CN103468835A - Waterproof leather prepared via polymerization deposition of low-temperature plasmas and preparation method of waterproof leather - Google Patents

Abstract

The waterproof leather prepared by low-temperature plasma polymerization deposition disclosed by the present invention and the method thereof are: siloxane or acrylic or acrylic ester or fluorine-containing acrylic ester or fluorosilane monomer in vacuum degree 25-45Pa, temperature After being vaporized at 25-50°C, it enters the plasma reaction equipment at a certain flow rate, and reacts for 1-25min at a discharge power of 0.15-1.5W/cm ² to make it polymerize and deposit on the leather, and the waterproof material deposited on the surface of the leather The thickness of the film is micron or below, its static contact angle is 136-155°, rolling angle is 7-22°, and clearly intertwined collagen fibers can be seen from scanning electron microscope observation. The method of the present invention has the advantages of simple treatment process, short time, high efficiency and low energy consumption, and the obtained waterproof film layer is thin, which can not only maintain the real leather feeling of the leather surface of nubuck leather, suede leather, fur leather dual-purpose leather, etc., but also maintain its natural Hygienic properties of leather.

Description

Waterproof leather prepared by low temperature plasma polymerization deposition and method thereof

technical field

The invention belongs to the technical field of functional leather and its preparation, and in particular relates to a waterproof leather prepared by low-temperature plasma polymerization deposition and a method thereof.

Background technique

The waterproof treatment of the surface of ordinary leather is generally completed through a finishing process, and the waterproof finishing agent used is mainly composed of silicone polymers or fluorine-containing acrylate polymers. For example, Gao Futang et al. (Gao Futang et al. Synthesis and Application of Hydroxyl Silicone Oil Modified Acrylic Resin Leather Finishing Agent. Leather Science and Engineering. 2006,16(1):63-66) studied the synthesis of acrylic resin modified with hydroxyl silicone oil The study shows that the introduction of silicone oil can improve the water resistance of leather; An Qiufeng et al. (Film-forming properties, XPS characterization and hydrophobic properties of fluoroacrylate copolymer emulsion FSLDH. Fine Chemical Industry. 2010,27(5):486-490) studied the film-forming properties of fluoroacrylate copolymer emulsion and the hydrophobicity of treated cotton fabrics. The results showed that acrylic fluorine-containing emulsions can endow cotton fabrics with good hydrophobicity. In addition, organic fluorine monomers can also be used to synthesize multifunctional leather finishing agents, that is, grafting organic fluorine in the molecule, so that the finishing agent has special functions, such as waterproof, oil-proof, anti-fouling and flame-retardant properties (organic fluorine compounds Structure and properties and its application in leather industry. China Leather. 2006,35(15):42-47). However, the above-mentioned waterproof finishing agents are all organically synthesized silicon-containing or fluorine-containing high molecular polymers. Although they can indeed significantly improve the water resistance of leather, on the one hand, the synthesis process of these finishing agents is complicated, resulting in high costs. On the other hand, the coating of these finishing agents on the leather surface will completely cover the collagen fibers on the leather surface and the pores on the leather surface, which will greatly affect the hygienic performance of natural leather (mainly water vapor permeability), thereby reducing the quality of the leather. Wearing comfort (Ding Haiyan et al. Application of organosilicon in leather chemical materials. Daily Chemical Industry, 2003, 33(5): 317-319; Cong Jianhua et al. Organic fluorine water and oil repellent multifunctional finishing agent DM Discussion on the application process of -3640C. Printing and Dyeing Auxiliaries, 2008,25(5):28-30).

In addition, after the leather sticks to water, it is very easy to produce water marks, which will not only affect the appearance of the leather, but also reduce its service life, especially for nubuck leather, suede leather, and wool leather dual-purpose leather. And because these leather products are difficult to adopt traditional finishing process to finish it, its waterproof problem is difficult to solve. Therefore, the waterproof treatment of leather, especially the surface of non-painted leather is an important technical problem faced by the leather industry. It would be of great benefit to the application of these leathers if at least part of the surface of the leathers had a level of hydrophobicity that had never been achieved before.

Low-temperature plasma is a fast, simple and surface treatment technology that can maintain the overall performance of materials. The treatment process is to excite the surface of the substrate or atmosphere substances through plasma discharge in a certain atmosphere (the energy generated by plasma high-energy particles bombarding the surface of the material Generally several to tens of electron volts, the energy exceeds the bond energy of common chemical bonds, leading to the breakage of chemical bonds) to generate free radicals, which can initiate chemical reactions on the surface of the substrate, thereby completing the treatment of the surface of the substrate and endowing the substrate with Special properties of the material surface. The properties of the substrate surface depend primarily on the composition of the plasma atmosphere. At present, there are mainly two types of plasma reaction atmospheres, one is common gases, namely air, H ₂ , O ₂ , N ₂ , CO ₂ , Ar, He, CF ₄ , etc., and the other is based on these gases as carrier Gas flows through liquid organic substances (such as hexamethyldisiloxane, orthosilicate, etc.), so that a small amount of organic substances and carrier gas flow form plasma gas (Claire Tendero et al. Atmospheric pressure plasmas: Areview. Spectrochimica Acta Part B, 2006 , 61:2–30). Obviously, these existing gases limit the application range of plasma. In addition, the content of organic matter vaporized by carrier gas is difficult to control, and the existence of carrier gas flow will also affect the surface properties of substrates improved by organic matter.

Contents of the invention

The purpose of the present invention is to aim at the defect that the leather surface is easily wetted by water and produce water marks, which affects its use value, lifespan and surface appearance. First, it provides a method for preparing waterproof leather by low-temperature plasma polymerization deposition.

Another object of the present invention is to provide a waterproof leather prepared by the above method.

The method for preparing waterproof leather by low-temperature plasma polymerization deposition provided by the invention, the process steps and conditions of the method are as follows:

1) Put at least one of siloxane or acrylic or acrylate or fluorine-containing acrylate or fluorosilane monomer into the vaporization tank, and then put the leather to be treated face up into the plasma reaction In the reaction chamber of the equipment, the vaporization tank is connected with the plasma reaction equipment;

2) Vacuumize the vacuum in the reaction chamber of the vaporization tank and the plasma reaction equipment to 25-45Pa, and at the same time raise the temperature of the vaporization tank to 25-50°C to vaporize the monomer in the vaporization tank, then use 7× The flow rate of 10 ^-5 -9×10 ^-4 ml/min·cm ² enters the reaction chamber of the plasma reaction equipment, under the discharge reaction power of 0.15-1.5W/cm ² , react for 1-25min, you can get Polymeric deposition for leather with a water repellent surface.

The siloxane compounds described in the above method are preferably hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, six Methyldisiloxane and vinyltriethoxysilane, more preferably hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and vinyltriethoxysilane; acrylic monomers are preferably acrylic acid and Methacrylic acid; acrylate monomers are preferably methyl acrylate, butyl acrylate and methyl methacrylate, more preferably butyl acrylate; fluorine-containing acrylate monomers are preferably hexafluorobutyl acrylate, hexafluorobutyl methacrylate ester, dodecafluoroheptyl methacrylate, tridecafluorooctyl acrylate and tridecafluorooctyl methacrylate, more preferably hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate and tridecafluorooctyl acrylate Fluorosilane monomer is preferably dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, tridecafluorooctyltrimethoxysilane and 4-methyl-( Perfluorohexylethyl)propyltrimethoxysilane, more preferably tridecafluorooctyltrimethoxysilane and 4-methyl-(perfluorohexylethyl)propyltrimethoxysilane.

The vacuum degree described in the above method is preferably 25-35Pa, more preferably 30-35Pa; the temperature is preferably 25-45°C, more preferably 30-45°C; the flow rate is preferably 7×10 ^-5 -8×10 ^-4 ml/min·cm ² , more preferably 8×10 ^-5 -6×10 ^-4 ml/min·cm ² ; said power is preferably 0.15-1.0W/cm ² , more preferably 0.3-1.0W/cm ² ; the preferred 5-20min of the reaction time, more preferably 5-15min.

The leather described in the above method is any one of uncoated front leather, suede leather, nubuck leather or dual-purpose leather of wool and leather.

In the waterproof leather prepared by the above method provided by the present invention, the thickness of the waterproof film deposited on the surface of the leather is micron or below, the static contact angle is 136-155°, the rolling angle is 7-22°, and the Observed under a microscope, clearly intertwined collagen fibers can be seen.

Compared with the prior art, the present invention has the following advantages:

1. Since the present invention adopts plasma polymerization deposition to make the leather surface adhere to a waterproof film of micron level or below, not only the film layer is thin, but also the deposited polymer will not close the collagen fibers on the leather surface like the coating. On the one hand, it can maintain the genuine leather feeling of the leather surface, and on the other hand, it can also maintain the hygienic performance of natural leather.

2. Since the waterproof film obtained by plasma polymerization deposition in the present invention is not only thin, but also uniform and dense, the static contact angle of water on it can reach as high as 150°, and the rolling angle is very low, the lowest can be lower than 10° , so that the leather surface obtains good hydrophobicity.

3. Due to the plasma polymerization deposition method adopted in the present invention, the liquid monomer can be vaporized at a low temperature under the cooperation of the vacuum degree, and the plasma discharge polymerization deposition, so not only the monomer flow rate is low in the processing process, the material consumption is small, but also the processing time Short, high efficiency, and energy-saving features.

4. Since the present invention adopts plasma polymerization deposition method to prepare waterproof leather, compared with liquid emulsion coating, no follow-up treatment is required, which not only reduces processing procedures and processing costs, but also has higher efficiency.

5. Since the present invention uses the plasma polymerization deposition method to prepare waterproof leather, it will not cause damage to the leather itself, so it can solve the waterproof problem of non-painted leather such as nubuck leather, suede leather, and wool leather dual-purpose leather. It fills the gap of water repellent treatment for non-painted leather.

Description of drawings

Figure 1 is a curve of the static contact angle of the uncoated cowhide front leather surface without plasma treatment as a function of contact time. It can be seen from the figure that as the contact time prolongs, the contact angle gradually decreases, which indicates that the water droplets have slowly soaked the leather surface;

Fig. 2 is the variation curve of the static contact angle (about 141°) of the surface of the cowhide nubuck leather treated in Example 1 with the contact time. It can be seen from the figure that as the contact time increases, the contact angle remains unchanged, which means that the water droplet will not wet the leather surface;

Fig. 3 is the variation curve of the static contact angle (about 155°) of the surface of the cowhide nubuck leather treated in Example 2 with the contact time. It can be seen from the figure that as the contact time increases, the contact angle remains unchanged, which means that the water droplet will not wet the leather surface;

Fig. 4 is the variation curve of the static contact angle (about 136°) of the sheepskin front leather surface treated in Example 5 with the contact time. It can be seen from the figure that as the contact time increases, the contact angle remains unchanged, which means that the water droplet will not wet the leather surface;

Fig. 5 is the variation curve of the static contact angle (about 150°) with the contact time on the surface of pigskin suede treated in Example 15. It can be seen from the figure that as the contact time increases, the contact angle remains unchanged, which means that the water droplet will not wet the leather surface;

Figure 6 is a schematic diagram of the rolling situation of water droplets on the dual-purpose leather with different inclination angles, where (a) is the rolling situation of water droplets on the inclined non-plasma-treated dual-purpose leather, from the schematic diagram (a) ) It can be seen that when the inclination angle is large, the water droplets will still remain on the dual-purpose leather of wool and leather; and (b) and (c) are respectively the water droplets on the inclined embodiment 16 and embodiment 19 on the dual-purpose leather of wool and leather. For the rolling situation, it can be seen from the schematic diagrams (b) and (c) that when the angle of the inclined plate is relatively small, the water droplets can roll on the double-purpose leather and roll away from the leather surface, which shows that after Example 16 and Example 19 The treated wool and leather dual-purpose leather has strong hydrophobicity;

Fig. 7 is an atomic force microscope topography image of 10 μm×10 μm on the surface of cowhide front leather without plasma treatment. It can be seen from the figure that the surface of the leather is interwoven with collagen fibers;

Fig. 8 is an atomic force microscope topography image of 10 μm × 10 μm on the surface of the cowhide front leather treated in Example 10. It can be seen from the figure that the polymer particles deposited by plasma polymerization grow along the direction of the fibers and do not cover the gaps between the fibers;

Fig. 9 is a scanning electron microscope topography image of cowhide front leather without plasma treatment. From the picture, the pores on the surface of the cowhide front leather can be clearly observed;

Fig. 10 is a scanning electron microscope topography diagram of the cowhide front leather treated in Example 10. It can be clearly observed from the figure that the pores on the surface of the cowhide front leather after plasma treatment are not significantly different from those of the cowhide front leather without plasma treatment;

Fig. 11 is a scanning electron microscope topography image of conventionally finished cowhide front leather. It can be clearly observed from the figure that the pores on the surface of the cowhide front leather are completely covered by the finishing layer;

Figure 12 is a scanning electron microscope topography of the nubuck surface of cowhide nubuck leather without plasma treatment. From the picture, the fibers on the nubuck surface of the nubuck leather can be clearly observed;

Fig. 13 is a scanning electron microscope topography of the nubuck surface of cowhide nubuck leather treated in Example 12. It can be clearly observed from the figure that the fibers of the nubuck leather surface after plasma treatment are still clearly visible, and there is no obvious difference from the nubuck leather surface without plasma treatment;

Figure 14 is a picture of black water droplets rolling on the nubuck leather surface as the contact time prolongs, where (a) is a picture of water droplets rolling on the nubuck leather surface without plasma treatment, from the figure (a) It can be seen that the water drop not only does not roll on the non-treated cowhide nubuck leather frosted surface, but also produces black water marks on the cowhide nubuck leather frosted surface, and (b) is the water drop on the cowhide nubuck leather frosted surface after the treatment in Example 20 The picture of the rolling situation above, it can be seen from the figure (b) that the water droplets can roll freely on the nubuck leather surface after the treatment in Example 20, and the water droplets will not produce any water marks on the nubuck leather surface, which shows that its Very hydrophobic.

Detailed ways

The present invention is described in detail below by specific embodiment, needs explanation here, embodiment is only further illustration to the present invention, and the scope of application of the present invention is not limited by embodiment, all improvements done on the core content of the present invention And adjustment, all belong to the scope of protection of the present invention. The scope of the present invention is set forth in the claims.

It is worth noting that the static contact angles and rolling angles of the waterproof leather obtained in the following examples were all measured with the OCA20/6 contact angle measuring instrument produced by the German dataphysics company.

Example 1

Put the hexamethylcyclotrisiloxane into the vaporization tank, and then put the nubuck leather with the frosted side up into the reaction chamber of the plasma equipment connected with the vaporization tank; pump the vacuum to 30Pa, and raise the temperature of the vaporization tank at the same time to 30°C, vaporize hexamethylcyclotrisiloxane, and enter the plasma reaction chamber at a flow rate of 7×10 ^-5 ml/min·cm ² , and then discharge under the discharge reaction power of 0.15W/cm ² , continue the discharge reaction for 15 minutes, turn off the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the nubuck leather.

The static contact angle of the waterproof cowhide nubuck leather obtained in this embodiment is 141°±1°, and the rolling angle is 15°±2°.

Example 2

Put octamethylcyclotetrasiloxane into the vaporization tank, and then put the nubuck cowhide leather with the frosted side up into the reaction chamber of the plasma equipment connected with the vaporization tank; pump the vacuum to 30Pa, and raise the temperature of the vaporization tank at the same time to 30°C, vaporize octamethylcyclotetrasiloxane, and enter the plasma reaction chamber at a flow rate of 8×10 ^-5 ml/min·cm ² , and then discharge under the discharge reaction power of 0.5W/cm ² , continue the discharge reaction for 10 minutes, turn off the plasma discharge electrode, fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the nubuck leather.

The static contact angle of the waterproof cowhide nubuck leather obtained in this embodiment is 155°±2°, and the rolling angle is 8°±2°.

Example 3

Put decamethylcyclopentasiloxane into the vaporization tank, and then put the pigskin nubuck suede face up into the reaction chamber of the plasma equipment connected to the vaporization tank; vacuumize to 25Pa, and at the same time put the The temperature was raised to 25°C to vaporize decamethylcyclopentasiloxane, and it entered the plasma reaction chamber at a flow rate of 1×10 ^-4 ml/min·cm ² , and then the discharge reaction power was 1W/cm ² Then, continue the discharge reaction for 18 minutes, turn off the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of pigskin nubuck leather.

The static contact angle of the waterproof pigskin nubuck leather obtained in this embodiment is 145°±3°, and the rolling angle is 15°±2°.

Example 4

Put the hexamethyldisiloxane into the vaporization tank, and then put the cowhide front leather face up into the reaction chamber of the plasma equipment connected to the vaporization tank; vacuumize to 28Pa, and raise the temperature of the vaporization tank to 35 ℃, vaporize hexamethyldisiloxane, and enter the plasma reaction chamber at a flow rate of 3×10 ^-4 ml/min·cm ² , and then discharge continuously at a discharge reaction power of 1.5W/cm ² React for 5 minutes, turn off the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the cowhide front leather.

The static contact angle of the waterproof cowhide front leather obtained in this embodiment is 140°±3°, and the rolling angle is 20°±2°.

Example 5

Put dodecamethylcyclohexasiloxane into the vaporization tank, and then put the sheepskin front leather face up into the reaction chamber of the plasma equipment connected to the vaporization tank; vacuumize to 25Pa, and raise the temperature of the vaporization tank to to 30°C, vaporize dodecamethylcyclohexasiloxane, and enter the plasma reaction chamber at a flow rate of 8×10 ^-5 ml/min·cm ² , and then discharge the reaction power at 1.5W/cm ² Then, continue the discharge reaction for 1min, turn off the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the sheepskin front leather.

The static contact angle of the sheepskin front leather obtained in this embodiment is 136°±2°, and the rolling angle is 22°±2°.

Example 6

Put vinyltriethoxysilane into the vaporization tank, and then put the sheepskin front leather face up into the reaction chamber of the plasma equipment connected to the vaporization tank; vacuumize to 32Pa, and raise the temperature of the vaporization tank to 28 ℃, to vaporize vinyltriethoxysilane, and enter the plasma reaction chamber at a flow rate of 6×10 ^-4 ml/min·cm ² , and then continue the discharge reaction at a discharge reaction power of 1W/cm ² 3min, turn off the plasma discharge electrode, fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the sheepskin front leather.

The static contact angle of the waterproof sheepskin front leather obtained in this embodiment is 139°±2°, and the rolling angle is 15°±2°.

Example 7

Put the acrylic acid into the vaporization tank, then put the cowhide flat leather face up into the reaction chamber of the plasma equipment connected to the vaporization tank; pump the vacuum to 40Pa, and raise the temperature of the vaporization tank to 27°C at the same time to vaporize the acrylic acid. And enter the plasma reaction chamber at a flow rate of 8×10 ^-4 ml/min·cm ² , then continue the discharge reaction for 5 minutes under the discharge reaction power of 0.2W/cm ² , turn off the plasma discharge electrode, and in the plasma The reaction chamber is filled with air to remove unreacted monomers on the surface of the cowhide flat leather.

The static contact angle of the waterproof cowhide flat leather obtained in this embodiment is 140°±3°, and the rolling angle is 20°±2°.

Example 8

Put the methyl acrylate into the vaporization tank, and then put the nubuck cowhide leather with the frosted side up into the reaction chamber of the plasma equipment connected to the vaporization tank; pump the vacuum to 35Pa, and raise the temperature of the vaporization tank to 30°C at the same time, so that Methyl acrylate is vaporized and enters the plasma reaction chamber at a flow rate of 9×10 ^-4 ml/min·cm ² , and then the discharge reaction is continued for 20 minutes at a discharge reaction power of 0.5W/cm ² , and the plasma discharge is turned off For the electrode, it is sufficient to fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the nubuck leather.

The static contact angle of the waterproof cowhide nubuck leather obtained in this embodiment is 155°±3°, and the rolling angle is 7°±1°.

Example 9

Put trifluorooctyl acrylate into the vaporization tank, then put the double-purpose leather with the meat side up into the reaction chamber of the plasma equipment connected with the vaporization tank; vacuumize to 25Pa, and raise the temperature of the vaporization tank to to 45°C, vaporize trifluorooctyl acrylate, and enter the plasma reaction chamber at a flow rate of 5×10 ^-4 ml/min·cm ² , and then discharge reaction power at 0.3W/cm ² for a continuous Discharge reaction for 25 minutes, turn off the plasma discharge electrode, fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the leather dual-purpose leather.

The static contact angle of the waterproof wool leather dual-purpose leather obtained in this embodiment is 150°±3°, and the rolling angle is 12°±3°.

Example 10

Put trifluorooctyl methacrylate into the vaporization tank, then put the cowhide front leather face up into the reaction chamber of the plasma equipment connected with the vaporization tank; vacuumize to 30Pa, and simultaneously raise the temperature of the vaporization tank to At 30°C, tridefluorooctyl methacrylate was vaporized and entered into the plasma reaction chamber at a flow rate of 7×10 ^-5 ml/min·cm ² , and then at a discharge reaction power of 1.5W/cm ² , Continue the discharge reaction for 8 minutes, turn off the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the cowhide front leather.

The static contact angle of the waterproof cowhide front leather obtained in this embodiment is 140°±2°, and the rolling angle is 21°±2°.

Example 11

Put hexafluorobutyl acrylate into the vaporization tank, then put the double-purpose leather with the meat side up into the reaction chamber of the plasma equipment connected with the vaporization tank; vacuumize to 38Pa, and simultaneously raise the temperature of the vaporization tank to At 30°C, vaporize hexafluorobutyl acrylate, and enter the plasma reaction chamber at a flow rate of 9×10 ^-5 ml/min·cm ² , and then continue the discharge reaction at a discharge reaction power of 0.9W/cm ² After 12 minutes, turn off the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the dual-purpose leather.

The static contact angle of the waterproof wool leather dual-purpose leather obtained in this embodiment is 152°±3°, and the rolling angle is 12°±3°.

Example 12

Put dodecafluoroheptyl methacrylate into the vaporization tank, then put the cowhide nubuck leather with the frosted side up into the reaction chamber of the plasma equipment connected with the vaporization tank; vacuumize to 25Pa, and raise the temperature of the vaporization tank to to 40°C, vaporize dodecafluoroheptyl methacrylate, and enter the plasma reaction chamber at a flow rate of 8×10 ^-5 ml/min·cm ² , and then discharge at a power of 1W/cm ² , Continue the discharge reaction for 1 min, turn off the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the nubuck leather.

The static contact angle of the waterproof cowhide nubuck leather obtained in this embodiment is 149°±3°, and the rolling angle is 14°±2°.

Example 13

Put the butyl acrylate into the vaporization tank, then put the dual-purpose fur leather with the meat side up into the reaction chamber of the plasma equipment connected to the vaporization tank; pump the vacuum to 30Pa, and raise the temperature of the vaporization tank to 48°C at the same time , to vaporize butyl acrylate, and enter the plasma reaction chamber at a flow rate of 7×10 ^-4 ml/min·cm ² , then continue the discharge reaction for 25 minutes at a discharge reaction power of 1W/cm ² , and turn off the plasma For the discharge electrode, it is sufficient to fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the dual-purpose leather.

The static contact angle of the waterproof wool leather dual-purpose leather obtained in this embodiment is 152°±3°, and the rolling angle is 11°±2°.

Example 14

Put dodecafluoroheptylpropyltrimethoxysilane into the vaporization tank, then put the nubuck leather with the frosted side up into the reaction chamber of the plasma equipment connected to the vaporization tank; vacuumize to 45Pa, and at the same time put the vaporization tank The temperature was raised to 50°C to vaporize dodecafluoroheptylpropyltrimethoxysilane and enter the plasma reaction chamber at a flow rate of 9×10 ^-5 ml/min·cm ² , and then the discharge reaction power was Under 1W/cm ² , continue the discharge reaction for 10 minutes, turn off the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the cowhide nubuck leather.

The static contact angle of the waterproof cowhide nubuck leather obtained in this embodiment is 150°±2°, and the rolling angle is 10°±1°.

Example 15

Put dodecafluoroheptylpropylmethyldimethoxysilane into the vaporization tank, and then put the nubuck leather with the frosted side up into the reaction chamber of the plasma equipment connected with the vaporization tank; vacuumize to 25Pa, and simultaneously Raise the temperature of the vaporization tank to 40°C to vaporize dodecafluoroheptylpropylmethyldimethoxysilane, and enter the plasma reaction chamber at a flow rate of 7×10 ^-5 ml/min·cm ² , Then, under the discharge reaction power of 0.3W/cm ² , continue the discharge reaction for 15 minutes, close the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the cowhide nubuck leather.

The static contact angle of the waterproof cowhide nubuck leather obtained in this embodiment is 150°±2°, and the rolling angle is 10°±1°.

Example 16

Put tridecafluorooctyltrimethoxysilane into the vaporization tank, and then put the dual-purpose leather with the meat side up into the reaction chamber of the plasma equipment connected with the vaporization tank; vacuumize to 30Pa, and at the same time put the vaporization tank The temperature is raised to 40°C to vaporize tridecafluorooctyltrimethoxysilane, and enter the plasma reaction chamber at a flow rate of 7×10 ^-5 ml/min·cm ² , and then the discharge reaction power is 0.15W /cm ² , continue the discharge reaction for 1min, turn off the plasma discharge electrode, and fill the plasma reaction chamber with air to remove unreacted monomers on the surface of the leather dual-purpose leather.

The static contact angle of the waterproof wool leather dual-purpose leather obtained in this embodiment is 151°±2°, and the rolling angle is 15°±1°.

Example 17

Put 4-methyl-(perfluorohexylethyl)propyltrimethoxysilane into the vaporization tank, then put the nubuck leather with the frosted side up into the reaction chamber of the plasma equipment connected with the vaporization tank; vacuumize to 25Pa, and at the same time raise the temperature of the vaporization tank to 43°C to vaporize 4-methyl-(perfluorohexylethyl)propyltrimethoxysilane at a flow rate of 6×10 ^-4 ml/min·cm ² Enter the plasma reaction chamber, then continue the discharge reaction for 9 minutes under the discharge reaction power of 0.15W/ ^cm2 , close the plasma discharge electrode, fill the plasma reaction chamber with air to remove unreacted monomers on the surface of cowhide nubuck leather That's it.

The static contact angle of the waterproof cowhide nubuck leather obtained in this embodiment is 153°±2°, and the rolling angle is 13°±2°.

Example 18

Mix octamethylcyclotetrasiloxane and trifluorooctyl acrylate into the vaporization tank, and then put the leather dual-purpose leather face up into the reaction chamber of the plasma equipment connected to the vaporization tank; vacuumize to 30Pa, and at the same time raise the temperature of the vaporization tank to 40°C to vaporize the mixture of octamethylcyclotetrasiloxane and trifluorooctyl acrylate, and enter the plasma at a flow rate of 7×10 ^-5 ml/min·cm ² Then, under the discharge reaction power of 1W/cm ² , the discharge reaction was continued for 5 minutes, the plasma discharge electrode was closed, and air was filled in the plasma reaction chamber to remove the unreacted monomer on the surface of the leather dual-purpose leather. Can.

The static contact angle of the waterproof wool leather dual-purpose leather obtained in this embodiment is 153°±2°, and the rolling angle is 10°±1°.

Example 19

Mix decamethylcyclopentasiloxane and tridecafluorooctyltrimethoxysilane into the vaporization tank, then put the pigskin nubuck suede side up into the reaction chamber of the plasma device connected to the vaporization tank ; Vacuumize to 42Pa, and at the same time raise the temperature of the vaporization tank to 40°C to vaporize the mixture of decamethylcyclopentasiloxane and tridecafluorooctyltrimethoxysilane at 3×10 ^-4 ml/min· The flow rate of cm ² enters the plasma reaction chamber, and then under the discharge reaction power of 1.5W/cm ² , the discharge reaction is continued for 20 minutes, the plasma discharge electrode is turned off, and air is filled in the plasma reaction chamber to remove the pigskin plush Unreacted monomers on the leather surface are sufficient.

The static contact angle of the waterproof pigskin nubuck leather obtained in this example is 148°±2°, and the rolling angle is 15°±1°.

Example 20

Mix hexamethylcyclotrisiloxane and hexafluorobutyl acrylate into the vaporization tank, then put the nubuck leather with the frosted side up into the reaction chamber of the plasma equipment connected to the vaporization tank; vacuumize to 30Pa, At the same time, raise the temperature of the vaporization tank to 30°C to vaporize the mixture of hexamethylcyclotrisiloxane and hexafluorobutyl acrylate, and enter the plasma reaction chamber at a flow rate of 9×10 ^-5 ml/min·cm ² Then, under the discharge reaction power of 0.5W/cm ² , the discharge reaction was continued for 15 minutes and the plasma discharge electrode was turned off, and the plasma reaction chamber was filled with air to remove unreacted monomers on the surface of the cowhide nubuck leather.

The static contact angle of the waterproof cowhide nubuck leather obtained in this embodiment is 151°±2°, and the rolling angle is 9°±1°.

Claims (10)

1. The method for preparing waterproof leather with low-temperature plasma polymerization deposition, the process steps and conditions of the method are as follows: 1) Put at least one of siloxane or acrylic or acrylate or fluorine-containing acrylate or fluorosilane monomer into the vaporization tank, and then put the leather to be treated face up into the plasma reaction In the reaction chamber of the equipment, the vaporization tank is connected with the plasma reaction equipment; 2) Vacuumize the vacuum in the reaction chamber of the vaporization tank and the plasma reaction equipment to 25-45Pa, and at the same time raise the temperature of the vaporization tank to 25-50°C to vaporize the monomer in the vaporization tank, then use 7× The flow rate of 10 ^-5 -9×10 ^-4 ml/min·cm ² enters the reaction chamber of the plasma reaction equipment, under the discharge reaction power of 0.15-1.5W/cm ² , react for 1-25min, you can get Polymeric deposition for leather with a water repellent surface. 2. the method for preparing waterproof leather with low-temperature plasma polymerization deposition according to claim 1, the siloxane compound described in the method is hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane alkane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethyldisiloxane, and vinyltriethoxysilane; acrylic monomers are acrylic acid and methacrylic acid; acrylates The monomers are methyl acrylate, butyl acrylate and methyl methacrylate; the fluorine-containing acrylate monomers are hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, acrylic acid Trifluorooctyl and trifluorooctyl methacrylate; fluorosilane monomers are dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, tridecafluoroheptylpropylmethyldimethoxysilane, Fluorooctyltrimethoxysilane and 4-methyl-(perfluorohexylethyl)propyltrimethoxysilane. 3. The method for preparing waterproof leather by low-temperature plasma polymerization deposition according to claim 1, wherein the vacuum degree in the method is 25-35Pa; the temperature is 25-45°C. 4. The method for preparing waterproof leather by low-temperature plasma polymerization deposition according to claim 1, wherein the flow rate in the method is 7×10 ^-5 -8×10 ^-4 ml/min·cm ² . 5. The method for preparing waterproof leather by low-temperature plasma polymerization deposition according to claim 1 or 2 or 3 or 4, wherein the power in the method is 0.15-1.0 W/cm ² . 6. The method for preparing waterproof leather by low-temperature plasma polymerization deposition according to claim 1 or 2 or 3 or 4, wherein the reaction time in the method is 5-20min. 7. The method for preparing waterproof leather by low-temperature plasma polymerization deposition according to claim 5, wherein the reaction time described in the method is 5-20min. 8. according to claim 1 or 2 or 3 or 4 described method with low temperature plasma polymerization deposition to prepare waterproof leather, the leather described in the method is unpainted front leather, suede leather, nubuck leather or Any of the dual-purpose leathers of fur and leather. 9. the method for preparing waterproof leather with low-temperature plasma polymerization deposition according to claim 7, the leather described in the method is unpainted front leather, suede leather, nubuck leather or wool leather dual-purpose leather of any kind. 10. The waterproof leather prepared by the low-temperature plasma polymerization deposition according to claim 1, the thickness of the waterproof film deposited on the surface of the leather is micron or below, its static contact angle is 136-155 °, and the rolling angle is 7- 22°, and observed from the scanning electron microscope, clearly intertwined collagen fibers can be seen.

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