on radial nano TiO2Preparation method of lyophobic polyester fabric
CN110714325B (en) * 2019-10-30 2021-04-30 江南大学 Nano silicon dioxide-fluorine-free super-hydrophobic finishing agent and preparation method and application thereof
CN111441166B (en) * 2020-04-02 2024-08-27 海泰纺织(苏州)有限公司 Preparation method of oil-water separation fabric and oil-water separation fabric thereof

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