WO2016155451A1

WO2016155451A1 - Process for composite ion plating of waterproof breathable polyurethane film with nanometals and product thereof

Info

Publication number: WO2016155451A1
Application number: PCT/CN2016/075171
Authority: WO
Inventors: 朱家骏
Original assignee: 嘉兴中科奥度新材料有限公司
Priority date: 2015-03-31
Filing date: 2016-03-01
Publication date: 2016-10-06
Also published as: CN104831236A; CN104831236B

Abstract

A process for composite ion plating of a waterproof breathable polyurethane film with nanometals, with a substrate being the waterproof breathable polyurethane film, and the process comprising: (1) carrying out a vacuum dewatering degassing treatment on the substrate in a vacuum chamber with a vacuum degree of 10 Pa - 3.0×10^-4 Pa and a heating temperature of 60°C-120°C; (2) carrying out a plasma surface cleaning treatment on the substrate by a cathode ion film plating device with argon or nitrogen as a protection gas under a vacuum degree of 1.0×10^-1Pa-3.0×10^-4 Pa at a temperature of -1°C to -35°C at a substrate running speed of 3.0-30.0 m/min, generating metal ions and nanoparticles with a density of 1.0-10.0 g/m² by means of composite ion film plating with a metal as a target material, and plating the surface of the substrate with a nanometal plating layer with the nanoparticle particle size thereof being below 100 nm; and (3) cutting and metering the material and carrying out vacuum packaging. Also a product of waterproof breathable polyurethane film with nanometals composite-ion-plated thereon.

Description

Waterproof and breathable polyurethane film composite ion plating nano metal technology and products thereof

Technical field

The invention belongs to the field of functional polymer materials, and particularly relates to a waterproof and breathable polyurethane film composite ion plating nano metal technology and a product thereof.

Background technique

Nanometals (silver, copper, zinc, nickel, alloys, etc.) are nanomaterialized using advanced nanotechnology, the average size of which is a single particle or aggregate of particles of less than 100 nm. Nanometals produce powerful and long-lasting properties such as electrical conductivity, electromagnetic shielding, antistatic, thermal insulation, bactericidal, and antimicrobial properties. Nano-silver, nano-copper and nano-nickel alloy can kill a variety of bacteria and viruses in a few minutes, broad-spectrum sterilization and anti-bacterial without any drug resistance and toxic side effects. The excellent properties of nano-metal can be widely used in functional clothing. , protective equipment and hygiene products. When the surface of the substrate is coated with nano metal particles, there are still many technical problems. First, the number of nano metal particles is insufficient and the adhesion of the plating layer is not strong, so that various excellent functions of the material are not durable and sufficient; second, the nano metal plating layer has nanoparticles thereof. The distribution range is difficult to control, and the distribution of nanoparticles is uneven, so that the nano-scale metal plating layer becomes a sub-micron or even micro-scale metal plating layer, and the surface properties of the micro-scale metal layer and the performance of the surface of the nano-scale metal layer (such as There are huge differences in specific surface area, surface effect, volume effect and quantum size effect; thirdly, the cleanliness of the surface of the substrate directly affects the adhesion of the nano-metal coating.

Summary of the invention

The object of the present invention is to provide a waterproof and breathable polyurethane film composite ion plating nano metal process, which makes the nano-particles of the plating layer have a narrow distribution and uniform distribution, and the coating has strong adhesion, so as to improve the performance of the product.

In order to achieve the above object, the present invention provides a waterproof and breathable polyurethane film composite ion plating nano metal process, characterized in that the substrate is a waterproof and breathable polyurethane film, and the process comprises the following steps:

(1) The substrate is in a vacuum chamber, the degree of vacuum is 10 Pa to 3.0 × 10 -4 Pa, and the heating temperature is 60 ° C to 120 ° C, and the substrate is subjected to vacuum degassing treatment;

(2) Cathodic ion plating equipment is used, with argon or nitrogen as shielding gas, the degree of vacuum is 1.0×10-1Pa～3.0×10-4Pa, the temperature is -1°C～-35°C, and the substrate running speed is 3.0～30.0m. /min, the plasma surface cleaning treatment of the substrate, using metal as the target, using composite ion plating to produce metal ions and nanoparticles, the density of metal ions and nanoparticles is 1.0-5.0 g/m2, and the surface of the substrate is coated with nanometers. Metal plating, nano metal plating nanoparticles having a particle size of less than 100 nm;

(3) The above materials are cut, metered, and vacuum-packed.

The invention adopts a waterproof and breathable polyurethane film as a base body, first performs vacuum water removal and degassing treatment on the substrate, and then uses the composite ion plating method to plate the nano metal, the nano metal plating layer has a narrow nano particle distribution, the nano metal plating layer has good uniformity, and the nano metal Excellent performance and stability.

Further, the composite ion plating method is a combination of two types of coating methods: an arc ion plating film and a magnetron sputtering coating film. Arc ion plating and magnetron sputtering coating The combination of the membranes can well control the density of the produced metal ions and nanoparticles and the ratio between the two, so that the adhesion of the coating is stronger and the uniformity is better.

Further, the nanoparticles of the nano metal plating layer have a particle size of 10 to 60 nm. The nanoparticle distribution range is narrow, the nanoparticle distribution is uniform, the coating adhesion is stronger, and the measurement is better.

detailed description

The waterproof and breathable polyurethane film composite ion plating nano metal process of the invention has a base material which is a waterproof and breathable polyurethane film, and the waterproof and breathable polyurethane film has a large number of nanometer holes, and has good waterproof and gas permeability.

Example 1

The base body is a waterproof and breathable polyurethane film having a specific gravity of 1.21, a width of 1380 mm, a thickness of 0.015 mm, a moisture permeability of 12000 g/m2/24h, and a water resistance of 10000 mmH2O. Process steps include:

(1) The substrate is placed in a vacuum chamber at a vacuum of 1.0×10-1 Pa, a heating temperature of 60 to 90 ° C, and a heating time of 20 to 50 minutes, and the substrate is vacuum-dehydrated and degassed.

(2) Using a cathode ion plating equipment with a width of 1400 mm, the treated substrate is placed on the unwinding device of the coating equipment with a vacuum of 2.4×10-1 Pa, a temperature of -15 ° C, and a substrate running speed of 15.0 m. /min, with 99.9% argon as the shielding gas, the flow rate is 1200ml/min, the base plasma surface cleaning treatment, 99.99% high purity silver as the target, arc current 80 ~ 120A, magnetic control voltage 460 ~ 880V, The current is 12-20A, and the composite ion plating method is used to generate silver ions and nanoparticles. The density of silver ions and nanoparticles is 1.0-5.0 g/m2, and the surface of the substrate is coated with nano-silver coating, nanometer. The silver plated nanoparticles have a particle size of 10 to 30 nm. The obtained product is plated with a nano metal plating layer on the substrate, and the nano metal plating layer has a particle size of 10 to 30 nm. The thickness of the plating layer can be adjusted by controlling the power of the plasma power source and the unwinding speed.

(3) The above materials are cut, metered and vacuum-packed as required.

Example 2

The base body is a waterproof and breathable polyurethane film having a specific gravity of 1.21, a width of 1380 mm, a thickness of 0.020 mm, a moisture permeability of 12000 g/m2/24h, and a water resistance of 10000 mmH2O. Process steps include:

(1) The substrate is placed in a vacuum chamber at a vacuum of 1.0×10-1 Pa, a heating temperature of 60 to 90 ° C, and a heating time of 30 to 50 minutes, and the substrate is subjected to vacuum degassing.

(2) Using a cathode ion plating equipment with a width of 1400 mm, the treated substrate is placed on the unwinding device of the coating equipment with a vacuum of 2.6×10-1 Pa, a temperature of -15 ° C, and a substrate running speed of 10.0 m. /min, 99.9% argon gas as shielding gas, flow rate is 1200ml/min, base plasma surface cleaning treatment, 99.9% high purity metal aluminum as target, arc current 80～120A, magnetron voltage 360～460V The current is 22-28A, and the composite ion plating method is used to produce aluminum ions and nanoparticles. The density of aluminum ions and nanoparticles is 1.0-10.0g/m2, and the surface of the substrate is coated with nano-aluminum coating, and the particle size of nano-aluminum-coated nano-particles. It is 10 to 60 nm. The obtained product is plated with a nano metal plating layer on the substrate, and the nano metal plating layer has a particle size of 10 to 60 nm. The thickness of the plating layer can be adjusted by controlling the power of the plasma power source and the unwinding speed.

(3) The above materials are cut, metered and vacuum-packed as required.

In the step (1) of the present invention, the degree of vacuum may be selected from the range of 10 Pa to 3.0 x 10-4 Pa, and the heating temperature may be selected from the range of 60 ° C to 120 ° C, and the heating time is controlled to be 10 to 60 minutes. The step (1) can effectively remove moisture, bubbles and impurities on the substrate, and prepare for the subsequent coating, so that the coating has strong adhesion and is not easy to fall off. In the step (2), the shielding gas may be argon or nitrogen, the degree of vacuum is 1.0×10-1Pa to 3.0×10-4Pa, the temperature is −1° C. to −35° C., and the substrate operating speed is 3.0 to 30.0 m/min. The metal ions and nanoparticles have a density of 1.0 to 10.0 g/m2. The nano-metal plated nanoparticles have a particle size of less than 100 nm, and accordingly, the nano-metal plated nanoparticles of the obtained article have a particle size of less than 100 nm. The nano-metallized nanoparticles have a particle size of 10 to 60 nm, a narrow distribution of nanoparticles, a uniform distribution of nanoparticles, and a stronger adhesion and better measurement.

The composite ion plating method combines two methods of arc ion plating and magnetron sputtering coating, which can well control the density of the generated metal ions and nanoparticles and the ratio between the two, so that the adhesion of the coating is more Strong and uniform. The metals are gold, silver, aluminum, copper, zinc, iron, nickel, titanium, platinum, palladium, cobalt, rhodium, rare earth metals and mixtures and alloys thereof, and mixtures and alloys thereof, and the metals listed above are or relationship. The most preferred are precious metals, and other metals will be apparent to those skilled in the art.

The invention can design the nano metal plating layer according to the specific requirements of the material function, and obtain various functional materials through the superposition of the nano metal plating layer and the material compounding, such as conductivity, electromagnetic shielding property, antistatic property, heat insulation property, sterilization and antibacterial property, etc. Waterproof and breathable polyurethane film The performance of the body is fully reflected, and at the same time, the product has various functions and functions of the nano metal plating.

The invention has the advantages of narrow distribution of nanoparticles of nano metal plating layer, good uniformity of nano metal plating layer, excellent performance of nano metal, and the like, and can be continuously produced, with high yield, good quality, no pollution and excellent performance and stability. The obtained product has the functions of waterproofing and ventilating and filtering bacteria and viruses, and has the functions of sterilization, anti-static and anti-heating, and can be widely used in functional clothing, protective articles and sanitary products.

Claims

The waterproof and breathable polyurethane film composite ion plating nano metal process is characterized in that the substrate is a waterproof and breathable polyurethane film, and the process comprises the following steps:

(1) The substrate is in a vacuum chamber, the degree of vacuum is 10 Pa to 3.0 × 10 -4 Pa, and the heating temperature is 60 ° C to 120 ° C, and the substrate is subjected to vacuum degassing treatment;

(2) Cathodic ion plating equipment is used, with argon or nitrogen as shielding gas, the degree of vacuum is 1.0×10-1Pa～3.0×10-4Pa, the temperature is -1°C～-35°C, and the substrate running speed is 3.0～30.0m. /min, the plasma surface cleaning treatment of the substrate, metal as the target, composite ion plating to produce metal ions and nanoparticles, metal ions and nanoparticles with a density of 1.0 ~ 10.0g / m2, the surface of the substrate is coated with nano Metal plating, nano metal plating nanoparticles having a particle size of less than 100 nm;

(3) The above materials are cut, metered, and vacuum-packed.
The waterproof and breathable polyurethane film composite ion plating nano metal process according to claim 1, wherein the composite ion plating method is a combination of an arc ion plating film and a magnetron sputtering coating.
The method according to claim 2, wherein the nanoparticles of the nano metal plating layer have a particle size of 10 to 60 nm.
The method of composite metal ion plating nano-metal according to claim 3, wherein the metal is gold, silver, aluminum, copper, zinc, iron, nickel, titanium, platinum, palladium, cobalt, rhodium, Rare earth metals and mixtures and alloys thereof, and mixtures and alloys of these metals.
The waterproof and breathable polyurethane film composite ion plating nano metal process according to claim 4, wherein the waterproof and breathable polyurethane film has a specific gravity of 1.21, a thickness of 0.01 to 0.02 mm, a moisture permeability of 12,000 g/m2/24h, and a water resistance of 10000 mmH2O.
The waterproof gas-permeable polyurethane film composite ion plating nano metal process according to claim 5, wherein in the step (1), the heating time is 10 to 60 minutes.
The article prepared by the process of claim 1 is characterized in that the substrate is a waterproof and breathable polyurethane film, and the nano metal plating layer is plated on the substrate by a composite ion plating method, and the nano metal plating layer has a particle size of less than 100 nm.
The article according to claim 7, wherein the composite ion plating method is a combination of an arc ion plating film and a magnetron sputtering coating film.
The article of claim 8 wherein the nanoparticles of the nanometal plating have a particle size of from 10 to 60 nm.
The article according to claim 9, wherein the metal of the nanometal plating layer is gold, silver, aluminum, copper, zinc, iron, nickel, titanium, platinum, palladium, cobalt, rhodium, rare earth metals, and mixtures thereof. And alloys, as well as mixtures and alloys of these metals.