CN103468835A - Waterproof leather prepared via polymerization deposition of low-temperature plasmas and preparation method of waterproof leather - Google Patents
Waterproof leather prepared via polymerization deposition of low-temperature plasmas and preparation method of waterproof leather Download PDFInfo
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- CN103468835A CN103468835A CN2013104217889A CN201310421788A CN103468835A CN 103468835 A CN103468835 A CN 103468835A CN 2013104217889 A CN2013104217889 A CN 2013104217889A CN 201310421788 A CN201310421788 A CN 201310421788A CN 103468835 A CN103468835 A CN 103468835A
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Abstract
The invention discloses waterproof leather prepared via polymerization deposition of low-temperature plasmas and a preparation method of the waterproof leather. The method comprises the following steps: vaporizing siloxane monomers or crylic acid monomers or acrylate monomers or fluorinated acrylate monomers or fluorosilane monomers under the vacuum degree of 25Pa to 45Pa at the temperature of 25 DEG C to 50 DEG C; then adding the vaporized monomers into plasma reaction equipment according to a certain flow and reacting for 1 to 25 minutes under the discharge power within 0.15W/cm<2> to 1.5W/cm<2>; and depositing the monomers on the leather in the plasma reaction equipment, wherein the thickness of a waterproof membrane deposited on the surface of the leather in a polymerization manner is in a micron level or below the micron level, the static contact angle of the waterproof membrane is within 136 DEG to 155 DEG and the rolling angle of the waterproof membrane is within 7 DEG to 22 DEG, and stagger collagen fibers can be seen clearly by observing through a scanning electron microscope. The method is simple in treatment process, short in time, high in efficiency and low in energy consumption. The obtained waterproof membrane is thin, and not only can maintain the real leather feeling of the surfaces of stone washed leathers, suede leathers, double-purpose leathers and the like but also can maintain the sanitation performance of nature leathers.
Description
Technical field
The invention belongs to functional leather and preparing technical field thereof, be specifically related to a kind of Waterproof leather and method thereof with the preparation of low temperature plasma polymerization deposition.
Background technology
The WATER REPELLENT of common leather surface generally completes by covering with paint, lacquer, colour wash, etc. technique, and its waterproof finish agent used mainly forms with type siloxane polymkeric substance or acrylate containing fluorine polymkeric substance.As the people such as Gao Futang (Gao Futang etc. the synthetic and application of hydroxyl silicon oil modified acrylic resin hide finishes. leather science and engineering .2006,16 (1): 63-66) studied the hide finishes synthetic with hydroxyl silicon oil modified acrylic resin, this research shows, introduces silicone oil and can make the water tolerance of leather well be improved; The people such as An Qiufeng (film-forming properties of fluoro acrylic ester copolymer emulsion FSLDH, XPS characterize and hydrophobic performance. fine chemistry industry .2010,27 (5): the hydrophobicity of 486-490) having studied film-forming properties and the processing cotton fabric of fluoro acrylic ester copolymer emulsion, result shows, the vinylformic acid fluorine-containing latex can give cotton fabric good hydrophobicity.In addition, the organic fluorine monomer also can be used to synthetic multifunctional leather finishing agent, i.e. grafting organic fluorine in molecule, make finishing agent there is features, as waterproof, the performance such as grease proofing, antifouling and fire-retardant (structure of organofluorine compound and character and the application on leather industry thereof. Chinese leather .2006,35 (15): 42-47).But, above-mentioned waterproof finish agent is the siliceous of organic synthesis type or fluoro containing polymers polymkeric substance, although they can make the water-repellancy of leather be improved significantly really, but, the building-up process complexity of these finishing agents of one side, cause cost high, on the other hand, the coating that these finishing agents are coated in leather surface can hide the pore of the collegen filament of leather surface and leather surface fully, greatly affect the sanitation performance (being mainly the vapor pervious performance) of natural leather, thereby the snugness of fit of reduction leather (fourth petrel etc. the application of organosilicon in Leather Chemicals. daily chemical industry, 2003, 33 (5): 317-319, from Jian Hua etc. organic fluorine water-refusing oil-refusing multifunction finishing agent DM-3640C application art is inquired into. dyeing and printing auxiliary, 2008,25 (5): 28-30).
In addition, after the sticky water of leather, very easily produce washmarking, this not only will affect the surface aesthetic of leather, and will reduce its work-ing life, particularly to Buffed leather, velour, both fur and leather leather etc.And these leather products are covered with paint, lacquer, colour wash, etc. it owing to being difficult to the traditional covering with paint technique of employing, its water-repellancy problem is difficult to solve.Therefore, leather, the WATER REPELLENT that is especially non-covering with paint leather surface is the important technology difficult problem that leather industry faces.If at least the part surface of leather has before this from NO hydrophobicity level, will bring big advantages to the application of these leathers.
Low-temperature plasma is as a kind of quick, easy, process for treating surface that can keep the material monolithic performance, its treating processes is under certain atmosphere, (energy that plasma body high-energy particle bombardment material surface produces is generally a few to tens of ev to excite substrate surface or atmosphere material by plasma discharge, this energy surpasses the bond energy of common chemical bond, cause chemical bond rupture) the generation free radical, this free radical can cause substrate surface generation chemical reaction, thereby complete the processing to substrate surface, and give the substrate surface property.And the performance of substrate surface depends primarily on the composition of plasma atmosphere.At present, as two classes that mainly contain of plasma reaction atmosphere, a class is common gas, i.e. air, H
2, O
2, N
2, CO
2, Ar, He, CF
4deng, another kind of be using these gases as carrier gas stream through liquid state organics (as the hexamethyl disiloxane, tetraethoxy etc.), make a small amount of organism form plasma gas (the .Atmospheric pressure plasmas:Areview.Spectrochimica Acta Part B such as Claire Tendero together with carrier gas stream, 2006,61:2 – 30).Obviously, these existing gases define the application category of plasma body, and in addition, the organic content of vaporizing by carrier gas is difficult to control, and the existence of carrier gas stream simultaneously also can affect the surface property of the base material of organism improvement.
Summary of the invention
The objective of the invention is easily be soaked in water and produce washmarking for leather surface, affect the defect of its use value, life-span and surface aesthetic, at first a kind of method for preparing Waterproof leather by the low temperature plasma polymerization deposition is provided.
Another object of the present invention is to provide a kind of Waterproof leather prepared by aforesaid method.
The method for preparing Waterproof leather by the low temperature plasma polymerization deposition provided by the invention, processing step and the condition of the method are as follows:
1) at least one in type siloxane or acrylic acid or the like or esters of acrylic acid or acrylate containing fluorine or silicon fluoride class monomer put into to gasifying pot, then by the pending reaction chamber of putting into facing up plasma reaction device of leather, then gasifying pot is communicated with plasma reaction device;
2) vacuum tightness vacuumized in the reaction chamber that makes gasifying pot and plasma reaction device reaches 25-45Pa, the temperature of gasifying pot is risen to 25-50 ℃ simultaneously, after making the monomer vapor in gasifying pot, with 7 * 10
-5-9 * 10
-4ml/mincm
2flow enter in the reaction cavity of plasma reaction device, at exoelectrical reaction power, be 0.15-1.5W/cm
2under, reaction 1-25min, can obtain the leather that aggregation deposition has water-proof surface.
The preferred hexamethyl cyclotrisiloxane of siloxane compound described in above method, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes, hexamethyldisiloxane and vinyltriethoxysilane, more preferably hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane and vinyltriethoxysilane; The preferred vinylformic acid of acrylic monomer and methacrylic acid; The preferred methyl acrylate of acrylic ester monomer, butyl acrylate and methyl methacrylate, more preferably butyl acrylate; The preferred vinylformic acid hexafluoro of acrylate containing fluorine monomer butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, vinylformic acid ten trifluoro monooctyl esters and methacrylic acid ten trifluoro monooctyl esters, more preferably vinylformic acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate and vinylformic acid ten trifluoro monooctyl esters; Silicon fluoride class monomer is ten difluoro heptyl propyl trimethoxy silicanes, ten difluoro heptyl propyl group methyl dimethoxysilanes, ten trifluoro octyl group Trimethoxy silanes and 4-methyl-(perfluoro hexyl ethyl) propyl trimethoxy silicane preferably, more preferably ten trifluoro octyl group Trimethoxy silanes and 4-methyl-(perfluoro hexyl ethyl) propyl trimethoxy silicane.
The preferred 25-35Pa of vacuum tightness described in above method, more preferably 30-35Pa; The preferred 25-45 ℃ of described temperature, more preferably 30-45 ℃; Described flow preferably 7 * 10
-5-8 * 10
-4ml/mincm
2, more preferably 8 * 10
-5-6 * 10
-4ml/mincm
2; The preferred 0.15-1.0W/cm of described power
2, more preferably 0.3-1.0W/cm
2; Preferred 5-20min of described reaction times, more preferably 5-15min.
Leather described in above method is without any in obverse leather, velour, Buffed leather or the both fur and leather leather covered with paint, lacquer, colour wash, etc.
The Waterproof leather prepared by aforesaid method provided by the invention, the thickness of the waterproof membrane of this leather surface aggregation deposition is micron order or following, and its static contact angle is 136-155 °, and roll angle is 7-22 °, and observe the visible clear collegen filament that interweave from scanning electronic microscope.
The present invention compared with prior art, has the following advantages:
1, because the present invention is that the using plasma aggregation deposition makes leather surface adhere to one deck micron order or following waterproof membrane, thereby not only rete is thin, and the polymkeric substance deposited just can not seal the space between the leather surface collegen filament as covering with paint, lacquer, colour wash, etc., can keep the kishke feel of epidermis face on the one hand, also can keep on the other hand the sanitation performance of natural leather.
2, the waterproof membrane obtained due to using plasma aggregation deposition of the present invention is not only thin, and even compact, thereby water static contact angle thereon reaches as high as more than 150 °, and roll angle is very low, minimumly can, lower than 10 °, make leather surface obtain good hydrophobicity.
3, the plasma polymerization deposition mode adopted due to the present invention can make liquid monomer under the cooperation of vacuum tightness, in low-temperature vaporization, the plasma discharge aggregation deposition, thereby not only the treating processes flow of monomer is low, materials consumption is few, and the treatment time is short, efficiency is high, energy-conservation characteristics again.
What 4, adopt due to the present invention is that the plasma polymerization deposition mode prepares Waterproof leather, thereby covers with paint, lacquer, colour wash, etc. and compare with liquid emulsion, does not need subsequent disposal, has both reduced work program and tooling cost, and efficiency is higher again.
What 5, adopt due to the present invention is that the plasma polymerization deposition mode prepares Waterproof leather, can not cause damage to leather itself, thereby can solve the waterproof problem of the non-covering with paint leathers such as Buffed leather, velour, both fur and leather leather, filled up the blank of the WATER REPELLENT of non-covering with paint leather.
The accompanying drawing explanation
Fig. 1 is the change curve of the static contact angle of not covering with paint, lacquer, colour wash, etc. ox-hide obverse leather surface without Cement Composite Treated by Plasma with duration of contact.As seen from the figure, along with extend duration of contact, contact angle is reducing gradually, and this explanation water droplet slowly soaks leather surface;
The static contact angle (141 ° of left and right) on the ox-hide Buffed leather surface that Fig. 2 is embodiment 1 processing is with the change curve of duration of contact.As seen from the figure, along with extend duration of contact, contact angle remains unchanged, and this explanation water droplet can not soak leather surface;
The static contact angle (155 ° of left and right) on the ox-hide Buffed leather surface that Fig. 3 is embodiment 2 processing is with the change curve of duration of contact.As seen from the figure, along with extend duration of contact, contact angle remains unchanged, and this explanation water droplet can not soak leather surface;
Fig. 4 is that embodiment 5 processes the change curve of the static contact angle (136 ° of left and right) on sheepskin obverse leather surface with duration of contact.As seen from the figure, along with extend duration of contact, contact angle remains unchanged, and this explanation water droplet can not soak leather surface;
Fig. 5 is that embodiment 15 processes the change curve of the static contact angle (150 ° of left and right) on pig suede upper leather surface with duration of contact.As seen from the figure, along with extend duration of contact, contact angle remains unchanged, and this explanation water droplet can not soak leather surface;
Fig. 6 is the rolling situation schematic diagram of water droplet on the both fur and leather leather of differing tilt angles, wherein (a) is the rolling situation of water droplet on the leather of the both fur and leather without Cement Composite Treated by Plasma tilted, from this schematic diagram (a), when angle of inclination is larger, water droplet still can be retained on the both fur and leather leather; And (b) and (c), being respectively water droplet processes the rolling situation on the both fur and leather leather at the embodiment 16 tilted and embodiment 19, from this schematic diagram (b) and (c), when Inclined Angle is smaller, water droplet can roll on the both fur and leather leather, and roll from leather surface, the both fur and leather leather of this explanation after embodiment 16 and embodiment 19 processing has very strong hydrophobicity;
Fig. 7 is the atomic force microscope shape appearance figure without the surperficial 10 μ m of the ox-hide obverse leather of Cement Composite Treated by Plasma * 10 μ m.As seen from the figure, leather surface is that collegen filament are interwoven;
The atomic force microscope shape appearance figure of the ox-hide obverse leather surface 10 μ m that Fig. 8 is embodiment 10 processing * 10 μ m.As seen from the figure, the aggregated particles thing of plasma polymerization deposition, along the direction growth of fiber, can't cover interfibrous space;
Fig. 9 is the scanning electronic microscope shape appearance figure without the ox-hide obverse leather of Cement Composite Treated by Plasma.Can significantly observe the pore on ox-hide obverse leather surface from figure;
The scanning electronic microscope shape appearance figure of the ox-hide obverse leather that Figure 10 is embodiment 10 processing.Can significantly observe the pore on the ox-hide obverse leather surface after plasma treatment from figure, not compare not significantly difference with the ox-hide obverse leather without plasma treatment;
Figure 11 is the conventional scanning electronic microscope shape appearance figure of covering with paint, lacquer, colour wash, etc. the ox-hide obverse leather of processing.The pore that can significantly observe ox-hide obverse leather surface from figure is covered fully by coatings;
Figure 12 is the scanning electronic microscope shape appearance figure without the ox-hide Buffed leather frosting of Cement Composite Treated by Plasma.Can significantly observe the fiber of ox-hide Buffed leather frosting from figure;
The scanning electronic microscope shape appearance figure of the ox-hide Buffed leather frosting that Figure 13 is embodiment 12 processing.The fiber that can significantly observe the ox-hide Buffed leather frosting after plasma treatment from figure is still high-visible, with the not significantly difference of ox-hide Buffed leather frosting without plasma treatment;
Figure 14 is along with extend duration of contact, the black water droplet is rolling picture on ox-hide Buffed leather frosting, wherein (a) is that water droplet is at the rolling situation picture without on Cement Composite Treated by Plasma ox-hide Buffed leather frosting, from this figure (a), water droplet not only can not roll on untreated ox-hide Buffed leather frosting, and water droplet has produced the black washmarking on ox-hide Buffed leather frosting, and the rolling situation picture on ox-hide Buffed leather frosting that is (b) water droplet after embodiment 20 processes, from this figure (b), water droplet can Free-rolling on ox-hide Buffed leather frosting after embodiment 20 processes, and water droplet can not produce any washmarking on ox-hide Buffed leather frosting, this illustrates that its hydrophobicity is very strong.
Embodiment
Below by specific embodiment, the present invention is described in detail; need explanation at this; embodiment further illustrates of the present invention; the scope of application of the present invention is not subject to the restriction of embodiment; all improvement of doing on core content of the present invention and adjustment, all belong to the scope of protection of present invention.Scope of the present invention proposes in detail in claims.
What deserves to be explained is, below each embodiment to process the static contact angle of Waterproof leather of gained and roll angle be all that the OCA20/6 type contact angle instrument of producing with German dataphysics company records.
Embodiment 1
Hexamethyl cyclotrisiloxane is put into to gasifying pot, then ox-hide Buffed leather frosting is upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 30Pa, the temperature of gasifying pot risen to 30 ℃ simultaneously, make the hexamethyl cyclotrisiloxane vaporization, and with 7 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.15W/cm
2under, continuous discharge reaction 15min, close the plasma discharge electrode, is filled with air removal ox-hide Buffed leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali Buffed leather of the present embodiment gained is 141 ° ± 1 °, and roll angle is 15 ° ± 2 °.
Embodiment 2
Octamethylcyclotetrasiloxane is put into to gasifying pot, then ox-hide Buffed leather frosting is upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 30Pa, the temperature of gasifying pot risen to 30 ℃ simultaneously, make the octamethylcyclotetrasiloxane vaporization, and with 8 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.5W/cm
2under, continuous discharge reaction 10min, close the plasma discharge electrode, is filled with air removal ox-hide Buffed leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali Buffed leather of the present embodiment gained is 155 ° ± 2 °, and roll angle is 8 ° ± 2 °.
Embodiment 3
Decamethylcyclopentaandoxane is put into to gasifying pot, then the positive suede leather of pigskin matte is upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 25 ℃ simultaneously, make the decamethylcyclopentaandoxane vaporization, and with 1 * 10
-4ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1W/cm
2under, continuous discharge reaction 18min, close the plasma discharge electrode, is filled with air and removes the positive suede of pigskin and remove from office surperficial unreacted monomer and get final product in plasm reaction cavity.
The static contact angle of the positive suede leather of the anti-carpincho of the present embodiment gained is 145 ° ± 3 °, and roll angle is 15 ° ± 2 °.
Embodiment 4
Hexamethyldisiloxane is put into to gasifying pot, then the ox-hide obverse leather is faced up and puts into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 28Pa, the temperature of gasifying pot risen to 35 ℃ simultaneously, make the hexamethyldisiloxane vaporization, and with 3 * 10
-4ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1.5W/cm
2under, continuous discharge reaction 5min, close the plasma discharge electrode, is filled with air removal ox-hide obverse leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali obverse leather of the present embodiment gained is 140 ° ± 3 °, and roll angle is 20 ° ± 2 °.
Embodiment 5
Ten diformazan basic ring six siloxanes are put into to gasifying pot, then the sheepskin obverse leather is faced up and puts into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 30 ℃ simultaneously, make ten diformazan basic ring six siloxanes vaporizations, and with 8 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1.5W/cm
2under, continuous discharge reaction 1min, close the plasma discharge electrode, is filled with air removal sheepskin obverse leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the present embodiment gained sheepskin obverse leather is 136 ° ± 2 °, and roll angle is 22 ° ± 2 °.
Embodiment 6
Vinyltriethoxysilane is put into to gasifying pot, then the sheepskin obverse leather is faced up and puts into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 32Pa, the temperature of gasifying pot risen to 28 ℃ simultaneously, make the vinyltriethoxysilane vaporization, and with 6 * 10
-4ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1W/cm
2under, continuous discharge reaction 3min, close the plasma discharge electrode, is filled with air removal sheepskin obverse leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the present embodiment gained waterproof sheepskin obverse leather is 139 ° ± 2 °, and roll angle is 15 ° ± 2 °.
Embodiment 7
Vinylformic acid is put into to gasifying pot, then ox-hide plane leather is faced up and puts into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 40Pa, the temperature of gasifying pot risen to 27 ℃ simultaneously, make the vinylformic acid vaporization, and with 8 * 10
-4ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.2W/cm
2under, continuous discharge reaction 5min, close the plasma discharge electrode, is filled with air and removes the ox-hide plane and remove from office surperficial unreacted monomer and get final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali of the present embodiment gained plane leather is 140 ° ± 3 °, and roll angle is 20 ° ± 2 °.
Embodiment 8
Methyl acrylate is put into to gasifying pot, then ox-hide Buffed leather frosting is upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 35Pa, the temperature of gasifying pot risen to 30 ℃ simultaneously, make the methyl acrylate vaporization, and with 9 * 10
-4ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.5W/cm
2under, continuous discharge reaction 20min, close the plasma discharge electrode, is filled with air removal ox-hide Buffed leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali Buffed leather of the present embodiment gained is 155 ° ± 3 °, and roll angle is 7 ° ± 1 °.
Embodiment 9
Vinylformic acid ten trifluoro monooctyl esters are put into to gasifying pot, then both fur and leather is removed from office to the reaction chamber that flesh noodles is upwards put into the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 45 ℃ simultaneously, make vinylformic acid ten trifluoro monooctyl ester vaporizations, and with 5 * 10
-4ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.3W/cm
2under, continuous discharge reaction 25min, close the plasma discharge electrode, is filled with air and removes both fur and leather and remove from office surperficial unreacted monomer and get final product in plasm reaction cavity.
The static contact angle of the present embodiment gained waterproof both fur and leather leather is 150 ° ± 3 °, and roll angle is 12 ° ± 3 °.
Methacrylic acid ten trifluoro monooctyl esters are put into to gasifying pot, then the ox-hide obverse leather is faced up and puts into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 30Pa, the temperature of gasifying pot risen to 30 ℃ simultaneously, make methacrylic acid ten trifluoro monooctyl ester vaporizations, and with 7 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1.5W/cm
2under, continuous discharge reaction 8min, close the plasma discharge electrode, is filled with air removal ox-hide obverse leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali obverse leather of the present embodiment gained is 140 ° ± 2 °, and roll angle is 21 ° ± 2 °.
Embodiment 11
Vinylformic acid hexafluoro butyl ester is put into to gasifying pot, then both fur and leather is removed from office to the reaction chamber that flesh noodles is upwards put into the plasma apparatus be communicated with gasifying pot; Be evacuated to 38Pa, the temperature of gasifying pot risen to 30 ℃ simultaneously, make the vaporization of vinylformic acid hexafluoro butyl ester, and with 9 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.9W/cm
2under, continuous discharge reaction 12min, close the plasma discharge electrode, is filled with air and removes both fur and leather and remove from office surperficial unreacted monomer and get final product in plasm reaction cavity.
The static contact angle of the present embodiment gained waterproof both fur and leather leather is 152 ° ± 3 °, and roll angle is 12 ° ± 3 °.
Embodiment 12
Dodecafluoroheptyl methacrylate is put into to gasifying pot, then ox-hide Buffed leather frosting is upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 40 ℃ simultaneously, make the dodecafluoroheptyl methacrylate vaporization, and with 8 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1W/cm
2under, continuous discharge reaction 1min, close the plasma discharge electrode, is filled with air removal ox-hide Buffed leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali Buffed leather of the present embodiment gained is 149 ° ± 3 °, and roll angle is 14 ° ± 2 °.
Embodiment 13
Butyl acrylate is put into to gasifying pot, then both fur and leather is removed from office to the reaction chamber that flesh noodles is upwards put into the plasma apparatus be communicated with gasifying pot; Be evacuated to 30Pa, the temperature of gasifying pot risen to 48 ℃ simultaneously, make the butyl acrylate vaporization, and with 7 * 10
-4ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1W/cm
2under, continuous discharge reaction 25min, close the plasma discharge electrode, is filled with air and removes both fur and leather and remove from office surperficial unreacted monomer and get final product in plasm reaction cavity.
The static contact angle of the present embodiment gained waterproof both fur and leather leather is 152 ° ± 3 °, and roll angle is 11 ° ± 2 °.
Embodiment 14
Ten difluoro heptyl propyl trimethoxy silicanes are put into to gasifying pot, then ox-hide Buffed leather frosting is upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 45Pa, the temperature of gasifying pot risen to 50 ℃ simultaneously, make ten difluoro heptyl propyl trimethoxy silicane vaporizations, and with 9 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1W/cm
2under, continuous discharge reaction 10min, close the plasma discharge electrode, is filled with air removal ox-hide Buffed leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali Buffed leather of the present embodiment gained is 150 ° ± 2 °, and roll angle is 10 ° ± 1 °.
Embodiment 15
Ten difluoro heptyl propyl group methyl dimethoxysilanes are put into to gasifying pot, then ox-hide Buffed leather frosting is upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 40 ℃ simultaneously, make ten difluoro heptyl propyl group methyl dimethoxysilane vaporizations, and with 7 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.3W/cm
2under, continuous discharge reaction 15min, close the plasma discharge electrode, is filled with air removal ox-hide Buffed leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali Buffed leather of the present embodiment gained is 150 ° ± 2 °, and roll angle is 10 ° ± 1 °.
Embodiment 16
Ten trifluoro octyl group Trimethoxy silanes are put into to gasifying pot, then both fur and leather is removed from office to the reaction chamber that flesh noodles is upwards put into the plasma apparatus be communicated with gasifying pot; Be evacuated to 30Pa, the temperature of gasifying pot risen to 40 ℃ simultaneously, make ten trifluoro octyl group Trimethoxy silane vaporizations, and with 7 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.15W/cm
2under, continuous discharge reaction 1min, close the plasma discharge electrode, is filled with air and removes both fur and leather and remove from office surperficial unreacted monomer and get final product in plasm reaction cavity.
The static contact angle of the present embodiment gained waterproof both fur and leather leather is 151 ° ± 2 °, and roll angle is 15 ° ± 1 °.
Embodiment 17
4-methyl-(perfluoro hexyl ethyl) propyl trimethoxy silicane is put into to gasifying pot, then ox-hide Buffed leather frosting upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 43 ℃ simultaneously, make 4-methyl-(perfluoro hexyl ethyl) propyl trimethoxy silicane vaporization, and with 6 * 10
-4ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.15W/cm
2under, continuous discharge reaction 9min, close the plasma discharge electrode, is filled with air removal ox-hide Buffed leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali Buffed leather of the present embodiment gained is 153 ° ± 2 °, and roll angle is 13 ° ± 2 °.
Embodiment 18
Octamethylcyclotetrasiloxane and vinylformic acid ten trifluoro monooctyl esters mixing are put into to gasifying pot, then both fur and leather is removed from office to the reaction chamber that flesh noodles is upwards put into the plasma apparatus be communicated with gasifying pot; Be evacuated to 30Pa, the temperature of gasifying pot risen to 40 ℃ simultaneously, make octamethylcyclotetrasiloxane and vinylformic acid ten trifluoro monooctyl ester mixture vaporizations, and with 7 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1W/cm
2under, continuous discharge reaction 5min, close the plasma discharge electrode, is filled with air and removes both fur and leather and remove from office surperficial unreacted monomer and get final product in plasm reaction cavity.
The static contact angle of the present embodiment gained waterproof both fur and leather leather is 153 ° ± 2 °, and roll angle is 10 ° ± 1 °.
Embodiment 19
Decamethylcyclopentaandoxane and the mixing of ten trifluoro octyl group Trimethoxy silanes are put into to gasifying pot, then the positive suede leather of pigskin matte is upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 42Pa, the temperature of gasifying pot risen to 40 ℃ simultaneously, make decamethylcyclopentaandoxane and the vaporization of ten trifluoro octyl group Trimethoxy silane mixtures, and with 3 * 10
-4ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 1.5W/cm
2under, continuous discharge reaction 20min, close the plasma discharge electrode, is filled with air and removes the positive suede of pigskin and remove from office surperficial unreacted monomer and get final product in plasm reaction cavity.
The static contact angle of the positive suede leather of the anti-carpincho of the present embodiment gained is 148 ° ± 2 °, and roll angle is 15 ° ± 1 °.
Hexamethyl cyclotrisiloxane and the mixing of vinylformic acid hexafluoro butyl ester are put into to gasifying pot, then ox-hide Buffed leather frosting is upwards put into to the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 30Pa, the temperature of gasifying pot risen to 30 ℃ simultaneously, make hexamethyl cyclotrisiloxane and the vaporization of vinylformic acid hexafluoro butyl ester mixture, and with 9 * 10
-5ml/mincm
2flow enter in plasma reaction chamber, at exoelectrical reaction power, be then 0.5W/cm
2under, continuous discharge reaction 15min closes the plasma discharge electrode, is filled with air removal ox-hide Buffed leather surface unreacted monomer and gets final product in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali Buffed leather of the present embodiment gained is 151 ° ± 2 °, and roll angle is 9 ° ± 1 °.
Claims (10)
1. prepare the method for Waterproof leather by the low temperature plasma polymerization deposition, processing step and the condition of the method are as follows:
1) at least one in type siloxane or acrylic acid or the like or esters of acrylic acid or acrylate containing fluorine or silicon fluoride class monomer put into to gasifying pot, then by the pending reaction chamber of putting into facing up plasma reaction device of leather, then gasifying pot is communicated with plasma reaction device;
2) vacuum tightness vacuumized in the reaction chamber that makes gasifying pot and plasma reaction device reaches 25-45Pa, the temperature of gasifying pot is risen to 25-50 ℃ simultaneously, after making the monomer vapor in gasifying pot, with 7 * 10
-5-9 * 10
-4ml/mincm
2flow enter in the reaction cavity of plasma reaction device, at exoelectrical reaction power, be 0.15-1.5W/cm
2under, reaction 1-25min, can obtain the leather that aggregation deposition has water-proof surface.
2. the method for preparing the water-repellancy leather by low temperature plasma polymerization deposition according to claim 1, the siloxane compound described in the method is hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes, hexamethyldisiloxane and vinyltriethoxysilane; Acrylic monomer is vinylformic acid and methacrylic acid; Acrylic ester monomer is methyl acrylate, butyl acrylate and methyl methacrylate; The acrylate containing fluorine monomer is vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, vinylformic acid ten trifluoro monooctyl esters and methacrylic acid ten trifluoro monooctyl esters; Silicon fluoride class monomer is ten difluoro heptyl propyl trimethoxy silicanes, ten difluoro heptyl propyl group methyl dimethoxysilanes, ten trifluoro octyl group Trimethoxy silanes and 4-methyl-(perfluoro hexyl ethyl) propyl trimethoxy silicane.
3. the method for preparing the water-repellancy leather by low temperature plasma polymerization deposition according to claim 1, the vacuum tightness described in the method is 25-35Pa; Described temperature is 25-45 ℃.
4. the method for preparing the water-repellancy leather by low temperature plasma polymerization deposition according to claim 1, the flow described in the method is 7 * 10
-5-8 * 10
-4ml/mincm
2.
5. according to claim 1 or 2 or the 3 or 4 described methods that prepare the water-repellancy leather by the low temperature plasma polymerization deposition, the power described in the method is 0.15-1.0W/cm
2.
6. according to claim 1 or 2 or the 3 or 4 described methods that prepare the water-repellancy leather by the low temperature plasma polymerization deposition, the reaction times described in the method is 5-20min.
7. the method for preparing the water-repellancy leather by low temperature plasma polymerization deposition according to claim 5, the reaction times described in the method is 5-20min.
8. according to claim 1 or 2 or the 3 or 4 described methods for preparing the water-repellancy leather by low temperature plasma polymerization deposition, the leather described in the method is without any in obverse leather, velour, Buffed leather or the both fur and leather leather of covering with paint.
9. the method that prepare the water-repellancy leather by low temperature plasma polymerization deposition according to claim 7, the leather described in the method is without any in obverse leather, velour, Buffed leather or the both fur and leather leather of covering with paint.
10. the Waterproof leather prepared by low temperature plasma polymerization deposition claimed in claim 1, the thickness of the waterproof membrane of this leather surface aggregation deposition is micron order or following, its static contact angle is 136-155 °, roll angle is 7-22 °, and observe the visible clear collegen filament that interweave from scanning electronic microscope.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04370269A (en) * | 1991-06-18 | 1992-12-22 | Unitika Ltd | Processing of animal hair cloth |
| WO2003060166A1 (en) * | 2002-01-15 | 2003-07-24 | Conciaricerca Italia S.R.L. | Method for the processing of leather |
| KR20040068051A (en) * | 2004-06-21 | 2004-07-30 | 이규용 | The Plasma equipment for reforming full grain leather processed by plasma |
| CN1925764A (en) * | 2003-12-30 | 2007-03-07 | 健乐士有限公司 | Breathable waterproof sole for shoes |
| JP2012021201A (en) * | 2010-07-16 | 2012-02-02 | Dainippon Printing Co Ltd | Method for producing water-repellent coating film and releasing paper |
| CN102797166A (en) * | 2012-09-05 | 2012-11-28 | 上海华峰超纤材料股份有限公司 | Water-repellent oil-repellent superfine fiber synthetic leather and preparation method thereof |
| RU2475544C1 (en) * | 2011-06-27 | 2013-02-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Казанский национальный исследовательский технологический университет" | Method of hydrophobisation of leather and fur materials |
-
2013
- 2013-09-16 CN CN201310421788.9A patent/CN103468835B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04370269A (en) * | 1991-06-18 | 1992-12-22 | Unitika Ltd | Processing of animal hair cloth |
| WO2003060166A1 (en) * | 2002-01-15 | 2003-07-24 | Conciaricerca Italia S.R.L. | Method for the processing of leather |
| CN1925764A (en) * | 2003-12-30 | 2007-03-07 | 健乐士有限公司 | Breathable waterproof sole for shoes |
| KR20040068051A (en) * | 2004-06-21 | 2004-07-30 | 이규용 | The Plasma equipment for reforming full grain leather processed by plasma |
| JP2012021201A (en) * | 2010-07-16 | 2012-02-02 | Dainippon Printing Co Ltd | Method for producing water-repellent coating film and releasing paper |
| RU2475544C1 (en) * | 2011-06-27 | 2013-02-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Казанский национальный исследовательский технологический университет" | Method of hydrophobisation of leather and fur materials |
| CN102797166A (en) * | 2012-09-05 | 2012-11-28 | 上海华峰超纤材料股份有限公司 | Water-repellent oil-repellent superfine fiber synthetic leather and preparation method thereof |
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| CN104947074A (en) * | 2014-11-19 | 2015-09-30 | 叶羽敏 | Textile surface high-polymer coating method based on chemical vapor deposition |
| US11845105B2 (en) | 2017-08-23 | 2023-12-19 | Molecular Plasma Group Sa | Soft plasma polymerization process for a mechanically durable superhydrophobic nanostructured coating |
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| JP7458976B2 (en) | 2017-08-23 | 2024-04-01 | モレキュラー・プラズマ・グループ・ソシエテ・アノニム | Soft plasma polymerization method for mechanically durable superhydrophobic nanostructured coatings |
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