CN103468835B - 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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- CN103468835B CN103468835B CN201310421788.9A CN201310421788A CN103468835B CN 103468835 B CN103468835 B CN 103468835B CN 201310421788 A CN201310421788 A CN 201310421788A CN 103468835 B CN103468835 B CN 103468835B
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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 Waterproof leather and the method thereof of the preparation of a kind of low temperature plasma polymerization deposition.
Background technology
The WATER REPELLENT of common leather surface has generally been come by Coating technology, and its waterproof finish agent used is mainly with siloxane type polymers or acrylate containing fluorine polymkeric substance composition.As the people such as Gao Futang (Gao Futang etc. the Synthesis and application of hydroxyl silicon oil modified acrylic resin hide finishes. leather science and engineering .2006,16 (1): 63-66) have studied the hide finishes with hydroxyl silicon oil modified acrylic resin synthesis, this research shows, introduces silicone oil and the water tolerance of leather can be made well to be improved; The people such as An Qiufeng (film-forming properties, the XPS of fluoro acrylic ester copolymer emulsion FSLDH characterize and hydrophobic performance. fine chemistry industry .2010,27 (5): 486-490) then have studied the film-forming properties of fluoro acrylic ester copolymer emulsion and the hydrophobicity of process cotton fabric, result shows, vinylformic acid fluorine-containing latex can give cotton fabric good hydrophobicity.In addition, organic fluorine monomer also can be used to synthesis multifunctional leather finishing agent, i.e. grafting organic fluorine in the molecule, finishing agent is made to have features, as waterproof, the performance such as grease proofing, antifouling and fire-retardant (structures and characteristics of organofluorine compound and the application in 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 of these finishing agents is complicated on the one hand, cause cost high, on the other hand, the pore of the collegen filament of leather surface and leather surface can hide by coating that these finishing agents are coated in leather surface completely, greatly affect the sanitation performance (mainly vapor pervious performance) of natural leather, thus 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 leather glues water, 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 due to the Coating technology that very difficult employing is traditional, its water-repellancy problem is difficult to solve.Therefore, leather is that the WATER REPELLENT of non-covering with paint leather surface is the important technology difficult problem that leather industry faces especially.If at least the part surface of leather has before this from NO hydrophobicity level, then bring big advantages by the application of these leathers.
Low-temperature plasma is as a kind of quick, easy, process for treating surface that can keep 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 species by plasma discharge, this energy exceedes the bond energy of chemical bonds typical, cause chemical bond rupture) produce free radical, this free radical can cause substrate surface generation chemical reaction, thus the process completed substrate surface, and give substrate surface property.And the performance of substrate surface depends primarily on the composition of plasma atmosphere.Mainly contain two classes at present as 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 Hexamethyldisiloxane, tetraethoxy etc.), a small amount of organism is made to 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 being vaporized 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 that organism improves.
Summary of the invention
The object of the invention is easily be soaked in water for leather surface and produce washmarking, affect the defect of its use value, life-span and surface aesthetic, first provide a kind of low temperature plasma polymerization to deposit the method preparing Waterproof leather.
Another object of the present invention is to provide a kind of Waterproof leather prepared by aforesaid method.
Low temperature plasma polymerization deposition provided by the invention prepares the method for Waterproof leather, and 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 is put into gasifying pot, then by the pending reaction chamber towards above putting into plasma reaction device of leather, then gasifying pot is communicated with plasma reaction device;
2) vacuum tightness vacuumized in the reaction chamber making gasifying pot and plasma reaction device reaches 25-45Pa, the temperature of gasifying pot is risen to 25-50 DEG C, after making the monomer vapor in gasifying pot, with 7 × 10 simultaneously
-5-9 × 10
-4ml/mincm
2flow enter in the reaction cavity of plasma reaction device, be 0.15-1.5W/cm at exoelectrical reaction power
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; Acrylate containing fluorine monomer preferred vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, vinylformic acid ten trifluoro monooctyl ester and methacrylic acid ten trifluoro monooctyl ester, more preferably vinylformic acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate and vinylformic acid ten trifluoro monooctyl ester; Silicon fluoride class monomer is ten difluoro heptyl propyl trimethoxy silicanes, ten difluoro heptyl hydroxypropyl methyl dimethoxysilane, 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 DEG C of described temperature, more preferably 30-45 DEG C; 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 one in the obverse leather covered with paint, lacquer, colour wash, etc., velour, Buffed leather or both fur and leather leather.
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 from scanning electronic microscope, the collegen filament of visible clear intertexture.
The present invention compared with prior art, has the following advantages:
1, because the present invention is that using plasma aggregation deposition adheres to one deck micron order or following waterproof membrane to make leather surface, thus not only rete is thin, and the polymkeric substance deposited would not close the space between leather surface collegen filament as covering with paint, lacquer, colour wash, etc., the kishke feel in epidermis face can be kept on the one hand, also can keep the sanitation performance of natural leather on the other hand.
2, the waterproof membrane due to using plasma aggregation deposition acquisition of the present invention is not only thin, and even compact, thus water static contact angle thereon reaches as high as more than 150 °, and roll angle is very low, minimumly can, lower than 10 °, leather surface be made to 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, plasma discharge aggregation deposition, thus not only treating processes flow of monomer is low, materials consumption is few, and the treatment time is short, the feature that efficiency is high, energy-conservation again.
4, due to the present invention adopt be plasma polymerization deposition mode to prepare Waterproof leather, compared with thus covering with paint, lacquer, colour wash, etc. with liquid emulsion, do not need subsequent disposal, both decreased work program and tooling cost, efficiency is higher again.
5, due to the present invention's employing is that plasma polymerization deposition mode is to prepare Waterproof leather, damage can not be caused to leather itself, thus can solve the waterproof problem of the non-covering with paint leathers such as Buffed leather, velour, both fur and leather leather, fill up the blank of the WATER REPELLENT of non-covering with paint leather.
Accompanying drawing explanation
Fig. 1 is the change curve of static contact angle with duration of contact not covering with paint, lacquer, colour wash, etc. ox-hide obverse leather surface without Cement Composite Treated by Plasma.As seen from the figure, along with duration of contact extends, contact angle is reducing gradually, and this illustrates that water droplet slowly soaks leather surface;
Fig. 2 is the change curve of static contact angle (about 141 °) with duration of contact on the ox-hide Buffed leather surface that embodiment 1 processes.As seen from the figure, along with duration of contact extends, contact angle remains unchanged, and this illustrates that water droplet can not soak leather surface;
Fig. 3 is the change curve of static contact angle (about 155 °) with duration of contact on the ox-hide Buffed leather surface that embodiment 2 processes.As seen from the figure, along with duration of contact extends, contact angle remains unchanged, and this illustrates that water droplet can not soak leather surface;
Fig. 4 is the change curve of static contact angle (about 136 °) with duration of contact that embodiment 5 processes sheepskin obverse leather surface.As seen from the figure, along with duration of contact extends, contact angle remains unchanged, and this illustrates that water droplet can not soak leather surface;
Fig. 5 is the change curve of static contact angle (about 150 °) with duration of contact that embodiment 15 processes pig suede upper leather surface.As seen from the figure, along with duration of contact extends, contact angle remains unchanged, and this illustrates that 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 both fur and leather leather; And (b) and (c) are respectively water droplet and process rolling situation on both fur and leather leather in the embodiment 16 tilted and embodiment 19, from this schematic diagram (b) and (c), when Inclined Angle is smaller, water droplet can roll on both fur and leather leather, and being rolled off leather surface, this illustrates that the both fur and leather leather after embodiment 16 and embodiment 19 process has very strong hydrophobicity;
Fig. 7 is the atomic force microscope shape appearance figure on 10 μm × 10 μm, the ox-hide obverse leather surface without Cement Composite Treated by Plasma.As seen from the figure, leather surface is that collegen filament are interwoven;
Fig. 8 is the atomic force microscope shape appearance figure on 10 μm × 10 μm, the ox-hide obverse leather surface that embodiment 10 processes.As seen from the figure, the aggregated particles thing of plasma polymerization deposition grows along the direction of fiber, interfibrous space can't be covered;
Fig. 9 is the scanning electronic microscope shape appearance figure of the ox-hide obverse leather without Cement Composite Treated by Plasma.The pore on ox-hide obverse leather surface significantly can be observed from figure;
Figure 10 is the scanning electronic microscope shape appearance figure of the ox-hide obverse leather that embodiment 10 processes.Significantly can observe the pore on the ox-hide obverse leather surface after plasma treatment from figure, significantly not distinguish compared with the ox-hide obverse leather without plasma treatment;
Figure 11 is the conventional scanning electronic microscope shape appearance figure covering with paint, lacquer, colour wash, etc. the ox-hide obverse leather of process.The pore significantly can observing ox-hide obverse leather surface from figure is covered completely by coatings;
Figure 12 is the scanning electronic microscope shape appearance figure of the ox-hide Buffed leather frosting without Cement Composite Treated by Plasma.The fiber of ox-hide Buffed leather frosting significantly can be observed from figure;
Figure 13 is the scanning electronic microscope shape appearance figure of the ox-hide Buffed leather frosting that embodiment 12 processes.The fiber significantly can observing the ox-hide Buffed leather frosting after plasma treatment from figure is still high-visible, does not significantly distinguish with the ox-hide Buffed leather frosting without plasma treatment;
Figure 14 is along with duration of contact extends, black water droplet is rolling picture on ox-hide Buffed leather frosting, wherein (a) is for water droplet is without the rolling situation picture 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 creates black washmarking on ox-hide Buffed leather frosting, and (b) is the rolling situation picture of water droplet after embodiment 20 processes on ox-hide Buffed leather frosting, 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; explanation is needed at this; embodiment is only further illustrate of the present invention; the scope of application of the present invention is not by 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 the claims in detail.
What deserves to be explained is, the static contact angle of the Waterproof leather of following embodiment process gained and roll angle are all record with the OCA20/6 type contact angle instrument that German dataphysics company produces.
Embodiment 1
Hexamethyl cyclotrisiloxane is put into gasifying pot, then ox-hide Buffed leather frosting is upwards put 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 DEG C simultaneously, hexamethyl cyclotrisiloxane is vaporized, and with 7 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 0.15W/cm at exoelectrical reaction power
2under, continuous discharge reaction 15min, closes plasma discharge electrode, is filled with air and removes ox-hide Buffed leather surface unreacted monomer 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 gasifying pot, then ox-hide Buffed leather frosting is upwards put 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 DEG C simultaneously, octamethylcyclotetrasiloxane is vaporized, and with 8 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 0.5W/cm at exoelectrical reaction power
2under, continuous discharge reaction 10min, closes plasma discharge electrode, is filled with air and removes ox-hide Buffed leather surface unreacted monomer 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 gasifying pot, then positive for pigskin suede leather matte is upwards put into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 25 DEG C simultaneously, decamethylcyclopentaandoxane is vaporized, and with 1 × 10
-4ml/mincm
2flow enter in plasma reaction chamber, be then 1W/cm at exoelectrical reaction power
2under, continuous discharge reaction 18min, closes plasma discharge electrode, is filled with the positive suede of air removal pigskin and removes from office surperficial unreacted monomer 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 gasifying pot, then ox-hide obverse leather is faced up and put 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 DEG C simultaneously, hexamethyldisiloxane is vaporized, and with 3 × 10
-4ml/mincm
2flow enter in plasma reaction chamber, be then 1.5W/cm at exoelectrical reaction power
2under, continuous discharge reaction 5min, closes plasma discharge electrode, is filled with air and removes ox-hide obverse leather surface unreacted monomer 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 gasifying pot, then sheepskin obverse leather is faced up and put 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 DEG C simultaneously, make ten diformazan basic ring six siloxanes vaporizations, and with 8 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 1.5W/cm at exoelectrical reaction power
2under, continuous discharge reaction 1min, closes plasma discharge electrode, is filled with air and removes sheepskin obverse leather surface unreacted monomer 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 gasifying pot, then sheepskin obverse leather is faced up and put 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 DEG C simultaneously, vinyltriethoxysilane is vaporized, and with 6 × 10
-4ml/mincm
2flow enter in plasma reaction chamber, be then 1W/cm at exoelectrical reaction power
2under, continuous discharge reaction 3min, closes plasma discharge electrode, is filled with air and removes sheepskin obverse leather surface unreacted monomer 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 gasifying pot, then ox-hide plane leather is faced up and put 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 DEG C simultaneously, vinylformic acid is vaporized, and with 8 × 10
-4ml/mincm
2flow enter in plasma reaction chamber, be then 0.2W/cm at exoelectrical reaction power
2under, continuous discharge reaction 5min, closes plasma discharge electrode, is filled with air removal ox-hide plane and removes from office surperficial unreacted monomer in plasm reaction cavity.
The static contact angle of the anti-Corii Bubali plane leather of the present embodiment gained is 140 ° ± 3 °, and roll angle is 20 ° ± 2 °.
Embodiment 8
Methyl acrylate is put into gasifying pot, then ox-hide Buffed leather frosting is upwards put into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 35Pa, the temperature of gasifying pot risen to 30 DEG C simultaneously, methyl acrylate is vaporized, and with 9 × 10
-4ml/mincm
2flow enter in plasma reaction chamber, be then 0.5W/cm at exoelectrical reaction power
2under, continuous discharge reaction 20min, closes plasma discharge electrode, is filled with air and removes ox-hide Buffed leather surface unreacted monomer 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 ester is put into gasifying pot, then both fur and leather is removed from office the reaction chamber that the plasma apparatus be communicated with gasifying pot upwards put into by flesh noodles; Be evacuated to 25Pa, the temperature of gasifying pot risen to 45 DEG C simultaneously, vinylformic acid ten trifluoro monooctyl ester is vaporized, and with 5 × 10
-4ml/mincm
2flow enter in plasma reaction chamber, be then 0.3W/cm at exoelectrical reaction power
2under, continuous discharge reaction 25min, closes plasma discharge electrode, is filled with air removal both fur and leather and removes from office surperficial unreacted monomer 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 °.
Embodiment 10
Methacrylic acid ten trifluoro monooctyl ester is put into gasifying pot, then ox-hide obverse leather is faced up and put 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 DEG C simultaneously, methacrylic acid ten trifluoro monooctyl ester is vaporized, and with 7 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 1.5W/cm at exoelectrical reaction power
2under, continuous discharge reaction 8min, closes plasma discharge electrode, is filled with air and removes ox-hide obverse leather surface unreacted monomer 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 gasifying pot, then both fur and leather is removed from office the reaction chamber that the plasma apparatus be communicated with gasifying pot upwards put into by flesh noodles; Be evacuated to 38Pa, the temperature of gasifying pot risen to 30 DEG C simultaneously, vinylformic acid hexafluoro butyl ester is vaporized, and with 9 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 0.9W/cm at exoelectrical reaction power
2under, continuous discharge reaction 12min, closes plasma discharge electrode, is filled with air removal both fur and leather and removes from office surperficial unreacted monomer 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 gasifying pot, then ox-hide Buffed leather frosting is upwards put into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 40 DEG C simultaneously, dodecafluoroheptyl methacrylate is vaporized, and with 8 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 1W/cm at exoelectrical reaction power
2under, continuous discharge reaction 1min, closes plasma discharge electrode, is filled with air and removes ox-hide Buffed leather surface unreacted monomer 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 gasifying pot, then both fur and leather is removed from office the reaction chamber that the plasma apparatus be communicated with gasifying pot upwards put into by flesh noodles; Be evacuated to 30Pa, the temperature of gasifying pot risen to 48 DEG C simultaneously, butyl acrylate is vaporized, and with 7 × 10
-4ml/mincm
2flow enter in plasma reaction chamber, be then 1W/cm at exoelectrical reaction power
2under, continuous discharge reaction 25min, closes plasma discharge electrode, is filled with air removal both fur and leather and removes from office surperficial unreacted monomer 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 gasifying pot, then ox-hide Buffed leather frosting is upwards put into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 45Pa, the temperature of gasifying pot risen to 50 DEG C simultaneously, make ten difluoro heptyl propyl trimethoxy silicane vaporizations, and with 9 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 1W/cm at exoelectrical reaction power
2under, continuous discharge reaction 10min, closes plasma discharge electrode, is filled with air and removes ox-hide Buffed leather surface unreacted monomer 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 hydroxypropyl methyl dimethoxysilane are put into gasifying pot, then ox-hide Buffed leather frosting is upwards put into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 40 DEG C simultaneously, make ten difluoro heptyl hydroxypropyl methyl dimethoxysilane vaporizations, and with 7 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 0.3W/cm at exoelectrical reaction power
2under, continuous discharge reaction 15min, closes plasma discharge electrode, is filled with air and removes ox-hide Buffed leather surface unreacted monomer 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 gasifying pot, then both fur and leather is removed from office the reaction chamber that the plasma apparatus be communicated with gasifying pot upwards put into by flesh noodles; Be evacuated to 30Pa, the temperature of gasifying pot risen to 40 DEG C simultaneously, make ten trifluoro octyl group Trimethoxy silane vaporizations, and with 7 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 0.15W/cm at exoelectrical reaction power
2under, continuous discharge reaction 1min, closes plasma discharge electrode, is filled with air removal both fur and leather and removes from office surperficial unreacted monomer 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 gasifying pot, then ox-hide Buffed leather frosting upwards put into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 25Pa, the temperature of gasifying pot risen to 43 DEG C simultaneously, make 4-methyl-(perfluoro hexyl ethyl) propyl trimethoxy silicane vaporization, and with 6 × 10
-4ml/mincm
2flow enter in plasma reaction chamber, be then 0.15W/cm at exoelectrical reaction power
2under, continuous discharge reaction 9min, closes plasma discharge electrode, is filled with air and removes ox-hide Buffed leather surface unreacted monomer 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 the mixing of vinylformic acid ten trifluoro monooctyl ester are put into gasifying pot, then both fur and leather is removed from office the reaction chamber that the plasma apparatus be communicated with gasifying pot upwards put into by flesh noodles; Be evacuated to 30Pa, the temperature of gasifying pot risen to 40 DEG C simultaneously, make octamethylcyclotetrasiloxane and the vaporization of vinylformic acid ten trifluoro monooctyl ester mixture, and with 7 × 10
-5ml/mincm
2flow enter in plasma reaction chamber, be then 1W/cm at exoelectrical reaction power
2under, continuous discharge reaction 5min, closes plasma discharge electrode, is filled with air removal both fur and leather and removes from office surperficial unreacted monomer 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 gasifying pot, then positive for pigskin suede leather matte is upwards put into the reaction chamber of the plasma apparatus be communicated with gasifying pot; Be evacuated to 42Pa, the temperature of gasifying pot risen to 40 DEG C 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, be then 1.5W/cm at exoelectrical reaction power
2under, continuous discharge reaction 20min, closes plasma discharge electrode, is filled with the positive suede of air removal pigskin and removes from office surperficial unreacted monomer 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 °.
Embodiment 20
Hexamethyl cyclotrisiloxane and the mixing of vinylformic acid hexafluoro butyl ester are put into gasifying pot, then ox-hide Buffed leather frosting is upwards put 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 DEG C 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, be then 0.5W/cm at exoelectrical reaction power
2under, continuous discharge reaction 15min closes plasma discharge electrode, is filled with air and removes ox-hide Buffed leather surface unreacted monomer 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 (8)
1. prepare a method for water-repellancy leather by 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 silicon fluoride class monomer is put into gasifying pot, then by the pending reaction chamber towards above putting into plasma reaction device of leather, then gasifying pot is communicated with plasma reaction device;
2) vacuum tightness vacuumized in the reaction chamber making gasifying pot and plasma reaction device reaches 25-45Pa, the temperature of gasifying pot is risen to 25-50 DEG C, after making the monomer vapor in gasifying pot, with 7 × 10 simultaneously
-5-9 × 10
-4ml/mincm
2flow enter in the reaction cavity of plasma reaction device, be 0.15-1.5W/cm at exoelectrical reaction power
2under, the reaction times is 1-25min, can obtain the leather that aggregation deposition has water-proof surface,
Wherein, type siloxane monomer is hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes, hexamethyldisiloxane or vinyltriethoxysilane; Acrylic monomer is acrylic or methacrylic acid; Acrylic ester monomer is methyl acrylate, butyl acrylate, methyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, vinylformic acid ten trifluoro monooctyl ester or methacrylic acid ten trifluoro monooctyl ester; Silicon fluoride class monomer is ten difluoro heptyl propyl trimethoxy silicanes, ten difluoro heptyl hydroxypropyl methyl dimethoxysilane, ten trifluoro octyl group Trimethoxy silanes or 4-methyl-(perfluor is base ethyl) propyl trimethoxy silicane; The thickness of the waterproof membrane of gained water-repellancy leather surface aggregation deposition is below micron order or micron order, water-repellancy leather surface static contact angle is 136-155 °, roll angle is 7-22 °, and observes from scanning electronic microscope, the collegen filament of visible clear intertexture.
2. low temperature plasma polymerization deposition according to claim 1 prepares the method for water-repellancy leather, and the vacuum tightness described in the method is 25-35Pa; Described temperature is 25-45 DEG C.
3. low temperature plasma polymerization deposition according to claim 1 prepares the method for water-repellancy leather, and the flow described in the method is 7 × 10
-5-8 × 10
-4ml/mincm
2.
4. the method preparing water-repellancy leather by low temperature plasma polymerization deposition according to claim 1 or 2 or 3, the power described in the method is 0.15-1.0W/cm
2.
5. the method preparing water-repellancy leather by low temperature plasma polymerization deposition according to claim 1 or 2 or 3, the reaction times described in the method is 5-20min.
6. low temperature plasma polymerization deposition according to claim 4 prepares the method for water-repellancy leather, and the reaction times described in the method is 5-20min.
7. the method preparing water-repellancy leather by low temperature plasma polymerization deposition according to claim 1 or 2 or 3, the leather described in the method is without any one in the obverse leather covered with paint, lacquer, colour wash, etc., velour, Buffed leather or both fur and leather leather.
8. low temperature plasma polymerization deposition according to claim 6 prepares the method for water-repellancy leather, and the leather described in the method is without any one in the obverse leather covered with paint, lacquer, colour wash, etc., velour, Buffed leather or both fur and leather leather.
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| RU2791710C2 (en) * | 2017-08-23 | 2023-03-13 | Молекулар Плазма Груп Са (Molecular Plasma Group Sa) | Method of plasma polymerization under low-stress conditions for mechanically stable superhydrophobic nanostructured coating |
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| JP2859980B2 (en) * | 1991-06-18 | 1999-02-24 | ユニチカ株式会社 | Processing method of animal hair fiber fabric |
| ATE474939T1 (en) * | 2002-01-15 | 2010-08-15 | Conciaricerca Italia S R L | METHOD FOR TREATING LEATHER |
| ITPD20030312A1 (en) * | 2003-12-30 | 2005-06-30 | Geox Spa | BREATHABLE AND WATER RESISTANT SOLE FOR FOOTWEAR |
| KR20040068051A (en) * | 2004-06-21 | 2004-07-30 | 이규용 | The Plasma equipment for reforming full grain leather processed by plasma |
| JP5573445B2 (en) * | 2010-07-16 | 2014-08-20 | 大日本印刷株式会社 | Method for producing water repellent coating |
| 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 |
| CN102797166B (en) * | 2012-09-05 | 2014-01-22 | 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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