CN102444021B - Intelligent waterproof and moisture permeable fabric - Google Patents
Intelligent waterproof and moisture permeable fabric Download PDFInfo
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- CN102444021B CN102444021B CN201110242519.7A CN201110242519A CN102444021B CN 102444021 B CN102444021 B CN 102444021B CN 201110242519 A CN201110242519 A CN 201110242519A CN 102444021 B CN102444021 B CN 102444021B
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Abstract
The invention provides an intelligent waterproof and moisture permeable fabric and a preparation method thereof and relates to a preparation method of a waterproof and moisture permeable fabric. The preparation method comprises the following steps: carrying out surface modification on fiber by utilizing a plasma technique capable of realizing low-frequency normal-voltage corona discharging so as to generate plasma on the surface of the fiber; introducing hydrogel into surface of the fabric by chemical grafting modification; and adding a pore-forming agent so as to form a large amount of micropore structures in the gel. By using the preparation method, the stimulus response speed of the gel material on environment is obviously improved, the waterproof and moisture permeable properties of the fabric are enhanced, and the hand feeling and comfort level of the fabric are improved.
Description
Technical field
The present invention relates to a kind of waterproof moisture permeating fabric, especially aquogel is incorporated in fabric, obtain a kind of intelligent waterproof moisture permeating fabric and preparation method thereof.
Background technology
Along with the continuous change of human habitat, people improve constantly the demand of fabric multifunctional.Waterproof moisture permeating fabric is one of high value added product that people develop successively in recent years, is also a focus of current research.Waterproof moisture permeating fabric refers to that fabric can not seen through or soak into by water under certain hydraulic pressure, but the sweat steam that human body distributes but can be spread or is delivered to the external world by fabric, instead of between body surface and fabric, gather condensation and make people feel glutinous wet and sultry, thereby realize the unification of textile water-proof performance and water vapour permeability.Thereby with waterproof moisture permeating fabric make clothes can not only meet the needs of wearing in the bad weathers such as cold, sleet, strong wind, and also can perspire moisture-inhibiting under larger labour intensity, comfortable and easy to wear, can also be chemical, poisonous and infect and play isolated, filtration and moisture-inhibiting effect in environment.Therefore, the developed country such as the U.S., West Europe, Japan all classifies waterproof moisture permeating fabric as one of high-tech product geared to the 21st century.
For a long time, the product of waterproof moisture permeating fabric has following several: 1. polyurethane coating (PU) waterproof moisture permeating fabric has unique pliability, ABRASION RESISTANCE, low temperature properties, wettability, cohesiveness, glossiness and high cohesion and curing rate etc.; PU fabric, except having good block-water performance, also has good apparel construction, the designability of annex, to ensure dress fast and the sealing in water.But current this PU fabric is at home and abroad still in the research and development stage.2. multiple product adopts neoprene coated fabric or micropore PTFE film as the anti-layer material that soaks; 3. nylon fabrics, institutional framework mostly is Oxford and spins, and makees like this ABRASION RESISTANCE that can improve fabric surface, protects anti-dip-coating layer or the anti-film that soaks.
In recent years, many researchers conduct in-depth research waterproof moisture permeating fabric.Balance [balance, the development of thermo-responsive loomage water proof and moisture permeable dressing agent and performance study. Tianjin University of Technology's academic dissertation, 2005] by making the crystallization of flexible polyurethane section phase and introducing wherein the method such as crosslinked in chemistry, prepare critical transition temperature and be about the high poisture-penetrability shape memory polyurethane material of 20～26 DEG C, 15.6～21.0 DEG C of the most comfortable ambient air temperatures of a little higher than human body of this temperature range.[the Xu Xufan such as Xu Xufan, the research [J] of polyurethane PU coated fabric waterproofing and moisture-penetration performances. printing and dyeing assistant, 2003,20 (6): 23-25] PU resin N, dinethylformamide (DMF) solution coat is on base cloth, then put it into have affinity interaction with DMF and with the water-bath of polyurethane resin without affinity interaction in flood, prepared the Porous skin membrane of continuity pore, improved the waterproofing and moisture-penetration performances of PU film.[the Yun J.K such as Yun J.K, Preparation and properties of water borne polyurethaneurea/sodium alginate blends for high water vapor permeable coating materials[J] .Journal of Applied Polymer Science, 2007, 105:1168-1176] employing isophorone diisocyanate (IPDI), PTMG (PTMG), in the synthetic water-based PU of dihydromethyl propionic acid (DMPA), add mosanom, by its coating film forming on nylon cloth fabric, and then water is by mosanom stripping, the vapor transfer rate of coating is significantly increased.[the Hua Mingyang such as Hua Mingyang, the preparation method of aqueous polyurethane grafted siloxane wear-resistant soft finishing agent, Chinese patent, CN101161918A] in the raw material of synthetic waterproof moisture-penetrating urethane, add hydroxyl polysiloxanes, improve to a great extent flexibility and the ABRASION RESISTANCE of waterproof moisture-penetrating urethane coating.Sun Jun etc. [Sun Jun, a kind of waterproof moisture permeating fabric, Chinese patent, CN2526168Y] utilize the tetrafluoroethylene microporous barrier of better water resistance to be covered by fiber fabric layer the inside, have obtained the good fabric of resistance to water and water proofing property.[the Hao Xinmin such as Hao Xinmin, a kind of preparation method of polytetrafluoroethylwaterproof waterproof moisture permeating fabric, Chinese patent, CN101135115A] in polyurethane coating solution, add a small amount of natural plants powder, dry after-contraction has increased the porosity of polyurethane film, thereby has increased the water vapour permeability of the thin polyurethane rete of fabric face.
To sum up, above research mostly is polyurethane coating (PU) waterproof moisture permeating fabric.
Intellectual material refers to that material passes through self judgment can perception environmental change, realizes instruction and action executing.Aquogel is the swelling body of the cross-linked structure that forms with chemical bond or physical force between a kind of macromolecular chain, and the compound system being made up of water and macromolecule network, does not dissolve yet not melting, and small-molecule substance can permeate therein or spread.Some gel of research discovery can be made different responses and show distinctive intelligent multi-signals such as pH, temperature, magnetic field, electric field, light, chemical substances.Wherein, researcher's synthetic water gel monomer is the most common with acrylamide and derivative, acrylic acid and derivative thereof etc.In recent years, people have synthesized many kinds of novel high polymer gels, and this gellike is having a good application prospect aspect cell cultivation, drugrelease, fabric-modifying.
Plasma is called again electricity slurry, is first proposed in 1879 by English physicist William Crookes, and he has studied the character of ionized gas in vacuum tube, points out the existence of material the 4th state.Atom after being deprived of by portions of electronics and atom are ionized the ionized gas shape material that the positron-electron of rear generation forms.The plasma generating by gas discharge can roughly be divided into two classes.One class is high-temperature plasma, and its temperature is up to more than ten thousand degrees Celsius, and gas particle is all Ionized.Another kind of is low temperature plasma, relatively the former, it is suitable for carrying out preparation and the processing of high purity material by electrodeless discharge, process efficiency is high, for process choice provides more spaces.
Summary of the invention
Object of the present invention aims to provide a kind of intelligent waterproof moisture permeating fabric and preparation method thereof.
Using plasma treatment technology of the present invention, utilizes air as electric discharge carrier, through the corona of low frequency normal-pressure electric, produces free radical on fiber surface; Initiation grafting reaction again, is incorporated into aquogel in fabric, makes fabric face form intelligent gel layer, have the ability of " dry state-hygrometric state " environmental change being made to response, that is: in the environment of dry state, gel molecular is in contraction state, hole in fabric is open, and moisture-penetrable ventilated property is good; Once fabric is immersed in the water, gel layer is instant swollen rapidly, by the pore closure at different levels in fabric, stops water to permeate to fabric, the anti-function of soaking of performance.
The preparation method of intelligent waterproof moisture permeating fabric is as follows:
1, take 1 part of fabric, fiber is carried out to surface modification with plasma technique.
2, 0.0063～0.252 part of nitric acid and 0.0055～0.106 part of ammonium ceric nitrate are joined in redistilled water, then the fabric that plasma is contained in surface adds in ceric ammonium nitrate solution, after soaking 0.5～2h, take out, then under the effect of roll, remove the unreacted reactant on fabric, again fabric is put into 5.6～113 parts of NIPAs (NIPAM), 18.5～115 parts of methacrylic acid diethyl ethyl esters (DEAEMA), 5～20 parts of pore-foaming agents, 0.315～0.63 part of nitric acid, in the mixed solution of 8.16～40.8 parts of ethanol, in its mixed liquor, add the cross-linking agent aqueous solution that 32～100 parts of mass fractions are 5%～10% again, fill fast N
215～60min, reaction 8～24h.
3, react complete after, fabric, through cleaning removal of impurities, dry, obtains intelligent waterproof moisture permeating fabric.
Fabric of the present invention can be natural fabric or synthetic fiber.Natural fabric is as natural plant fibre (comprising cotton, fiber crops, fibre and soya etc.) silk, hair etc.Synthetic fiber are as terylene, nylon, acrylic fibers, polyvinyl, polypropylene fibre, polyvinyl chloride fibre, spandex etc.
The spendable working gas of apparatus for low-temperature plasma treatment of the present invention includes but not limited to following gas: O
2, H
2, N
2, NH
3, C
2h
4, CH
3, CF
4, C
2f
6deng.Low temperature plasma to the research of material surface modifying in, study the more two kinds of discharge types that mainly contain: high-frequency discharge and corona discharge.High-frequency discharge plasma treatment technology is the common technology in textile industry.High-frequency discharge need to be carried out under condition of high vacuum degree condition.When high-frequency discharge is carried out graft modification to material, conventionally adopt inert gas if He, Ar etc. are as electric discharge carrier, after electric discharge, matrix contacts with monomer solution.
Preferably, the present invention adopts corona discharge low temp plasma technology.Low frequency corona discharge corona discharge in air atmosphere, can carry out under normal pressure conventionally.Electronics has that sufficiently high energy makes that reactant excites, dissociation and ionization, and whole reaction system remains on lower temperature levels on the other hand, the destruction of having avoided high temperature may cause matrix.Low temperature plasma is easy to obtain simultaneously, and cost is lower.Matrix top layer can form free radical and trapped radical under the effect of various particles, after contacting, forms peroxy-radical with oxygen; In addition, also can follow the reactions such as crosslinked, degraded.These effects make matrix surface that marked change can occur.By water can be facilitated, intuitively be understood the variation of surface polarity in the mensuration of matrix surface contact angle.After modification, the polar group of matrix surface is more, and surface can be higher, and water droplet is just more easily sprawled, and contact angle is less.
More preferably, plasma surface of the present invention is modified as: after destarch, kiering, vacuum drying treatment, then on the apparatus for low-temperature plasma treatment that to be placed on power and to be 5KW, frequency be 2.45GHz, process 10～40s, obtain the fabric that plasma is contained on surface.
Above-mentioned said crosslinking agent is polyethylene glycol (200) double methacrylate (PEGDA), polyethylene glycol (400) double methacrylate (PEGDA) or N, N-methylene-bisacrylamide.
Said pore-foaming agent is (molecular weight is 400 or 600) polyethylene glycol or sodium chloride particle (average grain diameter is at 800～2500 orders).
Reacted fabric is put into distilled water and soak 12～24h, change distilled water therebetween three times; Boil 6～12h, remove the foreign material on fabric; Then fabric is immersed in the hydrochloric acid solution of 0.1mol/L after 4～10h, is taken out and use again distilled water rinsing 3～8h, after vacuumize 6～12h, obtain the intelligent waterproof moisture permeating fabric after aquogel modification.
The effect of ammonium ceric nitrate is as a kind of initator, causes methacrylic acid diethyl ethyl ester and N-isopropylacrylamide glycerol polymerization initiation reaction on fabric face.
The prepared intelligent waterproof moisture permeating fabric of the present invention has the following advantages:
(1) utilize the plasma treatment technique of low frequency normal-pressure electric corona to carry out surface modification to fiber, produce in its surface plasma, make fiber surface produce more long-life free radical, increasing its surface can, be conducive to aquogel in its surperficial grafting, also reduced process costs simultaneously.
(2) select N-isopropylacrylamide and methacrylic acid diethyl ester monomer to be prepared into aquogel, form there is higher swelling ability and to temperature, pH value compared with the macromolecule hydrogel of highly-responsive, improved feel and the comfort level of fabric; In gel-forming process, add pore-foaming agent simultaneously, at a large amount of microcellular structures of the inner formation of gel, significantly improve the response speed of gel rubber material to environmental stimulus, strengthen the waterproofing and moisture-penetration performances of fabric.
(3) N-isopropylacrylamide and methacrylic acid diethyl ester aquogel are weak polyelectrolyte aquogel, on strand with ionogenic functional group.Under the condition existing at electrolyte, the interaction between electric charge has a great impact the swelling behavior of gel, and in aquogel, the stability of the state of water and hydration hydrogen bond can be affected in addition.Sodium chloride in solution or polyglycols particle can make in modified fabric grafting strand become to curl, and interchain interaction strengthens, thereby causes itself and the interaction of water to weaken, and gel swelling degree declines, after modified fabric hydrolysis, and permeability rate raising.
Brief description of the drawings
Fig. 1 is the Waterproof Breathable principle of intelligent waterproof moisture permeating fabric: unmodified fabric unit, through after plasma surface modification, fabric face covers the closely knit plasma of one deck, adopt again graft-modification method, add monomer initiated polymerization, form the modified fabric unit of the progress in Intelligent Hydrogel with responsive to temperature performance.When fabric place in a humid environment, gel layer is rapidly instant swollen, by the pore closure at different levels in fabric, stops water to permeate to fabric, realizes the anti-function of soaking; When fabric is in the environment of dry state, gel molecular is in contraction state, and the hole in fabric is open, and moisture infiltrates from hole, realizes breathable moisture permeability.
Detailed description of the invention
Below by embodiment, the present invention will be further described.
Embodiment 1:
Step 1, take 1g fabric (nylon fiber), after destarch, kiering, vacuum drying treatment, then, on the apparatus for low-temperature plasma treatment that to be placed on power and to be 5KW, frequency be 2.45GHz, through low frequency Corona discharge Treatment 10s, obtain the fabric that plasma is contained on surface.
Step 2, 6.3mg nitric acid and 5.48mg ammonium ceric nitrate are joined in redistilled water (100mL), then the fabric that plasma is contained in surface adds in ceric ammonium nitrate solution, after soaking 0.5h, take out, then under the effect of roll, remove the unreacted reactant on fabric, again fabric is put into 5.6gN-N-isopropylacrylamide (NIPAM), 18.5g methacrylic acid diethyl ethyl ester (DEAEMA), 5g (molecular weight is 400) polyethylene glycol, 0.315g nitric acid, in the mixed solution of 8.16g ethanol, be 5% polyethylene glycol (200) double methacrylate (PEGDA) aqueous solution toward adding 32g mass fraction in its mixed liquor again, fill fast N
215min, reaction 8h.
Step 3, react complete after, reacted fabric is put into distilled water and soaks 12h, change distilled water therebetween three times; Boil 6h, remove the foreign material on fabric; Then fabric is immersed in the hydrochloric acid solution of 0.1mol/L after 4h, is taken out and use again distilled water rinsing 3h, after vacuumize 6h, obtain the intelligent waterproof moisture permeating fabric after aquogel modification.
Embodiment 2:
Step 1, take 1g fabric (cotton fabric), after destarch, kiering, vacuum drying treatment, then on the apparatus for low-temperature plasma treatment that to be placed on power and to be 5KW, frequency be 2.45GHz, process 20s, obtain the fabric that plasma is contained on surface.
Step 2, 0.0076g nitric acid and 0.0548g ammonium ceric nitrate are joined in redistilled water (140mL), then the fabric that plasma is contained in surface adds in ceric ammonium nitrate solution, after soaking 50min, take out, then under the effect of roll, remove the unreacted reactant on fabric, again fabric is put into 28.4g NIPA (NIPAM), 36.7g methacrylic acid diethyl ethyl ester (DEAEMA), 14g (molecular weight is 600) polyethylene glycol, 0.41g nitric acid, in the mixed solution of 20.4g ethanol, be 6% polyethylene glycol (400) double methacrylate (PEGDA) aqueous solution toward adding 48g mass fraction in its mixed liquor again, fill fast N
220min, reaction 10h.
Step 3, react complete after, reacted fabric is put into distilled water and soaks 16h, change distilled water therebetween three times; Boil 8h, remove the foreign material on fabric; Then fabric is immersed in the hydrochloric acid solution of 0.1mol/L after 5h, is taken out and use again distilled water rinsing 4h, after vacuumize 8h, obtain the intelligent waterproof moisture permeating fabric after aquogel modification.
Embodiment 3:
Step 1, take 1g fabric (natural ramie fiber), after destarch, kiering, vacuum drying treatment, then on the apparatus for low-temperature plasma treatment that to be placed on power and to be 5KW, frequency be 2.45GHz, process 28s, obtain the fabric that plasma is contained on surface.
Step 2, 0.164g nitric acid and 0.082g ammonium ceric nitrate are joined in redistilled water (160mL), then the fabric that plasma is contained in surface adds in ceric ammonium nitrate solution, after soaking 1h, take out, then under the effect of roll, remove the unreacted reactant on fabric, again fabric is put into 63.4g NIPA (NIPAM), 74.5g methacrylic acid diethyl ethyl ester (DEAEMA), 16g sodium chloride particle, 0.428g nitric acid, in the mixed solution of 26.1g ethanol, be 7% N toward adding 78.5g mass fraction in its mixed liquor again, the N-methylene-bisacrylamide aqueous solution, fill fast N
245min, reaction 16h.
Step 3, react complete after, reacted fabric is put into distilled water and soaks 18h, change distilled water therebetween three times; Boil 9h, remove the foreign material on fabric; Then fabric is immersed in the hydrochloric acid solution of 0.1mol/L after 8.5h, is taken out and use again distilled water rinsing 5h, after vacuumize 9h, obtain the intelligent waterproof moisture permeating fabric after aquogel modification.
Embodiment 4:
Step 1, take 1g fabric (terylene), after destarch, kiering, vacuum drying treatment, on the apparatus for low-temperature plasma treatment that to be then placed on power and to be 5KW, frequency be 2.45GHz, process 35s, obtain the fabric that plasma is contained on surface.
Step 2, 38g nitric acid and 16g ammonium ceric nitrate are joined in redistilled water (180mL), then the fabric that plasma is contained in surface adds in ceric ammonium nitrate solution, after soaking 1.5h, take out, then under the effect of roll, remove the unreacted reactant on fabric, again fabric is put into 88.6gN-N-isopropylacrylamide (NIPAM), 96.5g methacrylic acid diethyl ethyl ester (DEAEMA), 18.6g (molecular weight 600) polyethylene glycol, 0.252g nitric acid, in the mixed solution of 36.7g ethanol, be 8% polyethylene glycol (400) double methacrylate (PEGDA) aqueous solution toward adding 65g mass fraction in its mixed liquor again, fill fast N
245min, reaction 18h.
Step 3, react complete after, reacted fabric is put into distilled water and soaks 20h, change distilled water therebetween three times; Boil 10h, remove the foreign material on fabric; Then fabric is immersed in the hydrochloric acid solution of 0.1mol/L after 8h, is taken out and use again distilled water rinsing 6h, after vacuumize 10h, obtain the intelligent waterproof moisture permeating fabric after aquogel modification.
Embodiment 5:
Step 1, take 1g fabric (polyvinyl), after destarch, kiering, vacuum drying treatment, on the apparatus for low-temperature plasma treatment that to be then placed on power and to be 5KW, frequency be 2.45GHz, process 40s, obtain the fabric that plasma is contained on surface.
2, 252mg nitric acid and 109.6mg ammonium ceric nitrate are joined in redistilled water (200mL), then the fabric that plasma is contained in surface adds in ceric ammonium nitrate solution, after soaking 2h, take out, then under the effect of roll, remove the unreacted reactant on fabric, again fabric is put into 113gN-N-isopropylacrylamide (NIPAM), 115g methacrylic acid diethyl ethyl ester (DEAEMA), 20g sodium chloride particle, 0.63g nitric acid, in the mixed solution of 40.8g ethanol, be 10% N toward adding 100g mass fraction in its mixed liquor again, the N-methylene-bisacrylamide aqueous solution aqueous solution, fill fast N
260min, reaction 24h.
3, react complete after, reacted fabric is put into distilled water and soaks 24h, change distilled water therebetween three times; Boil 12h, remove the foreign material on fabric; Then fabric is immersed in the hydrochloric acid solution of 0.1mol/L after 10h, is taken out and use again distilled water rinsing 8h, after vacuumize 12h, obtain the intelligent waterproof moisture permeating fabric after aquogel modification.
Table 1 is implemented the waterproofing and moisture-penetration performances test result of each sample
Note: tension failure strength retention refers to the ratio of the tensile break strength of fabric before tensile break strength after fabric-modifying and modification.
Claims (4)
1. a preparation method for intelligent waterproof moisture permeating fabric, is characterized in that concrete steps are as follows:
Step 1, take 1 part of fabric, fiber is carried out to surface modification with plasma technique;
Step 2, 0.0063～0.252 part of nitric acid and 0.0055～0.106 part of ammonium ceric nitrate are joined in 100～200 parts of redistilled waters, then the fabric that plasma is contained in surface adds in ceric ammonium nitrate solution, after soaking 0.5～2h, take out, then under the effect of roll pressed, remove the unreacted reactant on fabric, again fabric is put into 5.6～113 parts of NIPAs, 18.5～115 parts of methacrylic acid diethyl amino ethyl group esters, 5～20 parts of pore-foaming agents, 0.315～0.63 part of nitric acid, in the mixed solution of 8.16～40.8 parts of ethanol, in its mixed liquor, add the cross-linking agent aqueous solution that 32～100 parts of mass fractions are 5%～10% again, fill fast N
215～60min, reaction 8～24h,
Step 3, react complete after, fabric, through cleaning removal of impurities, dry, obtains intelligent waterproof moisture permeating fabric: reacted fabric is put into distilled water and soak 12～24h, change distilled water therebetween three times; Boil 6～12h, remove the foreign material on fabric; Then fabric is immersed in the hydrochloric acid solution of 0.1mol/L after 4～10h, is taken out and use again distilled water rinsing 3～8h, after vacuumize 6～12h, obtain the intelligent waterproof moisture permeating fabric after aquogel modification;
Described crosslinking agent is polyethyleneglycol diacrylate or N, a kind of or its combination in N-methylene-bisacrylamide;
Described pore-foaming agent is a kind of or its combination in polyethylene glycol or sodium chloride particle.
2. the preparation method of a kind of intelligent waterproof moisture permeating fabric as claimed in claim 1, is characterized in that: the described plasma technique of step (1) is corona discharge plasma technology.
3. the preparation method of a kind of intelligent waterproof moisture permeating fabric as claimed in claim 1, it is characterized in that: the described surface modification of step (1) is: fabric is through after destarch, kiering, vacuum drying treatment, then on the apparatus for low-temperature plasma treatment that to be placed on power and to be 5KW, frequency be 2.45GHz, process 10～40s, obtain the fabric that plasma is contained on surface.
4. the preparation method of a kind of intelligent waterproof moisture permeating fabric as claimed in claim 1, is characterized in that: described pore-foaming agent average grain diameter is at 800～2500 orders.
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| CN102877285B (en) * | 2012-10-25 | 2014-12-17 | 愉悦家纺有限公司 | Desizing method of fabric |
| CN103271471A (en) * | 2013-06-13 | 2013-09-04 | 太仓协大申泰羊毛衫有限公司 | Antistatic, hygroscopic and degradable woolen sweater |
| CN103696088B (en) * | 2013-12-19 | 2016-02-24 | 吴江明敏制衣有限公司松陵分公司 | A kind of waterproof and dampproof fabric |
| CN103736140B (en) * | 2014-01-10 | 2016-04-27 | 中国人民解放军第三0二医院 | A kind of medical dressing hydrogel compound fabric and its preparation method and application |
| CN104179000B (en) * | 2014-09-12 | 2015-12-02 | 王朗 | A kind of manufacture method of waterproof woven thing |
| CN104264475B (en) * | 2014-10-10 | 2016-11-30 | 海门市彼维知识产权服务有限公司 | A kind of preparation method of Waterproof Breathable silk fabric |
| CN104264468A (en) * | 2014-10-22 | 2015-01-07 | 湖北久瑞核技术股份有限公司 | Preparation method for water-repellent textile |
| CN107201508A (en) * | 2016-03-16 | 2017-09-26 | 台湾神户电池股份有限公司 | The method for lifting the hydrophily and electric conductivity of carbon cloth |
| CN106498720B (en) * | 2016-11-18 | 2019-03-05 | 辽东学院 | A kind of temperature sensitive waterproof moisture permeable fabric and preparation method thereof |
| EP3470573A1 (en) * | 2017-10-16 | 2019-04-17 | Werner & Mertz GmbH | Method for producing a textile article with hydrophobised textile surface using plasma treatment and wet chemical processing |
| CN109778545A (en) * | 2019-01-22 | 2019-05-21 | 乐清市雅格狮丹服饰有限公司 | A kind of finishing technique of waterproof casings |
| CN111607893A (en) * | 2020-06-04 | 2020-09-01 | 浙江天晟信息技术有限公司 | Water-repellent non-woven fabric and preparation method thereof |
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