WO2015000135A1 - Method for preparing baseless cloth polyurethane gas-permeable membrane - Google Patents

Abstract

The present invention provides a method for preparing a baseless cloth polyurethane gas-permeable membrane. The method comprises the following steps: a) preprocessing base cloth, b) preparing coating liquid, c) coating for mounting, d) solidifying to form membrane, e) cleaning by hot water, f) drying, and g) release stripping. The base cloth of the gas-permeable membrane is TC cloth, and the coating liquid consistes of polyurethane, dimethylformamide, dispersant, air hole regulator, wear-resisting auxiliary agent and water repellent auxiliary agent.

Description

 Novel preparation method of PU-free wet waterproof and moisture-proof suspension and anti-slip gas-permeable membrane  Technical field

 The invention relates to the technical field of material preparation, in particular to a novel preparation method of a PU-free wet waterproof and moisture-proof suspension and anti-slip gas-permeable membrane.

 Background technique

With the advancement of society, the application of suspension materials has become more and more extensive, especially the application of sports equipment is changing with each passing day, and the competition is fierce. In order to overcome the relevant shock absorber materials in the process of material selection, various manufacturers must select a base fabric with high elasticity as the substrate, and the related fabric with high elasticity is easy to be pulled by the machine when coating. The elastic material is stretched by the machine, so that the elasticity of the suspension material is lowered, and the high elasticity which it should have cannot be effectively exhibited. In the prior art, the production process of such a suspension material is not only complicated but also seriously wastes resources, and more importantly, the manufactured product has poor mechanical properties and a short service life. The improvement of production process for suspension materials is an important issue that every manufacturer needs to solve. How to reduce the waste of resources and improve the mechanical properties and service life of products through process innovation is the main research direction. The new leather non-backing polyurethane wet PU leather layer can have more than five times the extension force, which is suitable for the related products on sports equipment and can improve the service life.

 Summary of the invention

In view of this, the present invention is directed to the absence of the prior art, and the main object thereof is to provide a novel preparation method for a PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane without a bottom cloth, and the production of the bottomless cloth PU wet method. The waterproof and moisture permeable suspension and anti-slip gas permeable membrane not only can effectively save materials, but also has good mechanical properties.

In order to achieve the above object, the present invention adopts the following technical solution: a novel preparation method of a PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane without a backing cloth, comprising the following steps:

a, pre-clothing treatment

The material of the base cloth is TC cloth, the thickness of which is 20~35 filaments, the base cloth is immersed in clear water, and the base cloth after soaking is dried by rollers, so that the water content of the base cloth is 10%~20%;

b, preparation of coating liquid

First, the polyurethane initial slurry is prepared by mixing polyurethane: dimethylformamide at a mass ratio of 3:7; at 25 ° C, the viscosity of the polyurethane primary slurry is 250,000 CPS, using dimethylformyl Ammonia dilutes the viscosity of the polyurethane primary slurry to 10,000 CPS to prepare a polyurethane slurry; then, adds 1 to 1.5 to the diluted 100 parts by mass of the polyurethane slurry. a mass of dispersant, 1 to 1.5 parts by mass of a pore regulator, 1.5 to 2.0 parts by mass of an abrasion-resistant auxiliary, and 1 to 1.5 parts by mass of a water-removing aid; and uniformly mixing to obtain a coating liquid;

c, coating on the machine

The coating liquid is poured into a coater, and the coating liquid is applied to the base cloth by a coater, and the coating amount can be adjusted according to the required thickness of the leather;

d, solidification film formation

The base cloth coated with the coating liquid is placed in the coagulating liquid of the coagulation tank to be solidified into a film, the temperature of the coagulating liquid is 20 to 30 ° C, and the solidification time is 20 to 30 minutes;

e, hot water cleaning

The composite material consisting of the base fabric and the leather material attached to the base fabric is washed in water, the water temperature is 70-75 ° C, and the cleaning time is 15-20 minutes;

f, dry

The cleaned composite material is baked in an oven at a baking temperature of 60 to 70 ° C and baked for 30 to 40 minutes;

g, release stripping

After drying, the film layer and the base fabric in the composite material can be peeled off, the base fabric is recycled, and the film layer is separately rolled up to remember the shock-absorbing and breathable gas-permeable membrane.

The polyurethane in the coating liquid is composed of polyester polyol, diisocyanate and 1-4 butanediol in a mass percentage of 100:20: The reaction of 10 is carried out, and the molecular weight of the polyester polyol is 3000 to 4000.

The dispersing agent is an anionic surfactant, the anionic surfactant is polyacrylamide, the polyacrylamide is a water-soluble polymer anionic surfactant; and the pore regulator is a nano silica modified ring Oxygen resin, the molecular dispersion thereof can affect the speed of displacement and the pore size of dimethylformamide (DMF) when it is replaced with water; the wear-resistant auxiliary agent is a silicon-based wear-resistant modifier; The water adjuvant is a fluorocarbon alcohol resin, and the fluorocarbon alcohol resin is an environmentally friendly ethylene glycol monoallyl ether (EGMAE) A monomer that has a hydrophobic function to reduce water absorption.

In the preparation process of the coating liquid, vacuum defoaming is required for 2 to 4 hours, and then it is allowed to stand for 24 hours, and after being matured, the coating machine is applied, and only one knife is coated on the base cloth.

The coagulating liquid in the coagulation tank contains 10% dimethylformamide.

During the hot water cleaning process, the four tanks are cleaned. The temperature of the first to third washing tanks is 70 ° C, and the temperature of the fourth washing tank is 75 ° C. The residual dimethyl group in the cleaned composite material. The amide drops below 500 PPM.

The invention has obvious advantages and beneficial effects compared with the prior art. Specifically, the above solution shows that the invention develops a bottomless cloth PU wet method through the bold exploration of the production process of the suspension material. The novel preparation method of the wet suspension and anti-slip gas permeable membrane, the product prepared by the method, not only can effectively improve the mechanical properties and the gas permeability of the suspension and anti-slip material, and through the improvement of the process, The base fabric can be recycled, and at the same time reduce the drying temperature and time, thereby effectively reducing the waste of materials and energy in the production process, low carbon environmental protection, reducing the production and raw material cost of the product, and improving the market competitiveness of the product. The preparation method of seismic materials is of great market value. The waterproof, moisture-permeable, shock-absorbing and anti-slip gas-permeable membrane can be replaced in water and can be peeled off from the base fabric. It can be bonded to other materials on various composites for entanglement of various shock-absorbing and anti-slip materials. band, Such as: bicycle grip winding belt, tennis racket winding belt, badminton racket winding belt, baseball grip winding belt, table tennis rack winding belt, various parts that need to be wound and shockproof and slippery can be used.

 DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a table showing the results of mechanical properties test of a PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane prepared in Examples 1 to 3 of the present invention.

2 is a table showing the anti-slip effect of the PU-free wet waterproof and moisture-permeable suspension and anti-slip breathable film prepared in Examples 1 to 3 of the present invention.

 detailed description

Example 1

The invention discloses a novel preparation method of a PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane without a bottom cloth, comprising the following steps:

a, pre-clothing treatment

The material of the base fabric is TC cloth, the thickness of which is 20~35 filaments, the base cloth is immersed in clear water for 30 minutes, and the base cloth after soaking is pressed by a roller to make the water content of the base cloth 10%;

b, preparation of coating liquid

First, the polyurethane initial slurry is prepared by mixing polyurethane: dimethylformamide at a mass ratio of 3:7; at 25 ° C, the viscosity of the polyurethane primary slurry is 250,000 CPS, using dimethylformyl Ammonia dilutes the viscosity of the polyurethane primary slurry to 10,000 CPS to prepare a polyurethane slurry; then, adds 1 to the diluted 100 parts by mass of the polyurethane slurry. a mass part dispersant, 1 part by mass of a pore regulator, 1.5 parts by mass of an abrasion aid, and 1 part by mass of a water-repellent aid; uniformly mixing to obtain a coating liquid; the polyurethane in the coating liquid is a polyester polyol, Diisocyanate and 1-4 butanediol by mass percentage 100 : 20 : The reaction of 10 is carried out, and the molecular weight of the polyester polyol is 3000 to 4000. The dispersing agent is an anionic surfactant, the anionic surfactant is polyacrylamide, the polyacrylamide is a water-soluble polymer anionic surfactant; and the pore regulator is a nano silica modified ring Oxygen resin, the molecular dispersion thereof can affect the speed of displacement and the pore size of dimethylformamide (DMF) when it is replaced with water; the wear-resistant auxiliary agent is a silicon-based wear-resistant modifier; The water adjuvant is a fluorocarbon alcohol resin, and the fluorocarbon alcohol resin is an environmentally friendly ethylene glycol monoallyl ether (EGMAE) A monomer that has a hydrophobic function to reduce water absorption.

c, coating on the machine

The coating liquid is poured into a coater, and the coating liquid is applied to the base cloth by a coater, and the coating amount can be adjusted according to the thickness of the desired leather; in the preparation process of the coating liquid, a vacuum is required. After defoaming for 2 to 4 hours, it is allowed to stand for 24 hours. After the aging, the coating machine is applied, and only one knife is applied on the base cloth.

d, solidification film formation

The base cloth coated with the coating liquid is placed in the coagulating liquid of the coagulation tank to be solidified into a film, the temperature of the coagulating liquid is 20 to 30 ° C, and the solidification time is 20 minutes; the coagulating liquid in the coagulation tank contains 10% Methylformamide (DMF).

e, hot water cleaning

The composite material consisting of the base fabric and the leather material attached to the base fabric is washed in water for 15 minutes; in the hot water cleaning process, the water is washed in four water tanks, and the temperature of the first to third cleaning tanks is cleaned. At 70 ° C, the temperature of the fourth cleaning bath is 75 ° C, and the residual dimethylformamide in the cleaned composite material drops below 500 PPM.

f, dry

The cleaned composite material is baked in an oven at a baking temperature of 60 ° C and baked for 40 minutes;

g, release stripping

After drying, the film layer and the base fabric in the composite material can be peeled off, the base fabric is recycled, and the film layer is separately rolled up to remember the shock-absorbing and breathable gas-permeable membrane.

Example 2

The invention discloses a novel preparation method of a PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane without a bottom cloth, comprising the following steps:

a, pre-clothing treatment

The base fabric is made of TC cloth and has a thickness of 30 filaments. The base fabric is immersed in clear water for 30 minutes, and the base cloth after soaking is pressed by a roller to make the water content of the base fabric 15%;

b, preparation of coating liquid

First, the polyurethane initial slurry is prepared by mixing polyurethane: dimethylformamide at a mass ratio of 3:7; at 25 ° C, the viscosity of the polyurethane primary slurry is 250,000 CPS, using dimethylformyl Ammonia dilutes the viscosity of the polyurethane primary slurry to 10,000 CPS to prepare a polyurethane slurry; then, adds 1 to the diluted 100 parts by mass of the polyurethane slurry. Parts by mass dispersant, 1.5 parts by mass of pore regulator, 2.0 parts by weight of wear-resistant additives and 1.5 a mass of water-removing aid; uniformly mixing to prepare a coating liquid; the polyurethane in the coating liquid is composed of polyester polyol, diisocyanate and 1-4 butanediol in a mass percentage of 100:20: The reaction of 10 is carried out, and the molecular weight of the polyester polyol is 3000 to 4000. The dispersing agent is an anionic surfactant, the anionic surfactant is polyacrylamide, the polyacrylamide is a water-soluble polymer anionic surfactant; and the pore regulator is a nano silica modified ring Oxygen resin, the molecular dispersion thereof can affect the speed of displacement and the pore size of dimethylformamide (DMF) when it is replaced with water; the wear-resistant auxiliary agent is a silicon-based wear-resistant modifier; The water adjuvant is a fluorocarbon alcohol resin, and the fluorocarbon alcohol resin is an environmentally friendly ethylene glycol monoallyl ether (EGMAE) A monomer that has a hydrophobic function to reduce water absorption.

c, coating on the machine

The coating liquid is poured into a coater, and the coating liquid is applied to the base cloth by a coater, and the coating amount can be adjusted according to the thickness of the desired leather; in the preparation process of the coating liquid, a vacuum is required. After defoaming for 2 to 4 hours, it is allowed to stand for 24 hours. After the aging, the coating machine is applied, and only one knife is applied on the base cloth.

d, solidification film formation

The base cloth coated with the coating liquid is placed in the coagulating liquid of the coagulation tank to be solidified into a film, the temperature of the coagulating liquid is 25 ° C, and the solidification time is 25 minutes; the coagulating liquid in the coagulation tank contains 10% dimethyl group Formamide (DMF).

e, hot water cleaning

The composite material consisting of the base fabric and the leather material attached to the base fabric is washed in water for 18 minutes; in the hot water cleaning process, the four tanks are cleaned, and the temperature of the first to third cleaning tanks is cleaned. At 70 ° C, the temperature of the fourth cleaning bath is 75 ° C, and the residual dimethylformamide in the cleaned composite material drops below 500 PPM.

f, dry

The cleaned composite material is baked in an oven at a baking temperature of 65 ° C and baked for 35 minutes;

g, release stripping

After drying, the film layer and the base fabric in the composite material can be peeled off, the base fabric is recycled, and the film layer is separately rolled up to remember the shock-absorbing and breathable gas-permeable membrane.

Example 3

The invention discloses a novel preparation method of a PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane without a bottom cloth, comprising the following steps:

a, pre-clothing treatment

The material of the base cloth is TC cloth, the thickness of which is 20~35 filaments, the base cloth is immersed in clear water for 30 minutes, and the base cloth after soaking is pressed with a roller to make the water content of the base cloth 20%;

b, preparation of coating liquid

First, the polyurethane initial slurry is prepared by mixing polyurethane: dimethylformamide at a mass ratio of 3:7; at 25 ° C, the viscosity of the polyurethane primary slurry is 250,000 CPS, using dimethylformyl Ammonia dilutes the viscosity of the polyurethane primary slurry to 10,000 CPS to prepare a polyurethane slurry; then, adds 1.5 to the diluted 100 parts by mass of the polyurethane slurry. Parts by mass dispersant, 1.5 parts by mass of pore regulator, 2.0 parts by weight of wear-resistant additives and 1.5 a mass of water-removing aid; uniformly mixing to prepare a coating liquid; the polyurethane in the coating liquid is composed of polyester polyol, diisocyanate and 1-4 butanediol in a mass percentage of 100:20: The reaction of 10 is carried out, and the molecular weight of the polyester polyol is 3000 to 4000. The dispersing agent is an anionic surfactant, the anionic surfactant is polyacrylamide, the polyacrylamide is a water-soluble polymer anionic surfactant; and the pore regulator is a nano silica modified ring Oxygen resin, the molecular dispersion thereof can affect the speed of displacement and the pore size of dimethylformamide (DMF) when it is replaced with water; the wear-resistant auxiliary agent is a silicon-based wear-resistant modifier; The water adjuvant is a fluorocarbon alcohol resin, and the fluorocarbon alcohol resin is an environmentally friendly ethylene glycol monoallyl ether (EGMAE) A monomer that has a hydrophobic function to reduce water absorption.

c, coating on the machine

The coating liquid is poured into a coater, and the coating liquid is applied to the base cloth by a coater, and the coating amount can be adjusted according to the thickness of the desired leather; in the preparation process of the coating liquid, a vacuum is required. After defoaming for 2 hours, it was allowed to stand for 24 hours. After the aging, the coating machine was applied, and only one knife was applied to the base fabric.

d, solidification film formation

The base cloth coated with the coating liquid is placed in a coagulating liquid of the coagulation tank to be solidified into a film, the temperature of the coagulating liquid is 30 ° C, and the solidification time is 20 minutes; the coagulating liquid in the coagulation tank contains 10% dimethyl group Formamide (DMF).

e, hot water cleaning

The composite material consisting of the base fabric and the leather material attached to the base fabric is washed in water for 20 minutes; in the hot water cleaning process, it is washed in four water tanks, and the temperature of the first to third cleaning tanks is cleaned. At 70 ° C, the temperature of the fourth cleaning bath is 75 ° C, and the residual dimethylformamide in the cleaned composite material drops below 500 PPM.

f, dry

The cleaned composite material is baked in an oven at a baking temperature of 70 ° C and baked for 30 minutes;

g, release stripping

After drying, the film layer and the base fabric in the composite material can be peeled off, the base fabric is recycled, and the film layer is separately rolled up to remember the shock-absorbing and breathable gas-permeable membrane.

The bottomless cloth PU wet waterproof moisture-permeable and shock-absorbing anti-slip gas-permeable film prepared by the examples 1 to 3 was tested, and the results were as follows:

1, mechanical properties (Figure 1)

2, anti-slip effect (Figure 2)

The invention focuses on: the invention develops a novel preparation method of a bottomless cloth PU wet waterproof moisture-permeable and shock-proof anti-slip gas-permeable membrane by improving the production process of the suspension material, and the product prepared by the method is The porous material has not only can effectively improve the mechanical properties and gas permeability of the suspension and anti-slip material, but also through the improvement of the process, the base fabric can be recycled, and the drying temperature and time are reduced, thereby effectively reducing the production of the product. The waste of materials and energy in the process, low carbon and environmental protection, reducing the production and raw material cost of the products, and improving the market competitiveness of the products, the preparation method of the suspension and anti-slip materials has great market value. The waterproof, moisture-permeable, shock-absorbing and anti-slip gas-permeable membrane can be replaced in water and can be peeled off from the base fabric. It can be bonded to other materials on various composites for entanglement of various shock-absorbing and anti-slip materials. band, Such as: bicycle grip winding belt, tennis racket winding belt, badminton racket winding belt, baseball grip winding belt, table tennis rack winding belt, various parts that need to be wound and shockproof and slippery can be used.

The above is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention. Therefore, any minor modifications, equivalent changes and modifications made to the above embodiments in accordance with the technical spirit of the present invention are Still falling within the scope of the technical solution of the present invention.

Claims (7)

 A novel preparation method for a PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane without a bottom cloth, characterized in that the method comprises the following steps: a, pre-clothing treatment The material of the base cloth is TC cloth, the thickness of which is 20~35 filaments, the base cloth is immersed in clear water, and the base cloth after soaking is dried by rollers, so that the water content of the base cloth is 10%~20%; b, preparation of coating liquid First, the polyurethane initial slurry is prepared by mixing polyurethane: dimethylformamide at a mass ratio of 3:7; at 25 ° C, the viscosity of the polyurethane primary slurry is 250,000 CPS, using dimethylformyl Ammonia dilutes the viscosity of the polyurethane primary slurry to 10,000 CPS to prepare a polyurethane slurry; then, adds 1 to 1.5 to the diluted 100 parts by mass of the polyurethane slurry. a mass of dispersant, 1 to 1.5 parts by mass of a pore regulator, 1.5 to 2.0 parts by mass of an abrasion-resistant auxiliary, and 1 to 1.5 parts by mass of a water-removing aid; and uniformly mixing to obtain a coating liquid; c, coating on the machine The coating liquid is poured into a coater, and the coating liquid is applied to the base cloth by a coater, and the coating amount can be adjusted according to the required thickness of the leather; d, solidification film formation The base cloth coated with the coating liquid is placed in the coagulating liquid of the coagulation tank to be solidified into a film, the temperature of the coagulating liquid is 20 to 30 ° C, and the solidification time is 20 to 30 minutes; e, hot water cleaning The composite material consisting of the base fabric and the leather material attached to the base fabric is washed in water, the water temperature is 70-75 ° C, and the cleaning time is 15-20 minutes; f, dry The cleaned composite material is baked in an oven at a baking temperature of 60 to 70 ° C and baked for 30 to 40 minutes; g, release stripping After drying, the film layer and the base fabric in the composite material can be peeled off, the base fabric is recycled, and the film layer is separately rolled up to remember the shock-absorbing and breathable gas-permeable membrane. 2 . The novel preparation method of the PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane according to claim 1 , wherein the polyurethane in the coating liquid is composed of polyester polyol, diisocyanate and 1 -4 butanediol by mass percentage 100 : 20 : 10 reaction, the polyester polyol has a molecular weight of 3000 to 4000. 3 . The novel preparation method of the PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane according to claim 1 , wherein the dispersing agent is an anionic surfactant, and the anionic surfactant is polypropylene. The phenolic modifier is a nano silica modified epoxy resin; the wear resistant auxiliary agent is a silicon based abrasion modifier; and the water repellent auxiliary is a fluorocarbon alcohol resin. 4. The novel preparation method of the PU-free wet waterproof and moisture-proof suspension and anti-slip gas-permeable membrane according to claim 1, characterized in that the pore regulator and the water-repellent auxiliary agent are combined to make the handle and the waterproof and breathable function. Enhanced. 5 . The novel preparation method of the PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane according to claim 1 , wherein in the preparation process of the coating liquid, vacuum defoaming is required for 2 to 4 hours. The mixture was allowed to stand for 24 hours, and after being cooked, the coating machine was applied, and only one knife was applied to the base fabric. A novel preparation method of a PU-free wet waterproof and moisture-permeable suspension and anti-slip gas-permeable membrane according to claim 1, wherein the coagulating liquid in the coagulation tank contains 10% dimethylformamide. 7. The novel preparation method of the PU-free wet waterproof and moisture-proof suspension and anti-slip gas-permeable membrane according to claim 1, characterized in that: in the hot water cleaning process, four water tanks are used for cleaning, first to first The temperature of the three washing tanks is 70 ° C, the temperature of the fourth washing tank is 75 ° C, and the residual dimethylformamide in the combined materials after washing is reduced to less than 500 PPM.

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