CN119331301A - Washable, waterproof and breathable composite material, preparation method thereof, fabric and clothing - Google Patents

Washable, waterproof and breathable composite material, preparation method thereof, fabric and clothing Download PDF

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Publication number
CN119331301A
CN119331301A CN202411370083.3A CN202411370083A CN119331301A CN 119331301 A CN119331301 A CN 119331301A CN 202411370083 A CN202411370083 A CN 202411370083A CN 119331301 A CN119331301 A CN 119331301A
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Prior art keywords
waterproof
moisture
ceramic
ceramic particles
fabric
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CN202411370083.3A
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Chinese (zh)
Inventor
王冀
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Shenzhen Zhihang HeYi Advanced Materials Co.,Ltd.
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Shenzhen Tianji Fabric Co ltd
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Priority to CN202411370083.3A priority Critical patent/CN119331301A/en
Publication of CN119331301A publication Critical patent/CN119331301A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B11/00—Hosiery; Panti-hose
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B17/00—Selection of special materials for underwear
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D1/00—Garments
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
    • A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D23/00—Scarves; Head-scarves; Neckerchiefs
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/02—Layered materials
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/10—Impermeable to liquids, e.g. waterproof; Liquid-repellent
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/10—Impermeable to liquids, e.g. waterproof; Liquid-repellent
    • A41D31/102—Waterproof and breathable
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/14—Air permeable, i.e. capable of being penetrated by gases
    • A41D31/145—Air permeable, i.e. capable of being penetrated by gases using layered materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明公开了一种耐水洗防水透湿复合材料及其制备方法、防水透湿面料以及服饰。耐水洗防水透湿复合材料包括三层复合结构，陶瓷涂层包括第一陶瓷颗粒，亲水涂层包括第二陶瓷颗粒和亲水聚合物，第一陶瓷颗粒的粒径D50大于所述微孔膜的最大孔径，第二陶瓷颗粒的粒径D50小于1000nm，第一陶瓷颗粒的粒径D50与第二陶瓷颗粒的粒径D50比值为0.1~10。本申请的耐水洗防水透湿复合材料能够用于制备防水透气面料。本申请的耐水洗防水透湿复合材料在保持良好透气性能的同时，有效提升了亲水涂层的剥离强度和整个耐水洗防水透湿复合材料的耐水洗性能。

The present invention discloses a washable, waterproof and breathable composite material and a preparation method thereof, a waterproof and breathable fabric and clothing. The washable, waterproof and breathable composite material comprises a three-layer composite structure, a ceramic coating comprises first ceramic particles, a hydrophilic coating comprises second ceramic particles and a hydrophilic polymer, a particle size D50 of the first ceramic particles is greater than the maximum pore size of the microporous membrane, a particle size D50 of the second ceramic particles is less than 1000nm, and a ratio of the particle size D50 of the first ceramic particles to the particle size D50 of the second ceramic particles is 0.1 to 10. The washable, waterproof and breathable composite material of the present application can be used to prepare waterproof and breathable fabrics. The washable, waterproof and breathable composite material of the present application effectively improves the peel strength of the hydrophilic coating and the washability of the entire washable, waterproof and breathable composite material while maintaining good air permeability.

Description

Washable waterproof moisture-permeable composite material, preparation method thereof, fabric and clothes
Technical Field
The application relates to the technical field of textiles and clothes, in particular to a washable waterproof and moisture permeable composite material, a preparation method thereof, a fabric and clothes.
Background
The microporous membrane has higher hydrostatic pressure resistance and moisture permeability, and is widely applied to the preparation of waterproof moisture permeable fabrics, waterproof moisture permeable clothing and the like. When the waterproof moisture-permeable fabric is processed, after the water washing and soaping processes, the microporous structure on the microporous membrane is changed, and the permeability of the microporous membrane is increased, so that the hydrostatic pressure of the microporous membrane is seriously attenuated after the water washing, and the waterproof function is gradually lost.
In order to enhance the water-washing resistance of the microporous waterproof and moisture-permeable membrane, the traditional technology generally adopts the method of coating a polyurethane coating on the surface of the microporous membrane to form a polyurethane non-porous membrane with micron-sized thickness, and the composite membrane formed by compositing the polyurethane non-porous membrane and the microporous membrane can improve the water-washing resistance and resist washing for a certain number of times. The method for coating the polyurethane coating on the surface of the microporous membrane improves the water-washing resistance of the waterproof moisture-permeable fabric, but has the following problems that the polyurethane coating is coated on the surface of the microporous membrane with low surface energy, the peeling strength of the coating is low, the polyurethane coating on the composite membrane is eluted or delaminated with the microporous membrane after the water washing is carried out for a certain number of times, the hydrostatic pressure of the composite membrane is still reduced, the waterproof function is gradually lost, and in addition, the polyurethane coating forms a polyurethane non-porous membrane which can cause the micropores of the microporous membrane to be covered or filled, so that the moisture permeability and the air permeability of the composite membrane are obviously reduced compared with the microporous membrane.
Disclosure of Invention
Based on this, it is necessary to provide a water-resistant, waterproof, moisture-permeable composite material. The washable waterproof and moisture permeable composite material can remarkably improve the water resistance and keep good air permeability.
The embodiment of the application provides a washable waterproof and moisture permeable composite material.
The utility model provides a waterproof moisture-permeable composite of washing-resistant, includes microporous membrane, range upon range of set up in ceramic coating of microporous membrane one side or two sides and range upon range of set up in ceramic coating's hydrophilic coating, ceramic coating includes first ceramic granule, hydrophilic coating includes second ceramic granule and hydrophilic polymer, the particle diameter D50 of first ceramic granule is greater than the biggest aperture of microporous membrane, the particle diameter D50 of second ceramic granule is less than 1000nm, the particle diameter D50 ratio of first ceramic granule and second ceramic granule is 0.1~10, waterproof moisture-permeable composite of washing-resistant's moisture-permeable is greater than 5000 g/(m 2.24 h).
In some of these embodiments, the first ceramic particles and the second ceramic particles satisfy at least one of the following characteristics:
(1) The particle size D50 of the first ceramic particles is 100-1000 nm, preferably 400-600 nm;
(2) The particle size D50 of the second ceramic particles is 100 nm-1000 nm, preferably 200 nm-600 nm;
(3) The ratio of the particle size D50 of the first ceramic particles to the particle size D50 of the second ceramic particles is 1-3.
In some embodiments, the ratio of the particle size D50 to D10 of the first ceramic particles is 1 to 3, preferably 1 to 1.5;
The ratio of the particle size D50 to the particle size D10 of the second ceramic particles is 1-3, preferably 1-1.5.
In some of these embodiments, the microporous membrane comprises a polyolefin microporous membrane, optionally selected from a polyethylene microporous membrane or a polypropylene microporous membrane.
In some of these embodiments, the water-resistant, waterproof, moisture-permeable composite also satisfies at least one of the following characteristics:
(1) The thickness of the microporous membrane is 1-30 mu m, preferably 5-20 mu m;
(2) The porosity of the microporous membrane is more than 30%, preferably 40% -70%;
(3) The average pore diameter of the microporous membrane is smaller than 100nm, preferably 10 nm-50 nm;
(4) The moisture permeability of the washable waterproof moisture permeable composite material is not less than 50% of the moisture permeability of the microporous membrane;
(5) The specific surface area of the water-washing-resistant waterproof moisture-permeable composite material is 10m 2/g~60m2/g, preferably 40m 2/g~60m2/g;
(6) The initial hydrostatic pressure of the water-resistant waterproof moisture-permeable composite material is more than 20Kpa, preferably 150-200 Kpa, and the hydrostatic pressure after 5 times of water washing is reduced by not more than 40% of the initial value.
In some of these embodiments, the water-resistant, waterproof, moisture-permeable composite also satisfies at least one of the following characteristics:
(1) The first ceramic particles include one or more of alumina particles, titania particles, silica particles, and zirconia particles;
(2) The second ceramic particles include one or more of alumina particles, titania particles, silica particles, and zirconia particles;
(3) The hydrophilic polymer comprises one or more of polyurethane, polyamide and polyester.
In some of these embodiments, the water-resistant, waterproof, moisture-permeable composite also satisfies at least one of the following characteristics:
(1) The thickness of the ceramic coating is 0.5-3 mu m;
(2) The thickness of the hydrophilic coating is 0.5-3 mu m;
(3) The gram weight of the ceramic coating is 0.8g/m 2~1.2g/m2;
(4) The gram weight of the hydrophilic coating is 0.5g/m 2~3.2g/m2.
The embodiment of the application also provides a preparation method of the washable waterproof moisture-permeable composite material.
A preparation method of the water-washing-resistant waterproof and moisture-permeable composite material is used for preparing the water-washing-resistant waterproof and moisture-permeable composite material and comprises the following steps:
preparing ceramic slurry containing first ceramic particles, coating the ceramic slurry on one or two sides of a microporous membrane, and drying to form a ceramic coating;
Preparing composite slurry comprising second ceramic particles and hydrophilic polymer, coating the composite slurry on the ceramic coating, and curing to form the hydrophilic coating.
In some of these embodiments, the ceramic slurry comprises the following components, based on 100 parts by weight total:
1-5 parts by weight of first ceramic particles;
0.1-6 parts by weight of an adhesive;
0.1-1 parts by weight of a dispersing agent;
and the balance of deionized water.
In some of these embodiments, the composite slurry comprises the following components, based on 100 parts by weight total:
10-20 parts by weight of second ceramic particles;
2-8 parts of micropore lignin;
10-20 parts by weight of hydrophilic polymer
0.2-0.6 Parts by weight of a dispersing agent;
2.8-5.0 parts by weight of a cross-linking agent;
The balance of solvent.
The embodiment of the application also provides the waterproof moisture-permeable fabric.
The waterproof and moisture permeable fabric comprises a fabric and the waterproof and moisture permeable composite material, or the waterproof and moisture permeable composite material prepared by the preparation method, wherein the waterproof and moisture permeable composite material is arranged on the surface of one side of the fabric along the thickness direction of the fabric.
In some embodiments, the moisture permeability of the waterproof moisture permeable fabric is greater than 5000 g/(m 2.24 h), the initial hydrostatic pressure of the waterproof moisture permeable fabric is greater than 20KPa, and the hydrostatic pressure of the waterproof moisture permeable fabric after 5 times of washing is not reduced by more than 40% of the initial value.
The embodiment of the application also provides a preparation method of the waterproof moisture-permeable fabric.
A preparation method of a waterproof and moisture permeable fabric comprises the following steps:
Laminating and compounding a microporous film on a surface of one side of the fabric in a thickness direction thereof, and
The ceramic coating and the hydrophilic coating of the water-washing-resistant waterproof and moisture-permeable composite material are prepared according to the preparation method of the water-washing-resistant waterproof and moisture-permeable composite material.
In some of these embodiments, laminating the microporous membrane to the fabric comprises the steps of:
And coating polyurethane hot melt adhesive on the fabric by using a rotary screen printing roller, distributing the polyurethane hot melt adhesive on the fabric in a dot form, covering the surface of the fabric with the polyurethane hot melt adhesive with the microporous membrane, and curing at 20-30 ℃ for at least 48 hours after lamination.
The embodiment of the application also provides a piece of clothing.
The garment is at least partially made of the waterproof and moisture-permeable fabric or the waterproof and moisture-permeable fabric prepared by the preparation method.
In some of these embodiments, the apparel includes, but is not limited to, apparel, socks, hats, scarves, facial tissues, gloves, and masks.
The waterproof moisture-permeable composite material comprises the microporous membrane, the ceramic coating and the hydrophilic coating, wherein ceramic particles are adhered to the microporous membrane, and then the hydrophilic coating is coated, so that the situation that the original microporous structure on the microporous membrane is covered and shielded by filling is avoided, and the peeling strength of the hydrophilic coating and the waterproof performance of the whole waterproof moisture-permeable composite material are effectively improved by adopting the interaction of the ceramic coating and the hydrophilic coating while the good air permeability of the microporous membrane is maintained.
Further, the second ceramic particles in the hydrophilic coating interact with the hydrophilic polymer to form the micropore structure, so that the strength of the hydrophilic coating can be effectively improved, the air permeability is improved, the moisture permeability is increased, and the comfort of a wearer is improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below. It is evident that the figures in the following description are only some embodiments of the application, from which other figures can be obtained without inventive effort for a person skilled in the art.
For a more complete understanding of the present application and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings. Wherein like reference numerals refer to like parts throughout the following description.
FIG. 1 is a schematic view of a scanning electron microscope of a microporous membrane according to example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a microporous membrane with a ceramic coating and a hydrophilic coating according to example 1 of the present invention;
FIG. 3 is a schematic view of a scanning electron microscope photograph of a microporous membrane compounded with a polyurethane hot melt adhesive according to comparative example 1.
Detailed Description
In the description of the present invention, the meaning of a number is one or more, the meaning of a number is two or more, and greater than, less than, exceeding, etc. are understood to exclude the present number, and the meaning of a number is understood to include the present number. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
Herein, "optional" refers to the presence or absence of the possibility, i.e., to any one of the two juxtaposed schemes selected from "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent. In the present application, "optionally containing", and the like are described, meaning "containing or not containing". "optional component X" means that component X is present or absent, or that component X is present or absent.
In the present invention, the sum of the parts of the components in the composition may be 100 parts by weight, if not stated to the contrary. The percentages (including weight percent) of the present invention are based on the total weight of the composition, unless otherwise indicated, and in addition, "wt%" herein means mass percent.
In the present application, a numerical range (i.e., a numerical range) is referred to, and, unless otherwise indicated, a distribution of optional values within the numerical range is considered to be continuous and includes two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range, and each numerical value between the two numerical endpoints. When a numerical range merely points to integers within the numerical range, unless expressly stated otherwise, both endpoints of the numerical range are inclusive of the integer between the two endpoints, and each integer between the two endpoints is equivalent to the integer directly recited. When multiple numerical ranges are provided to describe a feature or characteristic, the numerical ranges may be combined. In other words, unless otherwise indicated, the numerical ranges disclosed in this application are to be understood to include any and all subranges subsumed therein. The "numerical value" in the numerical interval may be any quantitative value, such as a number, a percentage, a proportion, or the like. "numerical interval" allows to broadly include quantitative intervals such as percentage intervals, proportion intervals, ratio intervals, etc.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The embodiment of the application provides a water-washing-resistant waterproof moisture-permeable composite material, which solves at least one of the problems that the peel strength of a coating is low, the polyurethane coating on the composite film is eluted or layered with the microporous film after washing for a certain number of times, the hydrostatic pressure of the composite film is still reduced and the waterproof function is gradually lost, and the polyurethane coating forms a polyurethane non-porous film which can cause the coverage and filling of micropores of the microporous film to cause the moisture permeability and the air permeability of the composite film to be obviously reduced compared with the microporous film. The water-wash-resistant waterproof moisture-permeable composite material will be described below with reference to examples. The washable waterproof moisture-permeable composite material can be used for waterproof clothing, sports goods preparation and other purposes.
The waterproof moisture-permeable composite material comprises a microporous membrane, ceramic coatings and a hydrophilic coating, wherein the ceramic coatings are arranged on one side or two sides of the microporous membrane in a laminated mode, the hydrophilic coating is arranged on the ceramic coatings in a laminated mode, the ceramic coatings comprise first ceramic particles, the hydrophilic coating comprises second ceramic particles and a hydrophilic polymer, the particle size D50 of the first ceramic particles is larger than the largest pore diameter of the microporous membrane, the particle size D50 of the second ceramic particles is smaller than 1000nm, the ratio of the particle size D50 of the first ceramic particles to the particle size D50 of the second ceramic particles is 0.1-10, and the moisture permeability of the waterproof moisture-permeable composite material is larger than 5000 g/(m 2.24 h). The lamination arrangement in the present application includes lamination in position and a certain connection relationship between two adjacent layers.
The microporous membrane such as polyolefin microporous membrane has the characteristics of high moisture permeability and high hydrostatic pressure, can be applied to waterproof moisture permeable fabric, but the microporous structure of the single-component polyolefin microporous membrane is easy to be damaged, the hydrostatic pressure attenuation after washing is serious, and based on the microporous membrane, the ceramic coating can keep the original micropores of the microporous membrane by compounding the ceramic coating and the hydrophilic coating on the surface of the microporous membrane, the waterproof and moisture permeable composite material has good air permeability, and the interaction of the ceramic coating and the hydrophilic coating is adopted to effectively improve the peeling strength of the hydrophilic coating and the water-washing resistance of the whole waterproof and moisture permeable composite material, so that the waterproof and moisture permeable composite material can be used for preparing waterproof and moisture permeable fabrics, and the problem of hydrostatic pressure attenuation of the waterproof and moisture permeable fabrics after washing in the traditional technology is solved.
In some embodiments, the particle size D50 of the first ceramic particles is 100nm to 1000nm, preferably 400nm to 600nm. The value of the particle diameter D50 of the first ceramic particles includes, but is not limited to, 100nm, 200nm, 400nm, 500nm, 600nm, 700nm, 900nm, 1000nm or a range between any two of the foregoing.
In some embodiments, the particle size D50 of the second ceramic particles is 100nm to 1000nm, preferably 200nm to 600nm. The value of the particle diameter D50 of the second ceramic particles includes, but is not limited to, 100nm, 200nm, 400nm, 500nm, 600nm, 700nm, 900nm, 1000nm or a range between any two of the foregoing.
In some embodiments, the ratio of the particle size D50 of the first ceramic particles to the particle size D50 of the second ceramic particles is 0.1-10, preferably 1-3. The ratio of the particle diameter D50 of the first ceramic particles to the particle diameter D50 of the second ceramic particles includes, but is not limited to, 0.1, 0.5, 1, 1.1, 1.3, 1.5, 2, 2.5, 3, 4, 5, 7, 9, 10 or a range between any two of the foregoing.
In some of these embodiments, the ratio of the particle size D50 of the first ceramic particles to D10 is 1 to 3, preferably 1 to 1.5, and more preferably 1 to 1.2. Such as 1, 1.05, 1.1, 1.2, 1.3, 1.5, 2, 2.5, 3 or ranges between any two of the foregoing. If the ratio of D50 to D10 is too large, it indicates that D10 is small, which tends to cause the first ceramic particles to enter the micropores of the microporous membrane, block the micropores, and reduce the moisture permeability.
The ratio of the particle diameter D50 of the second ceramic particles to D10 is 1 to 3, preferably 1 to 1.5, more preferably 1 to 1.2, such as 1, 1.05, 1.1, 1.2, 1.3, 1.5, 2, 2.5, 3 or a range between any two of the foregoing. If the ratio of D50 to D10 is too large, it indicates that the particle size distribution of the second ceramic particles is not uniform, thereby affecting the peel strength and moisture permeability of the hydrophilic coating. In the application, the characteristics of the D50/D10 are used for highlighting the average particle size of the first ceramic particles and the second ceramic particles, and the closer the ratio of the D50/D10 to 1, the better the effect is proved to be. In the present application, the particle diameters D50 and D10 of the first ceramic particles are preferably in the range of 1 to 1.5, more preferably 1 to 1.2, and the ratio of the particle diameters D50 and D10 of the second ceramic particles is 1 to 3, preferably 1 to 1.5, more preferably 1 to 1.2, i.e., the closer to 1 the more preferable.
In some of these embodiments, the microporous membrane comprises a polyolefin microporous membrane.
In some of these embodiments, the microporous membrane comprises one of a polyethylene microporous membrane (PE membrane), a polypropylene microporous membrane (PP membrane), or a microporous membrane of a blend of polyethylene and polypropylene as raw materials.
In some of these embodiments, the microporous membrane has a thickness of 1 μm to 30 μm. Preferably, the microporous membrane has a thickness of 5 μm to 20 μm. The thickness of the microporous membrane may be not limited to 1 μm, 3 μm, 5 μm, 9 μm, 10 μm, 11 μm, 12 μm, 15 μm, 17 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm or a range between any two of the foregoing. If the thickness of the microporous membrane is too low, the strength is too low, the hydrostatic pressure is too low, and the use requirement is not met, and if the thickness is too high, the moisture permeability is reduced, and the use requirement is not met.
In some of these embodiments, the microporous membrane has a porosity of greater than 30%. Preferably, the microporous membrane has a porosity of 40% -70%. The porosity of the microporous membrane includes, but is not limited to, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or a range between any two of the foregoing. If the porosity of the microporous membrane is too low, the moisture permeability is low, and the use requirement is not satisfied, and if the porosity is too high, the hydrostatic pressure is too low.
In some of these embodiments, the microporous membrane has an average pore size of less than 100nm, preferably 10nm to 70nm. The pore diameter of the microporous membrane is not limited to 10nm, 20nm, 25nm, 30nm, 40nm, 50nm, 60nm, 70nm or a range between any two of the foregoing. If the pore diameter of the microporous membrane is too low, the moisture permeability is low, and the use requirement is not met, and if the pore diameter is too large, the hydrostatic pressure is too low.
The microporous membrane with the thickness, the porosity range and the average pore diameter is selected, the moisture permeability is 10000 (g/m 2.24h) ~15000(g/m2.24 h), and the initial hydrostatic pressure is more than 20Kpa, preferably 150-200 Kpa.
In some of these embodiments, the moisture vapor transmission rate of the water-resistant, water-vapor permeable composite is not less than 50%, such as 50%, 55%, 60%, 70%, etc., of the moisture vapor transmission rate of the microporous membrane.
In some of these embodiments, the specific surface area of the water-resistant, moisture-permeable composite is 10m 2/g~60m2/g. Preferably, the specific surface area of the water-resistant waterproof moisture-permeable composite material is 40m 2/g~60m2/g. The specific surface area of the water-resistant waterproof moisture-permeable composite material has a value of 10m 2/g、20m2/g、30m2/g、40m2/g、50m2/g、60m2/g or a range between any two of the above.
In some embodiments, the initial hydrostatic pressure of the water resistant, water vapor permeable composite is greater than 20Kpa, preferably 150 Kpa to 200Kpa, such as 20Kpa, 50Kpa, 80 Kpa, 100 Kpa, 150 Kpa, 160 Kpa, 170 Kpa, 180 Kpa, 190 Kpa, 200Kpa, or a range therebetween. The hydrostatic pressure after washing for 5 times is reduced by not more than 40% of the initial value.
In some of these embodiments, the first ceramic particles comprise a mixture of one or more of alumina particles, titania particles, silica particles, and zirconia particles.
In some of these embodiments, the second ceramic particles comprise a mixture of one or more of alumina particles, titania particles, silica particles, and zirconia particles.
In some of these embodiments, the hydrophilic polymer comprises one or more of polyurethane, polyamide, and polyester. According to the application, the second ceramic particles and the hydrophilic polymer are added into the hydrophilic coating, so that the microporous structure formed by the second ceramic particles and the hydrophilic polymer can effectively improve the strength of the hydrophilic coating, improve the air permeability, increase the moisture permeability and improve the comfort of a wearer.
The embodiment of the application provides a preparation method of a washable waterproof and moisture permeable composite material.
In this example, the respective reaction steps may be performed in the order described herein or may be performed in a different order than described herein unless otherwise indicated. For example, other steps may be included between the respective reaction steps, and the order of the reaction steps may be appropriately changed. This can be determined by the skilled person based on routine knowledge and experience. Preferably, the reaction process in this example is performed sequentially.
A preparation method of a washable waterproof and moisture permeable composite material comprises the following steps:
S11, preparing ceramic slurry containing first ceramic particles, coating the ceramic slurry on one or both sides of the microporous membrane, and drying to form a ceramic coating.
S12, preparing composite slurry comprising second ceramic particles and hydrophilic polymer, coating the composite slurry on the ceramic coating, and curing to form the hydrophilic coating.
In some of these embodiments, the ceramic slurry comprises the following components, based on 100 parts by weight total:
1-5 parts by weight of first ceramic particles;
0.1-6 parts by weight of an adhesive;
0.1-1 parts by weight of a dispersing agent;
and the balance of deionized water.
In some of these embodiments, the composite slurry comprises the following components, based on 100 parts by weight total:
10-20 parts by weight of second ceramic particles;
2-8 parts of micropore lignin;
10-20 parts by weight of hydrophilic polymer
0.2-0.6 Parts by weight of a dispersing agent;
2.8-5.0 parts by weight of a cross-linking agent;
The balance of solvent.
In some of these embodiments, the adhesive comprises a combination of any one or more of acrylate, polyurethane, epoxy, vinyl acetate, modified epoxy, hydroxypropyl methylcellulose, ethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol.
In some of these embodiments, the dispersant comprises any one or more of polyvinylpyrrolidone, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyethylene glycol, hydroxypropyl methylcellulose, polyvinyl alcohol, N-dimethylformamide, N-methylpyrrolidone, sodium carboxymethyl cellulose, ammonium polyacrylate salts, ethylene oxide, ethylene glycol, and isopropyl alcohol.
In some of these embodiments, the crosslinker comprises a combination of any one or more of blocked isocyanate, triallyl cyanurate, trimethylolpropane triacrylate.
In some embodiments, the solvent comprises deionized water or a mixed solution of butanone and toluene, wherein the ratio of the butanone to the toluene in parts by weight is (10-13) to (10-21).
In some embodiments, in step S11 of the method for preparing the water-washable waterproof and moisture-permeable composite material, a micro-gravure roll coating method is used during coating.
In some embodiments, in step S11 of the preparation method of the water-washing-resistant waterproof moisture-permeable composite material, the water-washing-resistant waterproof moisture-permeable composite material is dried at a temperature of 60-90 ℃ for 1-2 min during drying treatment.
In some embodiments, in step S11 of the method for preparing the water-resistant, water-resistant and moisture-permeable composite, the net weight gain of the microporous membrane after the drying treatment is controlled to be 0.8g/m 2~1.2g/m2. The above-mentioned net weight increase refers to the weight of the ceramic coating layer formed by the ceramic slurry coated on the microporous membrane after drying.
In some of these embodiments, in step S12 of the method for preparing a water-washable waterproof and moisture-permeable composite material, the composite slurry is coated on the ceramic coating layer using a float-knife coater.
In some embodiments, in step S12 of the method for preparing a water-washable waterproof and moisture-permeable composite material, the viscosity of the composite slurry is controlled to be 12000 mpa.s-18000 mpa.s.
In some embodiments, in step S12 of the method for preparing a water-washable waterproof and moisture-permeable composite material, the curing temperature is 90 ℃ to 160 ℃ and the curing time is 3min to 5min during the curing treatment.
In some of these embodiments, in step S12 of the method for preparing a water-resistant, moisture-permeable composite, the net weight gain of the microporous membrane after the curing treatment is controlled to be 1.8g/m 2~2.2g/m2. The net weight of the microporous membrane is the weight of the hydrophilic coating formed by the composite slurry coated on the microporous membrane after curing.
The embodiment of the application provides a waterproof moisture-permeable fabric.
The waterproof and moisture permeable fabric comprises a fabric and the waterproof and moisture permeable composite material, or the waterproof and moisture permeable composite material prepared by the preparation method of the waterproof and moisture permeable composite material, wherein the waterproof and moisture permeable composite material is laminated on the surface of one side of the fabric along the thickness direction of the fabric.
In some embodiments, the moisture permeability of the waterproof moisture permeable fabric prepared by the preparation method of the water-resistant waterproof moisture permeable composite material is more than 5000 (g/m 2.24 h), the initial hydrostatic pressure of the waterproof moisture permeable fabric is more than 20KPa, the hydrostatic pressure of the waterproof moisture permeable fabric after 5 times of water washing is not more than 40% of the initial value, and the hydrostatic pressure is tested according to national standard GB/T8629.
The embodiment of the application provides a preparation method of a waterproof and moisture permeable fabric.
In this example, the respective reaction steps may be performed in the order described herein or may be performed in a different order than described herein unless otherwise indicated. For example, other steps may be included between the respective reaction steps, and the order of the reaction steps may be appropriately changed. This can be determined by the skilled person based on routine knowledge and experience. Preferably, the reaction process in this example is performed sequentially.
A preparation method of a waterproof and moisture permeable fabric comprises the following steps:
S21, laminating and compounding the microporous membrane on the surface of one side of the fabric along the thickness direction.
S22, preparing a ceramic coating and a hydrophilic coating of the water-washable waterproof and moisture-permeable composite material according to the preparation method of the water-washable waterproof and moisture-permeable composite material.
In some of these embodiments, in step S21, laminating and compounding the microporous membrane to the fabric comprises the steps of:
And coating polyurethane hot melt adhesive on the fabric by using a rotary screen printing roller, distributing the polyurethane hot melt adhesive on the fabric in a dot form, covering the surface of the fabric with the polyurethane hot melt adhesive with a microporous membrane, and curing at 20-30 ℃ for at least 48 hours after lamination.
In some of these embodiments, the polyurethane hot melt adhesive is a moisture-curable polyurethane hot melt adhesive.
In some of these embodiments, the order of steps S21 and S22 may be reversed.
An embodiment of the application provides a garment.
The clothing is prepared from the waterproof moisture-permeable fabric at least at part of the clothing or the waterproof moisture-permeable fabric prepared by the preparation method of the waterproof moisture-permeable fabric.
In some of these embodiments, apparel includes, but is not limited to, apparel, socks, hats, scarves, facial tissues, gloves, and masks.
The present application will be described below with reference to examples.
Unless otherwise specified, the materials involved in the embodiments of the present invention are all conventional materials in the art and are commercially available, and in particular, some of the information about the materials involved are as follows:
The first ceramic particles are specifically alumina ceramic particles, and are purchased from Shandong national porcelain functional materials Co., ltd;
The second ceramic particles are specifically alumina ceramic particles and are purchased from Shandong national porcelain functional materials Co., ltd;
Micropore lignin, purchased from Feicheng Living cellulose Limited;
Hydrophilic polymers, in particular polyurethanes, available from Hangao (China) investment Co., ltd;
The microporous membrane is specifically a PE microporous membrane or a PP microporous membrane, and is purchased from Shenzhen Star source materials and technologies Co., ltd.
Example 1
This example 1 provides a waterproof moisture permeable fabric.
The waterproof moisture permeable fabric of this example 1 was prepared by the following preparation method. The preparation method of the waterproof moisture-permeable fabric comprises the following steps:
1) The PE microporous membrane is selected as the microporous membrane, the thickness of the microporous membrane is 12 mu m, the porosity is 44%, the average pore diameter is 21nm, the maximum pore diameter is 75nm, the hydrostatic pressure is 150KPa, the moisture permeability is 11000 (g/m 2.24 h), and the scanning electron microscope photograph of the microporous membrane is shown in figure 1. And (3) coating polyurethane hot melt adhesive on the polyester woven fabric by using a rotary screen printing roller, coating the polyurethane hot melt adhesive on the fabric in a dot form, covering the surface of the fabric with the polyurethane hot melt adhesive with a microporous membrane, and curing for 48 hours at a temperature of 30 ℃ after lamination to realize the composite connection of the microporous membrane on the fabric.
2) And (3) adding 89 parts of deionized water into 5 parts of first ceramic particles with the particle size D50 of 500nm, 5 parts of acrylate adhesives and 1 part of ammonium polyacrylate dispersing agents, and mixing and stirring for 20min at the rotating speed of 1000 revolutions per minute in a double planetary mixer to obtain ceramic slurry. Wherein the ratio of the particle diameter D50 of the first ceramic particles to the particle diameter D10 is 1.1.
3) And (3) coating the ceramic slurry in the step (2) on the microporous membrane by adopting a micro-concave roller coating method, and drying at 60 ℃ for 2min to form a ceramic coating. The net weight gain of the microporous membrane after the drying treatment is controlled to be 1g/m 2. The microporous membrane compounded with the ceramic coating has the moisture permeability of 11090 (g/m 2.24 h), and the moisture permeability of the microporous membrane is not reduced, which indicates that the microporous structure on the microporous membrane is not completely filled and blocked, and the microporous membrane compounded with the ceramic coating has good air permeability.
4) Mixing and stirring 20 parts of aqueous polyurethane coating adhesive with 59.5 parts of solvent ionized water, sequentially adding 10 parts of second ceramic particles with the particle size D50 of 100nm, 5 parts of microporous lignin and 0.5 part of ammonium polyacrylate dispersant, stirring for 20min, adding 5 parts of cross-linking agent blocked isocyanate, and uniformly stirring to obtain composite slurry, wherein the viscosity of the composite slurry is controlled to be between 12000mPa.S and 16000 mPa.S. Wherein the ratio of the particle diameter D50 of the second ceramic particles to the particle diameter D10 is 1.1.
5) And (3) coating the composite slurry in the step (4) on the ceramic coating by adopting a floating knife type coating machine, curing at 90 ℃ for 5min, controlling the net weight gain of the microporous membrane to be 2g/m 2 after curing, and obtaining the hydrophilic coating, wherein the scanning electron microscope photograph of the microporous membrane compounded with the ceramic coating and the hydrophilic coating is shown in figure 2.
Example 2
The method for preparing the waterproof moisture-permeable fabric of example 2 is basically the same as that of example 1, except that in the waterproof moisture-permeable fabric of example 2, the particle diameter D50 of the second ceramic particles in the composite slurry of step 4) is 200nm.
Example 3
The method for preparing the waterproof moisture-permeable fabric of example 3 is basically the same as that of example 1, except that in the waterproof moisture-permeable fabric of example 3, the particle diameter D50 of the second ceramic particles in the composite slurry of step 4) is 500nm.
Example 4
The method for preparing the waterproof moisture-permeable fabric of example 4 is basically the same as that of example 1, except that in the waterproof moisture-permeable fabric of example 4, the particle diameter D50 of the second ceramic particles in the composite slurry of step 4) is 800nm.
Example 5
The preparation method of the waterproof moisture-permeable fabric of example 5 is basically the same as that of example 1, except that in the waterproof moisture-permeable fabric of example 5, the particle diameter D50 of the second ceramic particles in the composite slurry of step 4) is 1000nm.
Example 6
The method for producing the waterproof moisture-permeable fabric of example 6 is substantially the same as that of example 3, except that in the waterproof moisture-permeable fabric of example 6, the particle diameter D50 of the first ceramic particles in the ceramic slurry of step 1) is 100nm.
Example 7
The method for producing the waterproof moisture-permeable fabric of example 7 is substantially the same as that of example 3, except that in the waterproof moisture-permeable fabric of example 7, the particle diameter D50 of the first ceramic particles in the ceramic slurry of step 1) is 400nm.
Example 8
The method for producing the waterproof moisture-permeable fabric of example 8 is substantially the same as that of example 3, except that in the waterproof moisture-permeable fabric of example 8, the particle diameter D50 of the first ceramic particles in the ceramic slurry of step 1) is 600nm.
Example 9
The method for producing the waterproof moisture-permeable fabric of example 9 is substantially the same as that of example 3, except that in the waterproof moisture-permeable fabric of example 9, the particle diameter D50 of the first ceramic particles in the ceramic slurry of step 1) is 800nm.
Example 10
The preparation method of the waterproof moisture-permeable fabric of example 10 is basically the same as that of example 3, except that in the waterproof moisture-permeable fabric of example 10, the ratio of the particle size D50 of the first ceramic particles to the particle size D10 in the ceramic slurry of step 1) is 3, and the ratio of the particle size D50 of the second ceramic particles to the particle size D10 in the composite slurry of step 4) is 3.
Comparative example 1
The PE microporous membrane of example 1 was used, polyurethane hot melt adhesive was coated on a polyester woven fabric using a rotary screen printing roller, the polyurethane hot melt adhesive was coated on the fabric in a dot form, the microporous membrane was coated on the surface of the fabric having the polyurethane hot melt adhesive, and after lamination, the microporous membrane was cured at 30 ℃ for 48 hours, so that the microporous membrane was compositely connected to the fabric, and a waterproof moisture permeable fabric was obtained, as shown in FIG. 3.
Comparative example 2
Coating polyurethane hot melt adhesive on polyester woven fabric by using a rotary screen printing roller by adopting the PE microporous membrane of the embodiment 1, coating the polyurethane hot melt adhesive on the fabric in a dot form, covering the surface of the fabric with the polyurethane hot melt adhesive with the microporous membrane, and curing for 48 hours at 30 ℃ after lamination to realize the composite connection of the microporous membrane on the fabric;
And uniformly coating the polyurethane coating adhesive emulsion on the film surface of the composite fabric by using a knife coater. The polyurethane coating adhesive emulsion comprises 100 parts of aqueous polyurethane coating adhesive, 100 parts of deionized water and 5 parts of cross-linking agent. The dry weight gain of the coating is controlled to be 2g/m 2, the curing temperature is 90 ℃ and the curing time is 5 minutes. The polyurethane coating is cured. And obtaining the waterproof moisture permeable fabric with the surface coated with the polyurethane protective layer.
Comparative example 3
The waterproof moisture-permeable fabric of comparative example 3 was prepared in substantially the same manner as in example 3, except that in the waterproof moisture-permeable fabric of comparative example 3, steps 2) and 3) were not included, i.e., no ceramic coating was included, and the hydrophilic coating including the second ceramic particles was directly coated on the microporous membrane after step 1).
Comparative example 4
The preparation method of the waterproof and moisture-permeable fabric of comparative example 4 is basically the same as that of example 3, except that in the waterproof and moisture-permeable fabric of comparative example 4, the composition of the composite slurry in step 4) is 100 parts of aqueous polyurethane coating glue, 100 parts of deionized water, 5 parts of cross-linking agent and no second ceramic particles are contained.
Performance test:
(1) Appearance the waterproof moisture permeable material provided in example 1 was tested using a ZEISS scanning electron microscope, and a scanning electron microscope image of the surface of the composite separator provided in example 1 was obtained by the test and is shown in fig. 1.
(2) The porosity is detected by adopting Bei Shide BSD-660 high-performance specific surface area and aperture analyzer according to national standard GB/T36363-2018.
(3) Moisture permeability the waterproof moisture permeable fabric was tested according to GB/T12704.1.
(4) Hydrostatic pressure-test according to GB/T4744-2013.
(5) Hydrostatic pressure after 5 washes-test according to GB/T4744-2013 after 5 washes according to national standard GB/T8629.
(6) Pore size is tested according to ASTM F316-03 (2019).
(7) Peel strength test according to ISO 02111-2000.
(8) Specific surface area the test was carried out according to GB/T19587-2017.
The test results are shown in table 1:
TABLE 1
As can be seen from examples 1 to 10, the moisture permeability of the waterproof moisture permeable fabric prepared by the preparation method of the waterproof moisture permeable fabric is more than 9000 (g/m 2.24 h), the initial hydrostatic pressure of the waterproof moisture permeable fabric is more than 150KPa, and the hydrostatic pressure of the waterproof moisture permeable fabric after 5 times of water washing is not more than 40% of the initial value. Further, in example 10, the ratio of the particle size D50 of the first ceramic particles to D10 in the ceramic slurry of step 1) is 3, the ratio of the particle size D50 of the second ceramic particles to D10 in the composite slurry of step 4) is 3, the ratio of the particle size D50 of the first ceramic particles to D10 in example 3 is 1, the ratio of the particle size D50 of the second ceramic particles to D10 is 1, and it is understood from comparison of example 10 and example 3 that the moisture permeability of example 10 is 10600 (g/m 2.24 h) is reduced because a part of the first ceramic particles having small particle sizes enter the pore diameter to block micropores, resulting in a reduction in moisture permeability, and therefore, the ratio of the D50 of the first ceramic particles to D10 and the ratio of the D50 of the second ceramic particles to D10 are most preferably close to the ratio of 1.
As is clear from the comparison between example 1 and comparative example 1, comparative example 1 has no ceramic coating or hydrophilic coating, and therefore, the fabric prepared therefrom has a small specific surface area, and the hydrostatic pressure after 5 times of washing water is reduced to 5KPa.
As is apparent from comparison of example 1 with comparative example 2, in comparative example 2, the second ceramic particles were absent, and therefore, the hydrophilic coating formed by the composite slurry had no microporous structure, and the hydrophilic coating filled the ceramic coating and the microporous structure on the microporous membrane, resulting in a fabric formed by final compounding having a moisture permeability of 3200 (g/m 2.24 h) which is much smaller than 10920 (g/m 2.24 h) of example 1, and the composite slurry of comparative example 2, because the second ceramic particles were not added, the hydrophilic coating of comparative example 1 lacks the microporous structure formed by the powder, and therefore, it was difficult to raise the strength of the hydrophilic coating, and also resulted in a decrease in the air permeability of the produced fabric, and a significant decrease in the moisture permeability as compared with example 1. In addition, the fabric of comparative example 2 had an initial hydrostatic pressure of 175KPa, and the waterproof moisture permeable fabric of example 1 had an initial hydrostatic pressure of 189KPa, which are substantially equivalent to each other, but after 5 times of washing, the waterproof moisture permeable fabric of example 1 had a hydrostatic pressure of 167KPa, and the fabric of comparative example 2 had a hydrostatic pressure of 90KPa, and therefore, the structural strength of the fabric of comparative example 2 was also greatly reduced as compared with that of example 1.
As can be seen from the comparison of example 1 and comparative example 3, the lack of the ceramic coating in comparative example 3, the coating of the hydrophilic coating containing the second ceramic particles directly on the microporous membrane after step 1) resulted in an increase in the specific surface area of the fabric, and the hydrophilic coating, in the absence of the ceramic coating, filled and covered the microporous structure on the microporous membrane, resulting in a final composite fabric having a moisture transmission of 5900 (g/m 2.24 h) which is much less than 10920 (g/m 2.24 h) of example 1, and in addition, the initial hydrostatic pressure of the fabric of comparative example 3 was 162KPa, the performance of the fabric was lower than that of example 1, and the hydrostatic pressure of the fabric of comparative example 3 was 97KPa after 5 times of water washing, and therefore the structural strength of the fabric of comparative example 3 was also greatly reduced as compared with that of example 1.
As can be seen from the comparison between the example 3 and the comparative example 4, the composition of the composite slurry in the step 4) of the comparative example 4 is that 100 parts of the aqueous polyurethane coating glue, 100 parts of deionized water and 5 parts of the cross-linking agent do not contain the second ceramic particles, the hydrophilic coating formed by the composite slurry does not have a microporous structure, the hydrophilic coating fills and covers the ceramic coating and the microporous structure on the microporous membrane, the moisture permeability of the fabric formed by the final composite is 4700 (g/m 2.24 h), which is far smaller than 11700 (g/m 2.24 h) of the example 3, and the moisture permeability of the fabric is also greatly reduced compared with the example 3 because the hydrophilic coating of the comparative example 3 lacks the microporous structure formed by powder without the second ceramic particles and the microporous lignin, and the strength of the hydrophilic coating is difficult to be improved. In addition, the initial hydrostatic pressure of the fabric of comparative example 3 was 170KPa, the initial hydrostatic pressure of the waterproof and moisture permeable fabric of example 3 was 195KPa, and both were basically equivalent, but after 5 times of washing, the hydrostatic pressure of the waterproof and moisture permeable fabric of example 3 was 185KPa, and the hydrostatic pressure of the fabric of comparative example 3 was 65KPa, and thus the structural strength of the fabric of comparative example 3 was also greatly reduced compared to that of example 3.
In summary, the water-washing-resistant waterproof and moisture-permeable composite material comprises the microporous membrane, the ceramic coating and the hydrophilic coating, wherein ceramic particles are adhered to the microporous membrane, and then the hydrophilic coating is coated, so that the situation that the original microporous structure on the microporous membrane is completely filled and covered and shielded is avoided, and the peeling strength of the hydrophilic coating and the water-washing-resistant performance of the whole water-washing-resistant waterproof and moisture-permeable composite material are effectively improved by adopting the interaction of the ceramic coating and the hydrophilic coating while the good air permeability of the microporous membrane is maintained.
In the foregoing embodiments, the descriptions of the embodiments are emphasized, and for parts of one embodiment that are not described in detail, reference may be made to related descriptions of other embodiments.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (14)

1. The waterproof moisture-permeable composite material is characterized by comprising a microporous membrane, ceramic coatings arranged on one side or two sides of the microporous membrane in a lamination manner and a hydrophilic coating arranged on the ceramic coatings in a lamination manner, wherein the ceramic coatings comprise first ceramic particles, the hydrophilic coating comprises second ceramic particles and a hydrophilic polymer, the particle size D50 of the first ceramic particles is larger than the maximum aperture of the microporous membrane, the particle size D50 of the second ceramic particles is smaller than 1000nm, the ratio of the particle size D50 of the first ceramic particles to the particle size D50 of the second ceramic particles is 0.1-10, and the moisture permeability of the waterproof moisture-permeable composite material is larger than 5000 g/(m 2.24 h).
2. The water resistant, waterproof and moisture permeable composite according to claim 1, wherein the first ceramic particles and the second ceramic particles satisfy at least one of the following characteristics:
(1) The particle size D50 of the first ceramic particles is 100-1000 nm, preferably 400-600 nm;
(2) The particle size D50 of the second ceramic particles is 100 nm-1000 nm, preferably 200 nm-600 nm;
(3) The ratio of the particle size D50 of the first ceramic particles to the particle size D50 of the second ceramic particles is 1-3.
3. The water-resistant, waterproof and moisture-permeable composite according to claim 1, wherein,
The ratio of the particle size D50 to the particle size D10 of the first ceramic particles is 1-3, preferably 1-1.5;
The ratio of the particle size D50 to the particle size D10 of the second ceramic particles is 1-3, preferably 1-1.5.
4. The water-resistant, waterproof, moisture-permeable composite according to claim 1, wherein the microporous membrane comprises a polyolefin microporous membrane, optionally selected from polyethylene microporous membranes or polypropylene microporous membranes.
5. The water-resistant, waterproof, moisture-permeable composite according to claim 1, wherein the water-resistant, waterproof, moisture-permeable composite further satisfies at least one of the following characteristics:
(1) The thickness of the microporous membrane is 1-30 mu m, preferably 5-20 mu m;
(2) The porosity of the microporous membrane is more than 30%, preferably 40% -70%;
(3) The average pore diameter of the microporous membrane is smaller than 100nm, preferably 10 nm-50 nm;
(4) The moisture permeability of the washable waterproof moisture permeable composite material is not less than 50% of the moisture permeability of the microporous membrane;
(5) The specific surface area of the water-washing-resistant waterproof moisture-permeable composite material is 10m 2/g~60m2/g, preferably 40m 2/g~60m2/g;
(6) The initial hydrostatic pressure of the water-resistant waterproof moisture-permeable composite material is more than 20Kpa, preferably 150 Kpa-200 Kpa, and the hydrostatic pressure drop after 5 times of water washing is not more than 40% of the initial value.
6. The water-resistant, waterproof, moisture-permeable composite according to claim 1, wherein the water-resistant, waterproof, moisture-permeable composite further satisfies at least one of the following characteristics:
(1) The first ceramic particles include one or more of alumina particles, titania particles, silica particles, and zirconia particles;
(2) The second ceramic particles include one or more of alumina particles, titania particles, silica particles, and zirconia particles;
(3) The hydrophilic polymer comprises one or more of polyurethane, polyamide and polyester.
7. The water-resistant, waterproof, moisture-permeable composite according to any one of claims 1 to 6, characterized in that it further satisfies at least one of the following characteristics:
(1) The thickness of the ceramic coating is 0.5-3 mu m;
(2) The thickness of the hydrophilic coating is 0.5-3 mu m;
(3) The gram weight of the ceramic coating is 0.8g/m 2~1.2g/m2;
(4) The gram weight of the hydrophilic coating is 0.5g/m 2~3.2g/m2.
8. A method for preparing the water-washable waterproof and moisture-permeable composite material, which is characterized by being used for preparing the water-washable waterproof and moisture-permeable composite material according to any one of claims 1-7, and comprising the following steps:
preparing ceramic slurry containing first ceramic particles, coating the ceramic slurry on one or two sides of a microporous membrane, and drying to form a ceramic coating;
Preparing composite slurry comprising second ceramic particles and hydrophilic polymer, coating the composite slurry on the ceramic coating, and curing to form the hydrophilic coating.
9. The method according to claim 8, wherein,
The ceramic slurry comprises the following components in total of 100 parts by weight:
1-5 parts by weight of first ceramic particles;
0.1-6 parts by weight of an adhesive;
0.1-1 parts by weight of a dispersing agent;
and the balance of deionized water.
10. The method of claim 8, wherein the composite slurry comprises the following components in total amounts of 100 parts by weight:
10-20 parts by weight of second ceramic particles;
2-8 parts of micropore lignin;
10-20 parts by weight of hydrophilic polymer
0.2-0.6 Parts by weight of a dispersing agent;
2.8-5.0 parts by weight of a cross-linking agent;
The balance of solvent.
11. The waterproof and moisture permeable fabric is characterized by comprising a fabric and the waterproof and moisture permeable composite material with water washing resistance according to any one of claims 1-7 or the waterproof and moisture permeable composite material with water washing resistance prepared by the preparation method according to any one of claims 8-10, wherein the waterproof and moisture permeable composite material with water washing resistance is arranged on the surface of one side of the fabric along the thickness direction of the fabric.
12. The waterproof moisture permeable fabric according to claim 11, wherein the moisture permeable amount of the waterproof moisture permeable fabric is greater than 5000 g/(m 2.24 h), the initial hydrostatic pressure of the waterproof moisture permeable fabric is greater than 20Kpa, preferably 150 Kpa-200 Kpa, and the hydrostatic pressure of the waterproof moisture permeable fabric after 5 times of washing is reduced by not more than 40% of the initial value.
13. The preparation method of the waterproof and moisture permeable fabric is characterized by comprising the following steps of:
Laminating and compounding a microporous film on a surface of one side of the fabric in a thickness direction thereof, and
The ceramic coating and the hydrophilic coating of the water-washable waterproof and moisture-permeable composite material are prepared according to the preparation method of the water-washable waterproof and moisture-permeable composite material according to any one of claims 8 to 10.
14. A garment, wherein at least part of the garment is made of the waterproof and moisture permeable fabric according to any one of claims 11 to 12 or the waterproof and moisture permeable fabric made by the preparation method according to claim 13.
CN202411370083.3A 2024-09-29 2024-09-29 Washable, waterproof and breathable composite material, preparation method thereof, fabric and clothing Pending CN119331301A (en)

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CN202411370083.3A CN119331301A (en) 2024-09-29 2024-09-29 Washable, waterproof and breathable composite material, preparation method thereof, fabric and clothing

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Application Number Priority Date Filing Date Title
CN202411370083.3A CN119331301A (en) 2024-09-29 2024-09-29 Washable, waterproof and breathable composite material, preparation method thereof, fabric and clothing

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CN119331301A true CN119331301A (en) 2025-01-21

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