CN102251391A - Method for superhydrophobic finishing of textile - Google Patents
Method for superhydrophobic finishing of textile Download PDFInfo
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- CN102251391A CN102251391A CN 201010180559 CN201010180559A CN102251391A CN 102251391 A CN102251391 A CN 102251391A CN 201010180559 CN201010180559 CN 201010180559 CN 201010180559 A CN201010180559 A CN 201010180559A CN 102251391 A CN102251391 A CN 102251391A
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Abstract
The invention provides a method for superhydrophobic finishing of textile, comprising the following steps of: (1) padding the textile in silicon dioxide hydrosol, and drying; and (2) padding the textile treated in the step (1) in water emulsion of siloxane, polysiloxane and hydroxyl polydimethyl siloxane or the water emulsion of a mixture of the siloxane, the polysiloxane and hydroxyl polydimethyl siloxane in the presence of a catalytic synergistic agent, preliminarily drying and baking. The contact angle between the fabric treated with the method and water is greater than 150 degrees; the textile has the superhydrophobic performance; in the processing flow of the method disclosed by the invention, an organic solvent is prevented from being used from beginning to end; the fabric is completely treated in a waterborne system; the processing method is environment-friendly and is easy for industrialization; and the used raw materials have wide sources and low cost.
Description
Technical field:
The invention belongs to the super water repellent finish field in the finishing functions of textile fabrics, particularly relate to a kind of environmental friendliness, low cost, high efficiency, the super water-repellent finishing method of easy industrialized textiles.
Background technology:
Usually be the boundary with 90 ° of contact angles,, refuse water surface when contact angle then is called greater than 90 ° when water droplet claims that this surface is a water-wetted surface at the contact angle of the surface of solids during less than 90 °.Super refuse water surface then refer to the surface of solids to the static contact angle of water at [Nakajima A, Fujishima A.Adv Mater, 1999,11:1365] more than 150 °.From people [Onda T, Shibuichi S, SatohN, Tsujii K.Langmuir.1996,12:2125] such as Japanese scholar OndaT in 1996 successfully prepared first super refuse the water solid surface after, its potential application prospect becomes the focus of research in recent years.
Up to the present, bibliographical information super to refuse the water textiles be to carry out in organic solvent always based on sol-gel technology preparing, its arrangement process is earlier to handle textiles with the silica alcosol, and the textiles that colloidal sol was handled is handled a few hours and obtained to surpass and refuse the water effect in the organic solution of low surface free energy compound then.Silicon dioxide gel often adopts ethyl orthosilicate hydrolysis in ethanol to prepare.Low surface energy compounds is then selected fluorocarbons for use, particularly perfluoro capryl compound [Tadanaga K.J Sol-Gel Sci Tech.2003,26:705.; Shang H M.Thin Solid Films.2005,472:37.].Be that solvent prepares silicon dioxide gel and has many advantages such as easy control colloidal sol particle diameter with ethanol, but alcosol is handled and is made fabric hardening, feel variation.Ethanol evaporate in the fabric heat treatment process and causes working environment to worsen in the air, and inflammable and explosive potential danger increases.The perfluoro capryl compound has low-down surface free energy really.Its deficiency is to cost an arm and a leg, the production cost height.Especially in recent years verified perfluoro caprylic acid (PFOA) and the perfluoro octyl sulfonic acid salt (PFOS) that is used for water repellent finish of research is the organic pollution of difficult degradation and potential carcinogen.And these compounds of PFOA, PFOS to discharge fluorine compounds in the finish fabric process also be disadvantageous [Hogue C.Chem.Eng.News., 2005,83:5. to environment; Slaper.H.J.Hazard.Mater., 1998,61:77.; Schultz M.M.Environ.Eng.Sci., 2003,20:487.].Therefore, the eco-friendly super inevitable requirement that the water textiles is a Green Chemistry of refusing of preparation.
Except fluorocarbons, organic silicide especially polysiloxanes has low surface free energy equally, and silicone compounds is nontoxic substantially.Patent CN 101397754A and CN 101591853A have reported the super method of refusing the water textiles of sol-gel technology preparing of utilizing respectively.Although what use in these patents is eco-friendly silicone compounds, fabric after the arrangement has the good super water effect of refusing, but, the method of these patented inventions still is the method for sorting that follows in the foreign literature, promptly carry out in organic solvent, textiles needs to handle a few hours in the organic solution of silicone compounds.Method for sorting as patent CN 101397754A invention need be handled textiles 0.5-2 hour in the ethanolic solution of siloxanes, and patent CN101591853A then needs to handle 0.5-4 hour in the organic solution of siloxanes.Yet, in the industrial production of current textiles water repellent finish, require fabric in water repellent finishing agent, only need pad the several seconds and just can obtain to refuse the water effect.Therefore, it is extremely low to handle the super method production efficiency of refusing the water textiles of a few hours preparation in organic solution, and the cost height, non-ambient close friend.Lacking energy-saving, emission-reducing, environment friendly type product is one of outstanding problem of current dyeing and finishing industry existence.If under can complete aqueous conditions based on sol-gel technique, the aqueous systems formula technique is refused in innovation, improve the reactivity of water repellent, make it can in the several seconds, give textiles super water repellency, can effectively shorten the process-cycle like this, save time, raise the efficiency, beyond doubt to the breakthrough based on the super water repellent finish of textiles of sol-gel technique, industrialization is realization easily also.
Known to this patent inventor, the complete water-based system that yet there are no based on sol-gel technique prepares super patent and the document of refusing the water textiles down.Self-evident, invention high efficiency, the super water-repellent finishing method of easy industrialized textiles under complete water-based system condition have important practical significance.
Summary of the invention:
In order to overcome deficiency with an organic solvent extremely low in the prior art with production efficiency, the object of the present invention is to provide a kind of complete water-based, environmental protection, low cost, high efficiency, the super water-repellent finishing method of easy industrialized textiles.This method for sorting is handled fabric fully in water-based system, simple to operate, good finishing effect.The arrangement process is not only economical, safe but also environmentally friendly, meets the requirement of Green Chemistry.
The method of the super water repellent finish of the present invention's industrialized textiles of a kind of environmental protection low-cost and easy-to comprises the steps:
(1) textiles is padded in silica hydrosol-dry; With
(2) in the presence of catalytic synergist, the textiles after padding-dry in the step (1) is placed in the aqueous emulsion of siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture and pads-preliminary drying-bake.
The method of the super water repellent finish of textiles of the present invention not only safety is environmentally friendly again, high efficiency, and the textile touch softness after handling.
The specific embodiment
One preferred embodiment in, silica hydrosol used in the inventive method is by silicic acid C
1-4The Arrcostab hydrolysis makes.
Above-mentioned silicic acid C
1-4The chemical structural formula of Arrcostab is as follows:
R is methyl, ethyl, n-pro-pyl or normal-butyl etc. in the formula.
Silicic acid C
1-4The hydrolysis of Arrcostab is carried out under the catalysis of acid or alkali.For example, with positive silicic acid C
1-4Arrcostab joins in the water (as deionized water) that contains acid or base catalyst, stirs 10-240 minute under the room temperature, is prepared into silica hydrosol.
Described step (1) acid catalyst is inorganic acid or organic acid.Inorganic acid for example is hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid etc.Organic acid for example is acetate, propionic acid, ethanedioic acid, malonic acid, succinic acid, 2 hydroxy propanoic acid, hydroxysuccinic acid, 2,3-dyhydrobutanedioic acid, 3-hydroxyl-3-carboxyl glutaric acid.Described step (1) base catalyst comprises inorganic base or organic base.Inorganic base for example is ammoniacal liquor, NaOH or potassium hydroxide.Organic base for example is one or more in monoethanolamine, diethanol amine, triethanolamine, ethylenediamine or the propane diamine.
The addition of catalyst is generally 0.05～5 weight % in the step (1), is preferably 1～4 weight %, is benchmark with the gross weight of silica hydrosol.
Though do not want to be subjected to concrete theoretical constraint, think less with the average grain diameter of the silica hydrosol of the inventive method preparation, be generally 10～150 nanometers, be preferably 30～100 nanometers, have tangible Tyndall effect.
In the inventive method in the used silica hydrosol concentration of silicon dioxide decide on the processing request of condition of padding and textiles, be generally 0.1～10 weight %, preferred 1-5 weight % is a benchmark with the gross weight of silica hydrosol.
It should be noted that in dyeing padding with dipping is two kinds of different technologies, dipping is the batch (-type) operation, and does not need to roll; And pad is to work continuously on equipment for dyeing and finishing, and general 2-3 finished in second.
Used textiles comprises cellulose base fiber fabric, synthetic fabrics and the BLENDED FABRIC of being made up of them in the inventive method, and synthetic fabrics is particularly useful for knitted fabric.
By method for sorting conventional in this area textiles is padded in the silica hydrosol that makes-dries.The liquid carrying rate that pads is generally 60-100%, and preferred liquid carrying rate is 70-90%.Under normal condition, dry then, for example at 25～130 ℃, preferably 100～130 ℃ of oven dry 2-3 minute.If needed, pad operation and can repeat repeatedly, be generally two and soak two and roll, dry then.
The aqueous emulsion of used siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture can prepare as follows in the inventive method step (2): the concentrated emulsion of commercially available siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture is joined in an amount of water, add an amount of catalytic synergist then; Perhaps an amount of emulsifying agent, an amount of siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture and an amount of catalytic synergist are joined in an amount of water, after stirring, form aqueous emulsion, be used for the textiles after further arrangement has been handled with silica hydrosol then.
One preferred embodiment in, the inventive method is used the siloxanes with following chemical structural formula:
R in the formula
1Be vinyl, phenyl or alkyl C
nH
2n+1-, n=1～18 wherein, preferred 8～18, more preferably 16～18;
R
2Be C
1-2Alkyl;
R
3Be C
1-2Alkyl or C
1-2Alkoxyl.
In another preferred implementation, the inventive method use polysiloxanes be 162-1000000 as number-average molecular weight, be preferably poly-two C of 200-100000
1-2Alkylsiloxane or number-average molecular weight are 223-1000000, are preferably the poly-C of 400-100000
1-2The alkyl hydrogen siloxanes.
In another preferred implementation, the inventive method use the hydroxyl polysiloxanes be 252-1000000 as number-average molecular weight, be preferably poly-two C of hydroxyl of 300-100000
1-2Alkylsiloxane.
In the inventive method step (2) consumption of used siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture can be according to the weight of the textiles that once pads, pad conditions such as number of times and regulated, be generally 0.25～10 weight %, being preferably 1～5 weight %, is benchmark with the gross weight of siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture aqueous emulsion.
Comprise non-ionic surface active agent, cationic surfactant, anion surfactant or its mixture at the used surfactant of method of the present invention.
In a concrete embodiment, above-mentioned non-ionic surface active agent for example comprises fatty alcohol-polyoxyethylene ether (AEO) series, tween (Tween) series, sapn (Span) series, stearine, polyethylene glycol stearate or its mixture; Above-mentioned anion surfactant for example comprises lauryl sodium sulfate, neopelex, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, odium stearate, NaLS or its mixture; Above-mentioned cationic surfactant for example comprises Dodecyl trimethyl ammonium chloride, DTAB, hexadecyltrimethylammonium chloride, softex kw or its mixture.
The consumption of surfactant in the inventive method step (2) is generally below the 10 weight % so that siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture form aqueous emulsion is as the criterion, and is benchmark with the gross weight of above-mentioned aqueous emulsion.
Though do not want to be subjected to concrete theory, think that siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture molecule of emulsification in the presence of catalytic synergist can be rapidly, be firmly bonded on the textile fiber, produce the super water effect of refusing.
One preferred embodiment in, the used catalytic synergist of the present invention comprises zinc salt, titanium salt, titanate esters, zirconates, zirconocene, pink salt or their mixture.
In some preferred embodiments, above-mentioned zinc salt is a zinc chloride, zinc sulfate, zinc acetate, MALEIC ACID, ZINC SALT, diethyl zinc, zinc oxalate, zinc succinate, pentane dicarboxylic acid zinc, zinc pyrrolidone carboxylate or its mixture, above-mentioned titanium salt is a titanium tetrachloride, acetylacetone,2,4-pentanedione oxygen titanium, cyclopentadienyl titanium dichloride, the luxuriant trichlorine titanium of pentamethyl list, single indenes trichlorine titanium or its mixture, above-mentioned titanate esters is a tetraisopropyl titanate, butyl titanate, metatitanic acid four 2-ethylhexyls, two (ethyl acetoacetate) metatitanic acid diisopropyl ester, or its mixture, described zirconates is a zirconium chloride, basic zirconium chloride or its mixture, above-mentioned zirconocene is a bis cyclopentadienyl zirconium dichloride, dimethyl zirconocene or its mixture, above-mentioned pink salt are dibutyl tin dilaurate, dioctyl two laurate tin, three sad Monobutyltins, dibutyl two tin octoates, di-n-butylacetic acid tin, the dihydroxy dibutyl tin oxide, dibutyltin diacetate, butter of tin or its mixture.
In the method for the invention, above-mentioned catalytic synergist uses with catalytic amount, is generally 0.05～10 weight %, is preferably 0.3～5 weight %, is benchmark with the gross weight of siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture aqueous emulsion.
Then, textiles such as the COTTON FABRIC after will handling with silica hydrosol by method for sorting conventional in this area padded in the aqueous emulsion of the siloxanes that makes, polysiloxanes, hydroxyl polysiloxanes or its mixture-preliminary drying-bake.Liquid carrying rate when padding is generally 60-100%, and preferred liquid carrying rate is 70-90%.Textiles after will padding then preliminary drying under normal condition is for example at 30～130 ℃, preferably at 100～120 ℃ of preliminary drying 2-3 minutes.At last, pre-baked textiles is baked at 140～190 ℃, preferably baked 2-3 minute at 150～170 ℃.
If needed, padding operation and also can repeat repeatedly in the step (2) is generally two and soaks two and roll.
In sum, method provided by the invention is simple, and handling safety is used conventional equipment for dyeing and finishing, production efficiency height, easily industrialization; Good through the fabric water repellency that the present invention handles, contact angle is greater than 150 °, and trickle progression has super water repellency all greater than 90; Processing procedure is very little to the physical and mechanical properties influence of fabric, does not influence wearability of fabric; Processing procedure of the present invention is not used any organic solvent, and the chemicals of use has no side effect, the processing procedure environmental protection.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Experimental data among each embodiment is measured with the following method:
Contact angle is measured under environment temperature with DataPhysics OCA 40 optics contact angle measurements.The distillation water droplet that concrete mensuration process is 5 μ l begins to measure its contact angle to sample surfaces 60s.Same sample is measured 5 times at different parts, averages.
Trickle progression is measured on YG-301 type spray tester according to " AATCC method of testing 22-2001. water proofing property: spray test " standard.
Physical and mechanical properties is pressed GB/T 3923.1-1997 " the mensuration galley proof method of textiles ultimate strength elongation " standard, at YG (B) 026H-250 type fabric strength aircraft measurements ultimate strength.
Whiteness is to measure the CIE whiteness on Datacolor 400 computer color measurement and color match instrument, and each sample builds up 8 layers, and positive and negative is respectively surveyed 3 times, averages.
Embodiment 1
With the 0.5g mass percent concentration is that 37% hydrochloric acid joins in the 500g deionized water, stirs 10 minutes under the room temperature.Drip the 10g ethyl orthosilicate then, continue to stir 60 minutes, left standstill 15 minutes, obtain little blueing light, transparent silica hydrosol.It is obvious to observe this hydrosol Tyndall effect in the Tyndall phenomenon test instrument, is 65.3nm with the average grain diameter of this hydrosol of Zetasizer Nano ZS nano particle size analysis-e/or determining.With all-cotton fabric (poplin cloth, 40
s* 40
s/ 133 * 72, available from Hangzhou Tianrui printing and dyeing Co., Ltd) in the hydrosol of preparation, two soak two and roll 80%, 120 ℃ of oven dry of liquid carrying rate 2 minutes.
With 17.5g aqueous emulsion of dimethyl polysiloxane fluid (TW-304, available from T-Win (SHANGHAI) TradingLtd), 2.5g hydroxyl aqueous emulsion of dimethyl polysiloxane fluid (YMR7212, available from MOMENTIVEPerformance Materials), the 2g titanium tetrachloride joins in the 500g deionized water, stirring is mixed with dressing liquid.Then, will in above-mentioned dressing liquid, two soak two and roll through COTTON FABRIC that the hydrosol is handled, 80%, 110 ℃ of preliminary drying of liquid carrying rate 2 minutes, 170 ℃ baked 2 minutes, and obtained having the COTTON FABRIC of super waterproofing function.Soft.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 1:
The water repellency of table 1 finish fabric and physical and mechanical properties
Embodiment 2
With the 0.4g mass percent concentration is that 37% hydrochloric acid joins in the 500g deionized water, stirs 10 minutes under the room temperature.Drip the 10g methyl silicate then, continue to stir 60 minutes, left standstill 15 minutes, obtain little blueing light, transparent silica hydrosol.It is obvious to observe this hydrosol Tyndall effect in the Tyndall phenomenon test instrument, is 72.1nm with the average grain diameter of this hydrosol of Zetasizer Nano ZS nano particle size analysis-e/or determining.With all-cotton fabric (poplin cloth, 40
s* 40
s/ 133 * 72, available from Hangzhou Tianrui printing and dyeing Co., Ltd) in the hydrosol of preparation, two soak two and roll 80%, 120 ℃ of oven dry of liquid carrying rate 2 minutes.
30g aqueous emulsion of dimethyl polysiloxane fluid (TW-304 is available from T-Win (SHANGHAI) TradingLtd), 4g titanium tetrachloride are joined in the 500g deionized water, and stirring is mixed with dressing liquid.Then, will in above-mentioned dressing liquid, two soak two and roll through COTTON FABRIC that the hydrosol is handled, 90%, 110 ℃ of preliminary drying of liquid carrying rate 2 minutes, 160 ℃ baked 3 minutes, and obtained having the COTTON FABRIC of super waterproofing function.Soft.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 2:
The water repellency of table 2 finish fabric and physical and mechanical properties
Embodiment 3
With the 4g mass percent concentration is that 28% ammoniacal liquor joins in the 500g deionized water, stirs 10 minutes under the room temperature.Drip the 12g ethyl orthosilicate then, continue to stir 120 minutes, left standstill 30 minutes, obtain little blueing light, transparent silica hydrosol.It is obvious to observe this hydrosol Tyndall effect in the Tyndall phenomenon test instrument, is 98.4nm with the average grain diameter of this hydrosol of Zetasizer Nano ZS nano particle size analysis-e/or determining.With all-cotton fabric (poplin cloth, 40
s* 40
s/ 133 * 72, available from Hangzhou Tianrui printing and dyeing Co., Ltd) in the hydrosol of preparation, two soak two and roll 80%, 120 ℃ of oven dry of liquid carrying rate 2 minutes.
12.5g dodecyl triethoxy silica alkane emulsion, 7.5g hydroxyl aqueous emulsion of dimethyl polysiloxane fluid (YMR7212, MOMENTIVE Performance Materials), 2g titanium tetrachloride are joined in the 500g deionized water, and stirring is mixed with dressing liquid.Then, will in above-mentioned dressing liquid, one soak one and roll through COTTON FABRIC that the hydrosol is handled, 80%, 110 ℃ of preliminary drying of liquid carrying rate 2 minutes, 180 ℃ baked 1 minute, and obtained having the COTTON FABRIC of super waterproofing function.Soft.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 3:
The water repellency of table 3 finish fabric and physical and mechanical properties
Embodiment 4
With the 1.0g mass percent concentration is that 30% acetate joins in the 500g deionized water, stirs 10 minutes under the room temperature.Drip the 12g ethyl orthosilicate then, continue to stir 90 minutes, left standstill 30 minutes, obtain little blueing light, transparent silica hydrosol.It is obvious to observe this hydrosol Tyndall effect in the Tyndall phenomenon test instrument, is 22.7nm with the average grain diameter of this hydrosol of Zetasizer Nano ZS nano particle size analysis-e/or determining.With all-cotton fabric (poplin cloth, 40
s* 40
s/ 133 * 72, available from Hangzhou Tianrui printing and dyeing Co., Ltd) in the hydrosol of preparation, two soak two and roll 80%, 120 ℃ of oven dry of liquid carrying rate 2 minutes.
20g dodecyl triethoxy silica alkane emulsion, 1g zinc chloride are joined in the 500g deionized water, and stirring is mixed with dressing liquid.Then, will in above-mentioned dressing liquid, one soak one and roll through COTTON FABRIC that the hydrosol is handled, 90%, 110 ℃ of preliminary drying of liquid carrying rate 2 minutes, 170 ℃ baked 2 minutes, and obtained having the COTTON FABRIC of super waterproofing function.Soft.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 4:
The water repellency of table 4 finish fabric and physical and mechanical properties
Embodiment 5
With the 5g mass percent concentration is that 28% ammoniacal liquor joins in the 500g deionized water, stirs 10 minutes under the room temperature.Drip the 10g methyl silicate then, continue to stir 90 minutes, left standstill 30 minutes, obtain little blueing light, transparent silica hydrosol.It is obvious to observe this hydrosol Tyndall effect in the Tyndall phenomenon test instrument, is 135.7nm with the average grain diameter of this hydrosol of Zetasizer Nano ZS nano particle size analysis-e/or determining.With dacron (double jersey, 34D * 24D, 150g/m
2, sky, Zhangjiagang wing Fabritex S.r.l) in the hydrosol of preparation, one soak one and roll, 80%, 120 ℃ of oven dry of liquid carrying rate 2 minutes.
15g dodecyl triethoxy silica alkane emulsion, 5g hydroxyl aqueous emulsion of dimethyl polysiloxane fluid (YMR7212, MOMENTIVE Performance Materials), 1g acetylacetone,2,4-pentanedione oxygen titanium are joined in the 500g deionized water, and stirring is mixed with dressing liquid.Then, will two soak two and roll in above-mentioned dressing liquid through polyester knitting thing that the hydrosol is handled, liquid carrying rate bakes 2 minutes for 90%, 170 ℃, obtained having the polyester knitting thing of super waterproofing function.Soft.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 5:
The water repellency of table 5 finish fabric and physical and mechanical properties
Embodiment 6
With the 2.0g mass percent concentration is that 30% acetate joins in the 500g deionized water, stirs 10 minutes under the room temperature.Drip the 16g ethyl orthosilicate then, continue to stir 60 minutes, left standstill 30 minutes, obtain little blueing light, transparent silica hydrosol.It is obvious to observe this hydrosol Tyndall effect in the Tyndall phenomenon test instrument, is 35.9nm with the average grain diameter of this hydrosol of Zetasizer Nano ZS nano particle size analysis-e/or determining.With dacron (double jersey, 34D * 24D, 150g/m
2, sky, Zhangjiagang wing Fabritex S.r.l) in the hydrosol of preparation, two soak two and roll, 70%, 120 ℃ of oven dry of liquid carrying rate 2 minutes.
20g cetyl triethoxy silica alkane emulsion, 0.25g butyl titanate, 0.5g zinc succinate are joined in the 500g deionized water, and stirring is mixed with dressing liquid.Then, will in above-mentioned dressing liquid, two soak two and roll through polyester knitting thing that the hydrosol is handled, 75%, 110 ℃ of preliminary drying of liquid carrying rate 2 minutes, 170 ℃ baked 2 minutes, obtained having the polyester knitting thing of super waterproofing function.Soft.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 6:
The water repellency of table 6 finish fabric and physical and mechanical properties
Embodiment 7
With the 0.5g mass percent concentration is that 37% hydrochloric acid joins in the 500g deionized water, stirs 10 minutes under the room temperature.Drip the 12g ethyl orthosilicate then, continue to stir 60 minutes, left standstill 15 minutes, obtain little blueing light, transparent silica hydrosol.It is obvious to observe this hydrosol Tyndall effect in the Tyndall phenomenon test instrument, is 68.9nm with the average grain diameter of this hydrosol of Zetasizer Nano ZS nano particle size analysis-e/or determining.With all-cotton fabric (poplin cloth, 40
s* 40
s/ 133 * 72, available from Hangzhou Tianrui printing and dyeing Co., Ltd) in the hydrosol of preparation, two soak two and roll 80%, 120 ℃ of oven dry of liquid carrying rate 2 minutes.
With 17.5g aqueous emulsion of dimethyl polysiloxane fluid (TW-304, available from T-Win (SHANGHAI) TradingLtd), 2.5g hydroxyl aqueous emulsion of dimethyl polysiloxane fluid (YMR7212, available from MOMENTIVEPerformance Materials), the 2g basic zirconium chloride joins in the 500g deionized water, stirring is mixed with dressing liquid.Then, will in above-mentioned dressing liquid, two soak two and roll through COTTON FABRIC that the hydrosol is handled, 80%, 110 ℃ of preliminary drying of liquid carrying rate 2 minutes, 170 ℃ baked 2 minutes, and obtained having the COTTON FABRIC of super waterproofing function.Soft.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 7:
The water repellency of table 7 finish fabric and physical and mechanical properties
Embodiment 8
With the 0.4g mass percent concentration is that 37% hydrochloric acid joins in the 500g deionized water, stirs 10 minutes under the room temperature.Drip the 12g methyl silicate then, continue to stir 60 minutes, left standstill 15 minutes, obtain little blueing light, transparent silica hydrosol.It is obvious to observe this hydrosol Tyndall effect in the Tyndall phenomenon test instrument, is 72.8nm with the average grain diameter of this hydrosol of Zetasizer Nano ZS nano particle size analysis-e/or determining.With all-cotton fabric (poplin cloth, 40
s* 40
s/ 133 * 72, available from Hangzhou Tianrui printing and dyeing Co., Ltd) in the hydrosol of preparation, two soak two and roll 80%, 120 ℃ of oven dry of liquid carrying rate 2 minutes.
16g octadecyl triethoxy silica alkane emulsion, 2.5g poly dimethyl hydrogen siloxane emulsion (WS 60, available from Wacker Chemie AG), 2g di-n-butylacetic acid tin are joined in the 500g deionized water, and stirring is mixed with dressing liquid.Then, will in above-mentioned dressing liquid, two soak two and roll through COTTON FABRIC that the hydrosol is handled, 90%, 110 ℃ of preliminary drying of liquid carrying rate 2 minutes, 160 ℃ baked 3 minutes, and obtained having the COTTON FABRIC of super waterproofing function.Soft.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 8:
The water repellency of table 8 finish fabric and physical and mechanical properties
Reference example 1
Method according to patent CN 101397754A invention surpasses water repellent finish to COTTON FABRIC, is specially: with the 30ml mass concentration is that 25% ammoniacal liquor is added in the 500ml ethanol, stirs 30 minutes.Drip the 25ml tetraethyl orthosilicate then, continue to stir 90 minutes, still aging 30 minutes, obtain the silica alcosol.With all-cotton fabric (poplin cloth, 40
s* 40
s/ 133 * 72, available from Hangzhou Tianrui printing and dyeing Co., Ltd) impregnated in the alcosol 30 minutes, one soaks one rolls, 90%, 100 ℃ of preliminary drying of liquid carrying rate 2 minutes.
15ml cetyl trimethoxy siloxane is joined in the 500ml ethanol, add glacial acetic acid 15ml and deionized water 5ml, stir under the room temperature and obtained hydrolyzate in 30 minutes.To flood 30 minutes in said hydrolyzed liquid through the COTTON FABRIC that alcosol is handled, room temperature is dried, again 120 ℃ of oven dry 30 minutes.Obtain the super water COTTON FABRIC of refusing.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 9:
The water repellency of table 9 finish fabric and physical and mechanical properties
Reference example 2
Method according to patent CN 101591853A invention surpasses water repellent finish to COTTON FABRIC, be specially: preparation contains the aqueous solution of tetraethyl orthosilicate, BTCA and sodium hypophosphite, and wherein the mass percent concentration of tetraethyl orthosilicate, BTCA, sodium hypophosphite is respectively 5%, 6% and 4%; With solution supersonic oscillations 30 minutes, stirred 30 minutes, obtain the silicon dioxide gel of modification; With all-cotton fabric (poplin cloth, 40
s* 40
s/ 133 * 72, Hangzhou Tianrui printing and dyeing Co., Ltd) in the above-mentioned dressing liquid that obtains, two soak two and roll, 80%, 80 ℃ of preliminary drying of liquid carrying rate 3 minutes, 170 ℃ baked 2 minutes.
The ethanolic solution of the cetyl trimethoxy siloxane of preparation butane tetracarboxylic aqueous acid catalyzing hydrolysis, wherein BTCA and cetyl trimethoxy siloxane mass percent are respectively 0.5% and 4%.The fabric that front arrangement is obtained flood 2 hours in this solution, 80 ℃ of preliminary dryings 3 minutes, and 170 ℃ baked 2 minutes, obtained surpassing refusing the water COTTON FABRIC.
According to " AATCC method of testing 22-2001. water proofing property: spray test ", GB/T 3923.1-1997 standards such as " the mensuration galley proof methods of textiles ultimate strength elongation ", fabric to arrangement carries out water repellency and physical and mechanical properties test, concrete outcome such as following table 10:
The water repellency of table 10 finish fabric and physical and mechanical properties
Claims (10)
1. the method for the super water repellent finish of textiles comprises the steps:
(1) textiles is padded in silica hydrosol-dry; With
(2) in the presence of catalytic synergist, the textiles after padding-dry in the step (1) is padded in the aqueous emulsion of siloxanes, polysiloxanes, hydroxyl polysiloxanes or its mixture-preliminary drying-bake.
2. the method for the super water repellent finish of textiles as claimed in claim 1 is characterized in that: described silica hydrosol is by silicic acid C
1-4The Arrcostab hydrolysis makes.
3. the method for the super water repellent finish of textiles as claimed in claim 2 is characterized in that: described silicic acid C
1-4The chemical structural formula of Arrcostab is as follows:
R is methyl, ethyl, n-pro-pyl or normal-butyl in the formula.
4. the method for the super water repellent finish of textiles as claimed in claim 2 is characterized in that: silicic acid C
1-4The hydrolysis of Arrcostab is carried out under the catalysis of acid or alkali.
5. the method for the super water repellent finish of textiles as claimed in claim 1 is characterized in that: described catalytic synergist comprises zinc salt, titanium salt, titanate esters, zirconates, zirconocene, pink salt or their mixture.
6. the method for the super water repellent finish of textiles as claimed in claim 5, it is characterized in that: described zinc salt is a zinc chloride, zinc sulfate, zinc acetate, MALEIC ACID, ZINC SALT, diethyl zinc, zinc oxalate, zinc succinate, pentane dicarboxylic acid zinc, zinc pyrrolidone carboxylate or its mixture, described titanium salt is a titanium tetrachloride, acetylacetone,2,4-pentanedione oxygen titanium, cyclopentadienyl titanium dichloride, the luxuriant trichlorine titanium of pentamethyl list, single indenes trichlorine titanium or its mixture, described titanate esters is a tetraisopropyl titanate, butyl titanate, metatitanic acid four 2-ethylhexyls, two (ethyl acetoacetate) metatitanic acid diisopropyl ester, or its mixture, described zirconates is a zirconium chloride, basic zirconium chloride or its mixture, described zirconocene is a bis cyclopentadienyl zirconium dichloride, dimethyl zirconocene or its mixture, described pink salt are dibutyl tin dilaurate, dioctyl two laurate tin, three sad Monobutyltins, dibutyl two tin octoates, di-n-butylacetic acid tin, the dihydroxy dibutyl tin oxide, dibutyltin diacetate, butter of tin or its mixture.
7. the method for the super water repellent finish of textiles as claimed in claim 1 is characterized in that: the chemical structural formula of described siloxanes is as follows:
R in the formula
1Be vinyl, phenyl or alkyl C
nH
2n+1-, n=1～18 wherein;
R
2Be C
1-2Alkyl;
R
3Be C
1-2Alkyl or C
1-2Alkoxyl;
Described polysiloxanes is that number-average molecular weight is poly-two C of 162-1000000
1-2Alkylsiloxane or number-average molecular weight are the poly-C of 223-1000000
1-2The alkyl hydrogen siloxanes;
Described hydroxyl polysiloxanes is that number-average molecular weight is poly-two C of hydroxyl of 252-1000000
1-2Alkylsiloxane.
8. the method for the super water repellent finish of textiles as claimed in claim 1 is characterized in that: described aqueous emulsion makes with non-ionic surface active agent, cationic surfactant, anion surfactant or its emulsifying mixture.
9. the method for the super water repellent finish of textiles as claimed in claim 1 is characterized in that: padding in the described step (1) is to soak one to roll, two soak two and roll or soak more and roll more; Liquid carrying rate is 60-100%, and bake out temperature is 25～130 ℃.
10. the method for the super water repellent finish of textiles according to claim 1 is characterized in that: padding in the described step (2) is to soak one to roll, two soak two and roll or soak more and roll more; Liquid carrying rate is 60-100%, and the preliminary drying temperature is 100～130 ℃; Baking temperature is 140～190 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147281A (en) * | 2013-03-08 | 2013-06-12 | 天津微能新材料有限公司 | Super-hydrophobic fabric preparation method and super-hydrophobic functional fabric |
| CN103147248A (en) * | 2013-03-22 | 2013-06-12 | 东华大学 | Continuous processing equipment for superhydrophobic fabrics |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397754A (en) * | 2008-11-03 | 2009-04-01 | 东华大学 | Method for preparing floride-free super-hydrophobic cotton fabric |
| CN101591853A (en) * | 2009-06-23 | 2009-12-02 | 东华大学 | A kind of method for sorting of cellulosic fabric fluorine-free nano durable super hydrophobicity |
-
2010
- 2010-05-20 CN CN 201010180559 patent/CN102251391B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397754A (en) * | 2008-11-03 | 2009-04-01 | 东华大学 | Method for preparing floride-free super-hydrophobic cotton fabric |
| CN101591853A (en) * | 2009-06-23 | 2009-12-02 | 东华大学 | A kind of method for sorting of cellulosic fabric fluorine-free nano durable super hydrophobicity |
Non-Patent Citations (5)
| Title |
|---|
| 《印染》 20070515 李正雄等 棉织物溶胶-凝胶法的无氟拒水整理研究 , 第10期 * |
| 《印染助剂》 20080920 李正雄等 棉织物溶胶-凝胶法的超疏水整理 第25卷, 第09期 * |
| 《印染助剂》 20090720 高琴文等 纺织品无氟溶胶-凝胶法拒水整理 第26卷, 第07期 * |
| 《纺织学报》 20090515 高琴文等 棉织物无氟超疏水整理 第30卷, 第05期 * |
| 《纺织科技进展》 20081025 高琴文等 涤纶织物无氟溶胶-凝胶法拒水整理 , 第05期 * |
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| CN103147281A (en) * | 2013-03-08 | 2013-06-12 | 天津微能新材料有限公司 | Super-hydrophobic fabric preparation method and super-hydrophobic functional fabric |
| CN103147248A (en) * | 2013-03-22 | 2013-06-12 | 东华大学 | Continuous processing equipment for superhydrophobic fabrics |
| CN103147248B (en) * | 2013-03-22 | 2015-01-21 | 东华大学 | Continuous processing equipment for superhydrophobic fabrics |
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| 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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| CN107709654A (en) * | 2015-05-18 | 2018-02-16 | 帝人芳纶有限公司 | Textile and its manufacture method with water repellent finishing agent |
| CN105040450A (en) * | 2015-08-25 | 2015-11-11 | 无锡市长安曙光手套厂 | Water repellent fabric and manufacture method thereof |
| CN107236267A (en) * | 2017-06-06 | 2017-10-10 | 绍兴文理学院 | A kind of surface is modified the preparation method of jute lactic acid composite material |
| CN109403022A (en) * | 2017-08-16 | 2019-03-01 | 崑山科技大学 | Method for preparing aerogel/non-woven composite material with hydrophilicity or hydrophobicity and product thereof |
| CN109403022B (en) * | 2017-08-16 | 2021-04-30 | 崑山科技大学 | Method for preparing aerogel/non-woven composite material with hydrophilicity or hydrophobicity and product thereof |
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| CN110565369B (en) * | 2019-09-27 | 2022-01-21 | 南通大学 | Treatment method for improving fastness to soaping and fading of yarn dyed fabric and yarn dyed fabric |
| CN111607983A (en) * | 2020-05-15 | 2020-09-01 | 浙江理工大学 | Super-hydrophobic daytime passive radiation refrigeration fabric and preparation method thereof |
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