CN116278308A - Flexible composite material and preparation method thereof - Google Patents

Flexible composite material and preparation method thereof Download PDF

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Publication number
CN116278308A
CN116278308A CN202310166169.3A CN202310166169A CN116278308A CN 116278308 A CN116278308 A CN 116278308A CN 202310166169 A CN202310166169 A CN 202310166169A CN 116278308 A CN116278308 A CN 116278308A
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China
Prior art keywords
fiber fabric
gas barrier
layer
flexible composite
barrier layer
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CN202310166169.3A
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Chinese (zh)
Inventor
刘军虎
纪雪梅
盖须召
郑燕
赵伟涛
陈帅
李雅男
宋鑫
刘稀蒙
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China Lucky Group Corp
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China Lucky Group Corp
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Priority to CN202310166169.3A priority Critical patent/CN116278308A/en
Publication of CN116278308A publication Critical patent/CN116278308A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a flexible composite material and a preparation method thereof, wherein the flexible composite material comprises a weather-resistant film, a first gas barrier layer, a first adhesive layer, a second gas barrier layer, a plastic film, a second adhesive layer, a functional fiber fabric layer and a heat sealing layer which are sequentially laminated, the functional fiber fabric layer comprises fiber fabrics and modified substances, the modified substances are attached to the surfaces of fiber filaments of the fiber fabrics, and the modified substances comprise inorganic-organic hybrid polymers. Thus, the strength, weather resistance and gas barrier properties of the flexible composite material can be improved.

Description

Flexible composite material and preparation method thereof
Technical Field
The invention belongs to the field of aerostats, and particularly relates to a flexible composite material and a preparation method thereof.
Background
An aerostat is an aircraft which provides lift by using lighter-than-air gas, and is widely applied to the military and civil fields by virtue of the advantages of long dead time, energy conservation, environmental protection, economy and the like. The capsule material is an aerostat core structural component and is required to have higher strength, better weather resistance, better tear resistance, lower gas permeability, good processing manufacturability and the like. The capsule material is used as a main bearing structure, the performance requirement of the single material cannot be met, and the composite material has the problems of poor comprehensive performance and lower service life.
Thus, there is a need for improved flexible composites and methods of making the same.
Disclosure of Invention
This application was made based on the inventors' discovery of the following problems:
the composite materials in the related art generally include structures such as a weathering layer, a barrier layer, and a load bearing layer. The inventor finds that the capsule material can be subjected to environmental tests such as kneading, friction, bending, flexing, dragging, long-time continuous stress and the like in the processing or aerostat service process, and the composite material serving as the capsule material in the related art can reduce the strength, weather resistance and gas barrier performance due to repeated kneading and bending, so that the service life of the aerostat is influenced.
The present application aims to at least somewhat alleviate or solve at least one of the above mentioned problems.
In one aspect of the present application, a flexible composite material is provided, including a weather-resistant film, a first gas barrier layer, a first adhesive layer, a second gas barrier layer, a plastic film, a second adhesive layer, a functional fiber fabric layer, and a heat seal layer, which are sequentially stacked, the functional fiber fabric layer includes a fiber fabric and a modifying substance, the modifying substance is attached to a surface of the fiber fabric, and the modifying substance includes an inorganic-organic hybrid polymer. Thus, the strength, weather resistance and gas barrier properties of the flexible composite material can be improved.
According to an embodiment of the present invention, the fiber fabric includes at least one of a polyimide fiber fabric, a poly-p-phenylene bisoxazole fiber fabric, an ultra-high molecular weight polyethylene fiber fabric, an aromatic polyamide fiber fabric, an aromatic polyester fiber fabric, an aliphatic polyamide fiber fabric, and an aliphatic polyester fiber fabric. Thereby, the strength of the flexible composite material is further improved.
According to an embodiment of the invention, the first gas barrier layer comprises at least one of an inorganic hybrid modified hydroxyl polymer and an inorganic hybrid modified carboxyl polymer, and the second gas barrier layer comprises a barrier layer material comprising at least one of alumina, silica, silicon nitride, titania, and zirconia. Therefore, the gas barrier performance of the flexible composite material is further improved.
According to an embodiment of the invention, the fibrous web has a thickness of 30 μm to 250 μm and an areal density of 25g/m 2 -250g/m 2 . Thereby, the strength and the kneading resistance of the flexible composite material are further improved.
According to an embodiment of the invention, the thickness of the first gas barrier layer is 0.1 μm-2 μm. Therefore, the gas barrier performance of the flexible composite material is further improved.
According to an embodiment of the invention, the thickness of the second gas barrier layer is 10nm-100nm. Therefore, the gas barrier performance of the flexible composite material is further improved.
According to an embodiment of the invention, the flexible composite material fulfils at least one of the following conditions: the thickness of the weather-resistant film is 8-35 mu m; the thickness of the plastic film is 6-25 mu m; the thickness of the heat seal layer is 20-50 mu m; the first adhesive layer has a sizing amount of 3g/m 2 -15g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The second adhesive layer has a sizing amount of 10g/m 2 -30g/m 2 . Thus, the kneading resistance and weather resistance of the flexible composite material are further improved.
In another aspect of the invention, the invention provides a method of making the aforementioned flexible composite, comprising: modifying the fiber fabric to obtain a functional fiber fabric layer; corona treatment is carried out on one side surface of the weather-resistant film, and a first gas barrier layer is formed on the surface of the weather-resistant film, which is subjected to the corona treatment, through a first coating process, so that the gas barrier weather-resistant film is obtained; forming a second gas barrier layer on one side surface of the plastic film through a deposition process to obtain a gas barrier plastic film; the gas barrier weather-resistant film and the gas barrier plastic film are arranged oppositely, and the first gas barrier layer and the second gas barrier layer are bonded by using a first adhesive to obtain a first composite film; arranging the first composite film and the functional fiber fabric layer oppositely, and bonding the plastic film and the functional fiber fabric layer by using a second adhesive to obtain a second composite film; and forming the heat sealing layer on the surface of one side of the functionalized fiber fabric layer far away from the plastic film through a second coating process so as to obtain the flexible composite material. Therefore, the functional fiber fabric layer is obtained by modifying the fiber fabric, and the flexible composite material with better rubbing resistance, strength, gas resistance and weather resistance can be obtained by arranging the double-layer gas barrier layer.
According to an embodiment of the present invention, the modification treatment includes dip-coating the fiber fabric in a dip-coating liquid, and drying the fiber fabric subjected to the dip-coating treatment. Thus, a fibrous web containing a surface modifying substance can be obtained.
According to the embodiment of the invention, the dip-coating treatment time is 5s-120s, the drying treatment temperature is 80-135 ℃, and the drying treatment time is 2-3 min. Thereby, the formation of inorganic-organic hybrid polymer coating on the surface of the fiber fabric can be further promoted.
According to an embodiment of the present invention, the dip coating solution includes 1.5 to 25 parts by weight of a grafting agent, 0.2 to 2.5 parts by weight of a film forming agent, 0.01 to 0.5 parts by weight of an initiator, and 20 to 2000 parts by weight of a solvent. Thus, the grafting agent serves as a bridge, and promotes the combined action of the initiator and the film forming agent in the dipping liquid, so that a uniform inorganic-organic hybrid polymer coating is formed on the surface of the fiber fabric.
According to an embodiment of the present invention, the grafting agent includes at least one of methyl methacrylate, butyl acrylate, acrylic acid-hydroxypropyl ester, acrylic acid-hydroxyethyl ester, N-methylolacrylamide, propyl methacrylate-based triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanurate, gamma-ureidopropyltrimethoxysilane, gamma-ureidotriethoxysilane, gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatotriethoxysilane, and propenyl trimethyl phosphate, tetraisopropoxytitanium, triisopropoxyaluminum, aluminum trichloride, titanium tetrachloride, and zirconium tetrachloride. Therefore, the grafting agent is used as a bridge, and the adsorption of the grafting agent on the surface of the fiber fabric is realized through the active groups of the grafting agent, so that a uniform inorganic-organic hybrid polymer coating is formed on the surface of the fiber fabric.
According to an embodiment of the present invention, the film forming agent comprises a water soluble polymer comprising at least one of a polyacrylamide, a polyvinylpyrrolidone, a polyacrylic acid, a polymethacrylic acid, a poly (acrylic acid/methacrylic acid) copolymer, a polyvinyl alcohol, a polyethyleneimine, a polyethylene oxide, an ethylene-vinyl alcohol copolymer, a polyethylene-maleic anhydride copolymer, a styrene-maleic anhydride copolymer, a polysaccharide, chitosan, and cellulose. Thus, the film forming agent can promote the formation of a uniform inorganic-organic hybrid polymer coating on the surface of the fiber fabric.
According to an embodiment of the present invention, the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate and azobisisovaleronitrile, dopamine hydrochloride, azobisisobutyrimidine hydrochloride, azobisiso Ding Mi hydrochloride, azobisiso Ding Mi, and azobiscyano valeric acid. Thus, the unsaturated double bond or triple bond in the grafting agent is initiated to generate self-polymerization reaction, and the grafting agent and the film forming agent are promoted to form an inorganic-organic hybrid polymer coating on the surface of the fiber fabric.
According to an embodiment of the present invention, the solvent includes a mixed solution of water and an alcohol including at least one of methanol, ethanol, isopropanol, and n-propanol. Thereby helping to form a uniform inorganic-organic hybrid polymer coating on the surface of the fiber fabric.
Drawings
The foregoing and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a schematic structural view of a flexible composite material according to one embodiment of the present application;
FIG. 2 is a process flow diagram of preparing a flexible composite according to one embodiment of the present application.
Reference numerals illustrate:
10: a weatherable film; 20: a first gas barrier layer; 30: a first adhesive layer; 40: a second gas barrier layer; 50: a plastic film; 60: a second adhesive layer; 70: a functional fiber fabric layer; 80: and (3) a heat sealing layer.
Detailed Description
Embodiments of the present application are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary only for the purpose of explaining the present application and are not to be construed as limiting the present application.
In one aspect of the present invention, a flexible composite is provided, referring to fig. 2, comprising a weatherable film 10, a first gas barrier layer 20, a first adhesive layer 30, a second gas barrier layer 40, a plastic film 50, a second adhesive layer 60, a functionalized fiber fabric layer 70, and a heat seal layer 80, which are laminated in this order. Specifically, the functionalized fiber fabric layer 70 includes a fiber fabric and a modifying substance, the modifying substance is attached to the surface of the fiber fabric, and the modifying substance includes an inorganic-organic hybrid polymer, so that the rubbing and bending resistance of the fiber fabric is improved, thereby improving the rubbing resistance of the flexible composite material; the weather-resistant film 10 can improve the weather resistance of the flexible composite material; the first gas barrier layer 20 and the second gas barrier layer 40 effectively improve the barrier property of the flexible composite material to gas during the kneading and bending process, thereby improving the strength and gas barrier property of the flexible composite material during the kneading and bending process; the first adhesive layer 30 and the second adhesive layer 60 may improve structural stability of the flexible composite material, and the plastic film 50 may be able to effectively support the second gas barrier layer 60 thereon.
For ease of understanding, the following description will be given of the principle that the flexible composite material in the present application has the above-described advantageous effects:
the inventor finds that in the actual use process of the flexible composite material, as part of fiber filaments in the fiber fabric layer are broken in the kneading or bending process, the broken fiber filaments directly cause the strength of the flexible composite material to be obviously reduced. In the present application, the inventors found that when the surface of the filaments in the fibrous fabric has a uniform inorganic-organic hybrid polymer coating, the inorganic-organic hybrid polymer coating can effectively improve breakage of the filaments during kneading and bending, thereby enhancing flexibility and abrasion resistance of the fibrous fabric. On the other hand, the inorganic-organic hybrid polymer coating can improve the inertia of the surface of the high-modulus fiber fabric, improve the cohesiveness between the functional fiber fabric layer and the heat sealing layer, and further improve the integral rubbing resistance of the flexible composite material.
According to some embodiments of the present invention, the functionalized fiber fabric layer is formed by modifying the surface of the fiber fabric, wherein the modifying process is dip-coating the fiber fabric in a dip-coating solution, wherein the dip-coating solution comprises a grafting agent, a film-forming agent, an initiator and a solvent, and specifically, the dip-coating solution is capable of forming a uniform inorganic-organic hybrid polymer coating on the surface of the fiber filaments in the fiber fabric, the inorganic-organic hybrid polymer coating comprises an inorganic-organic hybrid polymer, and the inorganic-organic hybrid polymer comprises at least one of an inorganic-organic hybrid hydroxyl polymer, an inorganic-organic hybrid polyurethane polymer, an inorganic-organic hybrid carboxyl polymer and an inorganic-organic metal-oxygen-carbon bond polymer, thereby improving the kneading resistance of the flexible composite material by attaching the inorganic-organic hybrid polymer to the surface of the fiber fabric.
According to some embodiments of the present invention, the functionalized fiber fabric layer is used as the load bearing layer in the flexible composite material, and the type of the fiber fabric in the functionalized fiber fabric layer is not particularly limited, and for example, the fiber fabric may include at least one of polyimide fiber fabric, poly-p-phenylene bisoxazole fiber fabric, ultra-high molecular weight polyethylene fiber, aromatic polyamide fiber, aromatic polyester fiber, aliphatic polyamide fiber and aliphatic polyester fiber, whereby the foregoing fiber fabric may provide the functionalized fiber fabric layer with superior strength and load bearing effect.
According to some embodiments of the present invention, the fiber fabric is woven from fiber filaments, and the fineness of the fiber filaments in the fiber fabric is not particularly limited, for example, the fineness of the fiber filaments may be 5-1200 denier, and when the fineness of the fiber filaments is 5-1200 denier, the fiber fabric formed by weaving the fiber filaments with the fineness can improve the overall strength and the load-bearing effect of the functional fiber fabric layer, so that the surface density of the fiber fabric can meet the design requirement of the flexible composite material.
According to some embodiments of the invention, the first gas barrier layer and the second gas barrier layer are configured to provide the flexible composite material with a better gas barrier property, wherein the material of the first gas barrier layer may include at least one of an inorganic hybrid modified hydroxyl polymer and an inorganic hybrid modified carboxyl polymer, the second gas barrier layer includes a barrier layer material, and the barrier layer material may include at least one of alumina, silica, silicon nitride, titania, and zirconia, and wherein the particle size of the barrier layer material may be in a nanometer scale. Specifically, the first gas barrier layer formed by the inorganic hybridization modified hydroxyl polymer and/or the inorganic hybridization modified carboxyl polymer has higher specific strength and lower permeability, the second gas barrier layer formed by the barrier layer material with the particle size of nanometer level has better shearing stress, and the gas leakage phenomenon is not easy to occur due to break points in the repeated kneading process, so that the first gas barrier layer can improve the gas barrier performance of the second gas barrier layer, and the second gas barrier layer and the first gas barrier layer cooperate to effectively improve the gas barrier performance of the flexible composite material.
According to some embodiments of the present invention, the type of gas that the first gas barrier layer and the second gas barrier layer can block is not particularly limited, for example, the gas may include at least one of hydrogen, helium, and hot gas.
According to some embodiments of the present invention, the weather-resistant film as the weather-resistant unit in the flexible composite material is not particularly limited in kind, and for example, the weather-resistant film may include at least one of a polyvinyl fluoride film, a polyvinylidene fluoride film, an ethylene-tetrafluoroethylene copolymer film, a polyimide film, a polyurethane film, and a liquid-crystalline polyester film.
According to some embodiments of the present invention, the plastic film is used as the support of the second barrier film, and the kind thereof is not particularly limited, and for example, the kind of the plastic film may include at least one of a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyamide film, a polyethylene film, and a polypropylene film, and when the kind of the plastic film is the foregoing material, it is possible to effectively improve the weather resistance of the flexible composite material.
According to some embodiments of the present invention, the heat-sealing layer is a protective layer, and is disposed on the outermost layer of the flexible composite material, and the material of the heat-sealing layer is not particularly limited, for example, the heat-sealing layer may include at least one of a polyester polyurethane elastomer, a polyether polyurethane elastomer, a polycaprolactone polyurethane elastomer, a polyolefin elastomer, a polystyrene elastomer, a polyether ester elastomer, and a polyamide elastomer, and when the heat-sealing layer is made of the foregoing materials, on one hand, hydrogen bonds exist in the thermoplastic elastomer, so that the heat-sealing layer has good interfacial compatibility with the functional fiber fabric layer under the action of the hydrogen bonds, and on the other hand, the thermoplastic elastomer has a certain adhesion, so that the surface of the capsule material has anti-fouling and wear resistance, and the kneading resistance of the capsule material is improved.
According to some embodiments of the present invention, the adhesive layer may firmly bond the layers of the flexible composite material together, so that the flexible composite material does not slip between layers after being flexed for multiple times, and has good weather resistance, tensile strength and shear strength, and the materials of the first adhesive layer and the second adhesive layer are not particularly limited, for example, the materials of the first adhesive layer and the second adhesive layer may independently include at least one of a polyurethane adhesive, a polyester adhesive and a polyacrylate adhesive, respectively, and when the materials of the first adhesive layer and the second adhesive layer are the materials described above, the first adhesive layer may effectively bond the first gas barrier layer and the second gas barrier layer, and the second adhesive layer may effectively bond the plastic film and the functional fiber fabric layer.
According to some embodiments of the present invention, the thickness of the fiber fabric layer is not particularly limited, for example, the thickness of the fiber fabric may be 30 μm to 250 μm, when the thickness of the fiber fabric is less than 30 μm, the thickness of the fiber fabric is too thin, which may cause the functional fiber fabric layer to be easily broken during the kneading or bending process, thereby reducing the strength of the flexible composite material, when the thickness of the fiber fabric is more than 250 μm, the thickness of the fiber fabric is too thick, and when the total thickness of the flexible composite material is constant, the thickness of other layers is correspondingly reduced, which may eventually lead to a reduction in weather resistance, strength, gas barrier property and kneading resistance of the flexible composite material, and when the thickness of the fiber fabric is 30 μm to 250 μm, the flexible composite material has better kneading resistance and strength.
According to some embodiments of the invention, the areal density of the fibrous web is not particularly limited, for example, the areal density of the fibrous web may be 25g/m 2 -250g/m 2 When the areal density of the fibrous web is less than 25g/m 2 When the surface density of the fiber fabric is too small, the amount of inorganic-organic hybrid polymer capable of being adhered to the fiber surface in the fiber fabric is small, which can lead to the reduction of the rubbing resistance and strength of the flexible composite material, when the surface density of the fiber fabric is more than 250g/m 2 This results in a reduced flexibility of the flexible composite when the areal density of the fibre web is 25g/m 2 -250g/m 2 When the composite material is used, the flexible composite material has better kneading resistance and strength.
According to some embodiments of the present invention, the thickness of the first gas barrier layer is not particularly limited, for example, the thickness of the first gas barrier layer may be 0.1 μm to 2 μm, when the thickness of the first gas barrier layer is less than 0.1 μm, the thickness of the first gas barrier layer is too low, which may reduce the gas barrier performance of the first gas barrier layer, when the thickness of the first gas barrier layer is greater than 2 μm, the thickness of the first gas barrier layer is too thick, which may cause an increase in the areal density of the flexible composite material, which may cause a decrease in the effective load of the aerostat, which is disadvantageous for practical use of the aerostat, and when the thickness of the first gas barrier layer is 0.1 μm to 2 μm, the flexible composite material has better gas barrier performance.
According to some embodiments of the present invention, the thickness of the second gas barrier layer is not particularly limited, for example, the thickness of the second gas barrier layer may be 10nm to 100nm, and when the thickness of the second gas barrier layer is less than 10nm, the thickness of the second gas barrier layer is too low, which may reduce the gas barrier performance of the second gas barrier layer, and when the thickness of the second gas barrier layer is greater than 100nm, the thickness of the second gas barrier layer is too thick, which may result in an increase in the areal density and an increase in the material cost of the flexible composite material, and when the thickness of the second gas barrier layer is 10nm to 100nm, the flexible composite material has a better barrier gas performance by a double layer design of the first gas barrier layer and the second gas barrier layer.
According to some embodiments of the present invention, the thickness of the weather-resistant film is not particularly limited, and for example, the thickness of the weather-resistant film may be 8 μm to 35 μm, and when the thickness of the weather-resistant film is less than 8 μm, the thickness of the weather-resistant film is too low, which may reduce the weather resistance of the flexible composite material, and when the thickness of the weather-resistant film is greater than 35 μm, a higher thickness of the weather-resistant film may result in an increase in the areal density of the flexible composite material and an increase in the material cost, and when the thickness of the weather-resistant film is within the foregoing range, the weather resistance of the flexible composite material thus obtained may be better.
According to some embodiments of the present invention, the thickness of the plastic film is not particularly limited, and for example, the thickness of the plastic film may be 6 μm to 25 μm, and when the thickness of the plastic film is less than 6 μm, the plastic film is too thin, which may cause non-uniform film formation of the second gas barrier layer when the second gas barrier layer is formed using a deposition process, thereby reducing the effect of the second gas barrier layer on the barrier gas, and when the thickness of the plastic film is greater than 25 μm, the excessive thickness of the plastic film may cause an increase in the areal density of the flexible composite material and an increase in the material cost, and when the thickness of the plastic film is within the aforementioned range, the flexible composite material thus obtained has superior barrier gas performance.
According to some embodiments of the present invention, the thickness of the heat-sealing layer is not particularly limited, and for example, the thickness of the heat-sealing layer may be 20 μm to 50 μm, and when the thickness of the heat-sealing layer is less than 20 μm, the heat-sealing layer is too thin, the adhesion between the heat-sealing layer and the functional fiber fabric layer is reduced, and when the thickness of the heat-sealing layer is greater than 50 μm, an increase in the areal density of the flexible composite material and an increase in the material cost may be caused, and when the thickness of the heat-sealing layer is within the aforementioned range, the heat-sealing layer and the functional fiber fabric layer may be effectively adhered, thereby effectively protecting the functional fiber fabric layer, and further improving the rub resistance and strength of the flexible composite material.
According to some embodiments of the present invention, the first adhesive layer and the second adhesive layer are used as a medium for connecting the layers, so as to ensure that the flexible composite material does not slide relatively between the layers in the process of kneading and flexing, the first adhesive layer adheres the first gas barrier layer and the second gas barrier layer, and the second adhesive layer adheres the plastic film and the functional fiber fabric layer, so that the glue application amount of the first adhesive layer and the second adhesive layer is required to be moderate, the glue application amount is too low, the adhesion between the layers of the flexible composite material is poor, the risk of sliding between the layers of the flexible composite material is caused during the actual use, the surface density and the material cost of the flexible composite material are increased due to the too high glue application amount, and the glue application amount of the first adhesive layer is 3g/m 2 -15g/m 2 The second adhesive layer had a sizing amount of 10g/m 2 -30g/m 2 。
According to some embodiments of the invention, the areal density of the flexible composite may be 40g/m 2 -450g/m 2 The thickness may be from 90 μm to 500 μm when the areal density of the flexible composite is greater than 450g/m 2 When the surface density of the flexible composite material is too high, the aerostat obtained by the flexible composite material can increase in weight, so that the effective load of the aerostat is reduced, and when the surface density of the flexible composite material is less than 40g/m 2 When the surface density of the flexible composite material is 40g/m, the requirements of the aerostat on the material performance cannot be met due to the fact that the surface density of each layer of material forming the flexible composite material is correspondingly lower, and the kneading resistance and the strength of the flexible composite material are lower 2 -450g/m 2 When in use, the flexible composite material has better kneading resistance and strength, and can meet the requirement of aerostatRequirements for material properties.
In another aspect of the present invention, the present invention provides a method of preparing the aforementioned flexible composite material, referring to fig. 2, comprising the steps of:
s100: modifying the fiber fabric
According to some embodiments of the present invention, the fiber fabric is subjected to a modification treatment in the present step to obtain the functional fiber fabric layer, wherein the modification treatment process is to dip-coat the fiber fabric in a dip-coating solution, and the dip-coated fiber fabric is subjected to a drying treatment, wherein the time of the dip-coating treatment in the dip-coating process is not particularly limited, for example, the time of the dip-coating treatment may be 5s to 120s, and when the time of the dip-coating treatment is 5s to 120s, it may be promoted to form a uniform inorganic-organic hybrid polymer coating on the fiber filament surface of the fiber fabric.
According to some embodiments of the present invention, the dip-coated fiber fabric is subjected to a drying process such that a solvent in a dip-coating solution for dip-coating the surface of the fiber fabric is volatilized, wherein the drying process may be performed at a temperature of 80-135 ℃ for a time of 2-3 min.
According to some embodiments of the present invention, the composition of the dip coating liquid is not particularly limited, and for example, the dip coating liquid may include 1.5 to 25 parts by weight of a grafting agent, 0.2 to 2.5 parts by weight of a film forming agent, 0.01 to 0.5 parts by weight of an initiator, and 20 to 2000 parts by weight of a solvent. Therefore, the dip-coating liquid can form a uniform inorganic-organic hybrid polymer coating on the surface of the fiber, specifically, when the dosage of the grafting agent in the dip-coating liquid is more than 25 parts by weight, the excessive content of the grafting agent can cause the deterioration of the flexibility of the fiber fabric after dip-coating, and when the dosage of the grafting agent in the dip-coating liquid is less than 1.5 parts by weight, the excessive content of the grafting agent can cause the poor modification treatment effect of the fiber fabric, so that the kneading resistance and strength of the flexible composite material are difficult to improve; when the amount of the initiator in the dip coating liquid is more than 0.5 parts by weight, the stability of the dip coating liquid is deteriorated due to the excessively high amount of the initiator, and when the amount of the initiator in the dip coating liquid is less than 0.01 parts by weight, the coating formed on the surface of the fiber fabric is uneven due to the excessively low amount of the initiator, thereby affecting the modification treatment effect of the fiber fabric.
According to some embodiments of the invention, the grafting agent may either enhance adsorption of the fiber surface by itself activity or may act on the fiber surface in combination with an initiator and a film former to form a uniform protective layer. In the present invention, the grafting agent is an organic compound containing an unsaturated double bond or triple bond and/or contains a metal complex having 3 or more coordination centers such as aluminum, titanium, zirconium, etc., and specifically, the grafting agent may include at least one of methyl methacrylate, butyl acrylate, acrylic acid-hydroxypropyl ester, acrylic acid-hydroxyethyl ester, N-methylolacrylamide, propyl methacrylate-based triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanurate, γ -ureidopropyltrimethoxysilane, γ -ureidotriethoxysilane, γ -isocyanatopropyl trimethoxysilane, γ -isocyanatotriethoxysilane, and propenyl trimethyl phosphate, tetraisopropoxytitanium, triisopropoxyaluminum, aluminum trichloride, titanium tetrachloride, and zirconium tetrachloride.
According to some embodiments of the invention, the film former may include a water-soluble polymer including at least one of a polyacrylamide, a polyvinylpyrrolidone, a polyacrylic acid, a polymethacrylic acid, a poly (acrylic acid/methacrylic acid) copolymer, a polyvinyl alcohol, a polyethyleneimine, a polyethylene oxide, an ethylene-vinyl alcohol copolymer, a polyethylene-maleic anhydride copolymer, a styrene-maleic anhydride copolymer, a polysaccharide, chitosan, and cellulose, wherein the mass ratio of the grafting agent to the film former in the dip-coating liquid may be 3/5 to 250/2.
According to some embodiments of the invention, the initiator is capable of initiating self-polymerization of unsaturated double or triple bonds in the grafting agent, promoting the formation of inorganic-organic hybrid polymer coatings on the fiber filaments surfaces of the fiber fabric by the grafting agent and the film forming agent, wherein the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate and azobisisovaleronitrile, dopamine hydrochloride, azobisisobutyrimidine hydrochloride, azobisiso Ding Mi hydrochloride, azobisiso Ding Mi, and azobiscyano valeric acid, wherein the mass ratio of the initiator to the grafting agent in the dip may be 1/2500-1/3.
According to some embodiments of the present invention, the solvent comprises a mixed solution of water and alcohol, specifically, the alcohol comprises at least one of methanol, ethanol, isopropanol and n-propanol, the weight ratio of the alcohol to the water is 2/1-50/1, preferably, the mass ratio of the alcohol to the water is 3/1-10/1, wherein the addition of too little alcohol is unfavorable for the dispersion of the film forming agent, the grafting agent and the initiator in the solvent, so that the wettability of the dip coating liquid on the surface of the fiber fabric is poor, and the addition of too much alcohol is low in solid content of the dip coating liquid, so that the modification effect of the fiber fabric is affected.
According to some embodiments of the present invention, the solid content of the dip-coating liquid is not particularly limited, for example, the solid content of the dip-coating liquid may be 0.1% -10%, when the solid content of the dip-coating liquid is less than 0.1%, the solid content of the dip-coating liquid is too low, so that the inorganic-organic hybrid polymer content in the dip-coating liquid is too low, thereby causing the inorganic-organic hybrid polymer attached to the surface of the fiber fabric during the dip-coating process to be less or non-uniform, thereby reducing the effect of the modification treatment of the fiber fabric, and when the solid content of the dip-coating liquid is more than 10%, the solid content of the dip-coating liquid is too high, so that the inorganic-organic hybrid polymer attached to the surface of the fiber fabric during the dip-coating process is too high, thereby causing the flexibility of the functional fiber fabric layer to be deteriorated, thereby reducing the rub resistance of the flexible composite material.
According to some embodiments of the present invention, a fiber fabric is modified to obtain a functionalized fiber fabric layer, wherein the modification process is dip-coating the fiber fabric in a dip-coating solution capable of forming a uniform inorganic-organic hybrid polymer coating on the surface of fiber filaments in the fiber fabric, the inorganic-organic hybrid polymer including at least one of an inorganic-organic hybrid hydroxyl polymer, an inorganic-organic hybrid polyurethane polymer, an inorganic-organic hybrid carboxyl polymer, and an inorganic-organic metal-oxygen-carbon bond polymer, thereby improving the rub resistance of the flexible composite material by attaching the inorganic-organic hybrid polymer to the surface of the fiber fabric.
S200: corona-treating one side surface of the weather-resistant film, and forming a first gas barrier layer on the corona-treated one side surface by a first coating process
According to some embodiments of the present invention, in the step, a first gas barrier layer is formed by corona-treating one side surface of a weather-resistant film and by a first coating process on the corona-treated one side surface to obtain a gas barrier weather-resistant film, wherein the first coating process may include: at least one of roll coating, gravure coating, blade coating, slot coating, extrusion coating, air knife coating, dip coating, spray coating, casting process, and curtain coating.
S300: forming a second gas barrier layer on one side surface of the plastic film by a deposition process
According to some embodiments of the invention, in the step, the second gas barrier layer is formed on one side surface of the plastic film by a deposition process to obtain the gas barrier plastic film, wherein the deposition process may include at least one of vacuum thermal evaporation, electron beam evaporation, magnetron sputtering plating, and plasma chemical vapor deposition.
S400: bonding the first gas barrier layer to the second gas barrier layer with a first adhesive
According to some embodiments of the invention, in this step, the first gas barrier layer of the gas barrier Hou Baomo and the second gas barrier layer of the gas barrier plastic film are disposed opposite to each other, and the first gas barrier layer and the second gas barrier layer are bonded with a first adhesive to obtain a first composite film.
S500: bonding a plastic film to the functionalized fiber fabric layer using a second adhesive
According to some embodiments of the invention, in this step, the plastic film of the first composite film is disposed opposite the functionalized fiber fabric layer, and the plastic film is bonded to the functionalized fiber fabric layer with a second adhesive to obtain a second composite film.
S600: forming a heat sealing layer on the surface of one side of the functional fiber fabric layer far away from the plastic film through a second coating process
According to some embodiments of the invention, in the step, a heat-sealing layer is formed on a surface of the functionalized fiber fabric layer on a side away from the plastic film by a second coating process to obtain the flexible composite material, wherein the second coating process may include at least one of vacuum thermal evaporation, electron beam evaporation, magnetron sputtering plating, and plasma chemical vapor deposition.
According to some embodiments of the invention, the flexible composite material prepared by the method has good rubbing resistance, high strength, low surface density and good weather resistance, and can be widely applied to capsule materials of aerostats such as stratosphere airships, troposphere airships, tethered balls, high-altitude balloons and the like.
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Preparation of modified dip coating liquid: the grafting agent is prepared from 11.3 parts by weight of gamma-ureido propyl trimethoxy silane, the film forming agent is prepared from 0.5 part by weight of 5% polyvinyl alcohol solution, the initiator is prepared from 0.01 part by weight of azodiisobutyronitrile, and the solvent is prepared from water and isopropanol solution, wherein the weight parts of the solvent are 2000, and the mixture is uniformly mixed at normal temperature.
Preparation of a flexible composite material: the weather-proof film is made of polyvinyl fluoride film with thickness of 25 μm, the first gas barrier layer is made of polyvinyl alcohol/polyacrylic acid barrier coating liquid with thickness of 0.15 μm, the second gas barrier layer is made of silicon oxide barrier layer with thickness of 12nm, the plastic film is made of ethylene terephthalate film with thickness of 10 μm, and the fiber fabric of the functional fiber fabric layer is made of fiber fabric with surface density of 110g/m 2 Polyimide fiber fabric with thickness of 80 mu m, and heatThe seal layer is made of thermoplastic polyurethane, and the first adhesive layer and the second adhesive layer are made of two-component polyurethane adhesives.
The specific preparation process of the flexible composite material comprises the following steps: dip-coating the fiber fabric on dip-coating equipment, curing for 5min at the temperature of 85 ℃ after the dip-coating is finished, and winding to finish the preparation of the functionalized fiber fabric layer; corona the coating surface of the weather-resistant film, coating a first gas barrier layer polyvinyl alcohol/polyacrylic acid on micro gravure coating equipment, curing for 3min at the temperature of 85 ℃ after the coating is finished, and winding to finish the preparation of the helium-resistant weather-resistant film; forming a second gas barrier layer on one side surface of the plastic film through a deposition process to obtain a gas barrier plastic film, arranging the gas barrier weather-resistant film and the gas barrier plastic film oppositely, and adhering the first gas group barrier layer and the second gas barrier layer by using a first adhesive to obtain a first composite film; the first composite film and the functional chemical fiber fabric layer are arranged oppositely, and the plastic film and the functional chemical fiber fabric layer are bonded by using a second adhesive to obtain a second composite film; and forming a heat sealing layer on the surface of one side of the functional fiber fabric layer far away from the plastic film through a second coating process to obtain the flexible composite material.
Examples 2-18 were identical to example 1 except that the thickness of the functionalized fiber fabric layer, the areal density of the functionalized fiber fabric layer, the material of the functionalized fiber fabric layer, the amount of grafting agent, the amount of film forming agent, the amount of initiator, the amount of solvent, the thickness of the first gas barrier layer and the thickness of the second gas barrier layer were all as shown in table 1.
Comparative examples 1 to 9 are the same as example 1 except that the flexible composite of comparative example 1 does not have the first gas barrier layer, the flexible composite of comparative example 2 does not have the second gas barrier layer, the fiber fabric of the functional fiber fabric layer in comparative example 3 is not subjected to the surface modification treatment, the thicknesses of the functional fiber fabric layers, the areal densities of the functional fiber fabric layers, the materials of the functional fiber fabric layers, the amounts of grafting agent, the amounts of film forming agent, the amounts of initiator, the amounts of solvent, the thicknesses of the first gas barrier layer, and the thicknesses of the second gas barrier layer are specifically shown with reference to table 1.
TABLE 1
Figure BDA0004096038800000111
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Figure BDA0004096038800000121
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Figure BDA0004096038800000131
The flexible composites of the foregoing examples 1-18 and comparative examples 1-9 were tested as follows, with results shown in Table 2:
(1) Surface Density test: the test is carried out according to the national standard GB/T4669-2008 'determination of mass per unit length and mass per unit area of textile woven fabrics'.
(2) Tensile strength test: the measurement was performed according to the American Standard FED-STD-191A 5102.
(3) Helium permeability test: the measurement is carried out according to the national standard GB/T1038-2000 differential pressure method of plastic film and sheet gas permeability test method.
(4) Experiment of rub resistance: according to the American standard ASTMF392-93, the rubbing resistance test of the flexible composite material is carried out, specifically, the flexible composite material is cut into sample pieces with the length of 30cm and the width of 21cm, the flexible composite material is continuously rubbed for 1000 times on a blue light rubbing tester, and the tensile strength and the helium transmittance of the flexible composite material before and after rubbing are tested.
(5) Experiment of flexural resistance: the flex resistance test of the flexible composite material is carried out according to QB/T2714-2018 'determination of folding fastness of leather physical and mechanical test', specifically, the flexible composite material is cut into sample pieces with the length of 30cm and the width of 21cm, the sample pieces are continuously flexed 1000 times on a flex resistance tester, the helium permeability of the flexible composite material before and after flexing is tested, and the damage condition of the sample pieces after 1000 times of flexing is observed under a magnifying glass, wherein the apparent evaluation of the flex composite material after 1000 times of damage comprises: the excellent finger material has no obvious crease and good state; the crease of the good finger material is obvious, and the state is basically good; it can be referred to that the crease of the material is obvious, but no breakage is found; the difference means that the material is damaged and the layering between the membrane cloth is caused.
TABLE 2
Figure BDA0004096038800000132
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Figure BDA0004096038800000141
As can be seen from the above table, the flexible composite materials prepared in examples 1 to 18 all show excellent kneading resistance, the attenuation rate of the transverse and longitudinal tensile strength is less than 10% under the condition of kneading 1000 times, and the helium permeability of the prepared flexible composite material after kneading 1000 times is less than or equal to 0.5L/m 2 D.atm. The surface of the weather-resistant film of the flexible composite material in comparative example 1 is not coated with the first gas barrier layer, the helium resistance is poor, the flexible composite material in comparative example 2 does not contain the second gas barrier layer, the helium resistance is poor, the functionalized fiber fabric layer of the flexible composite material in comparative example 3 is not modified, the fabric damage is serious in the rubbing process, the tensile strength attenuation of the material is obvious, and leakage points appear in the first gas barrier layer, the second gas barrier layer and the weather-resistant film due to the breakage of the fiber fabric, air leakage occurs in the test process of the sample, and the fabric damage and the tensile strength attenuation of the material are obvious in the rubbing process of the flexible composite material due to the insufficient modification treatment of the functionalized fiber fabric layer in comparative examples 4 to 9.
As can be seen from the above table, the flexible composite materials in examples 1 to 18 were excellent in appearance, free from breakage, and less than or equal to 0.5L/m in helium permeability after 1000 times of kneading 2 D.atm. The flexible composites of comparative examples 1 to 9 were not sufficiently modified due to the lack of the gas barrier layer or the functionalized fiber fabric layer, and thus a gas leakage phenomenon occurred, thereby allowing the flexible composites to be formedThe material has poor kneading resistance and gas barrier property.
In the description of the present application, "a and/or B" may include any of the cases of a alone, B alone, a and B, wherein A, B is merely for example, which may be any technical feature of the present application using "and/or" connection.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (10)

1. A flexible composite material is characterized by comprising a weather-resistant film, a first gas barrier layer, a first adhesive layer, a second gas barrier layer, a plastic film, a second adhesive layer, a functional fiber fabric layer and a heat sealing layer which are sequentially laminated,
The functionalized fiber fabric layer comprises a fiber fabric and a modifying substance, wherein the modifying substance is attached to the surface of the fiber fabric, and the modifying substance comprises an inorganic-organic hybrid polymer.
2. The flexible composite of claim 1, wherein the fiber fabric comprises at least one of a polyimide fiber fabric, a poly-p-phenylene bisoxazole fiber fabric, an ultra-high molecular weight polyethylene fiber fabric, an aromatic polyamide fiber fabric, an aromatic polyester fiber fabric, an aliphatic polyamide fiber fabric, and an aliphatic polyester fiber fabric.
3. The flexible composite of claim 1, wherein the first gas barrier layer comprises at least one of an inorganic hybrid modified hydroxyl polymer and an inorganic hybrid modified carboxyl polymer, and the second gas barrier layer comprises a barrier layer material comprising at least one of alumina, silica, silicon nitride, titania, and zirconia.
4. The flexible composite of claim 1, wherein the fibrous web has a thickness of 30 μm to 250 μm and an areal density25g/m 2 -250g/m 2 。
5. The flexible composite of claim 1, wherein the first gas barrier layer has a thickness of 0.1 μιη to 2 μιη;
Optionally, the thickness of the second gas barrier layer is 10nm to 100nm.
6. The flexible composite of claim 1, wherein the flexible composite meets at least one of the following conditions:
the thickness of the weather-resistant film is 8-35 mu m;
the thickness of the plastic film is 6-25 mu m;
the thickness of the heat seal layer is 20-50 mu m;
the first adhesive layer has a sizing amount of 3g/m 2 -15g/m 2 ；
The second adhesive layer has a sizing amount of 10g/m 2 -30g/m 2 。
7. A method of making the flexible composite of any of claims 1-6, comprising:
modifying the fiber fabric to obtain a functional fiber fabric layer;
corona treatment is carried out on one side surface of the weather-resistant film, and a first gas barrier layer is formed on the surface of the weather-resistant film, which is subjected to the corona treatment, through a first coating process, so that the gas barrier weather-resistant film is obtained;
forming a second gas barrier layer on one side surface of the plastic film through a deposition process to obtain a gas barrier plastic film; the gas barrier weather-resistant film and the gas barrier plastic film are arranged oppositely, and the first gas barrier layer and the second gas barrier layer are bonded by using a first adhesive to obtain a first composite film;
Arranging the first composite film and the functional fiber fabric layer oppositely, and bonding the plastic film and the functional fiber fabric layer by using a second adhesive to obtain a second composite film;
and forming the heat sealing layer on the surface of one side of the functionalized fiber fabric layer far away from the plastic film through a second coating process so as to obtain the flexible composite material.
8. The method according to claim 7, wherein the modification treatment comprises dip-coating the fiber fabric in a dip-coating liquid, and drying the fiber fabric subjected to the dip-coating treatment;
optionally, the dip-coating treatment is carried out for 5s-120s, the drying treatment is carried out at a temperature of 80-135 ℃ and the drying treatment is carried out for 2-3 min.
9. The method of claim 8, wherein the dip coating solution comprises 1.5-25 parts by weight of the grafting agent, 0.2-2.5 parts by weight of the film forming agent, 0.01-0.5 parts by weight of the initiator, and 20-2000 parts by weight of the solvent.
10. The method of claim 9, wherein the grafting agent comprises at least one of methyl methacrylate, butyl acrylate, acrylic acid-hydroxypropyl ester, acrylic acid-hydroxyethyl ester, N-methylolacrylamide, propyl methacrylate-based triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanurate, gamma-ureidopropyltrimethoxysilane, gamma-ureidotriethoxysilane, gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatotriethoxysilane, and propenyl trimethyl phosphate, tetraisopropoxytitanium, triisopropoxyaluminum, aluminum trichloride, titanium tetrachloride, and zirconium tetrachloride;
Optionally, the film former comprises a water soluble polymer comprising at least one of polyacrylamide, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, poly (acrylic acid/methacrylic acid) copolymer, polyvinyl alcohol, polyethylenimine, polyethylene oxide, ethylene-vinyl alcohol copolymer, polyethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, polysaccharides, chitosan, and cellulose;
optionally, the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, and azobisisovaleronitrile, dopamine hydrochloride, azobisisobutyrimidine hydrochloride, azobisiso Ding Mi-in hydrochloride, azobisiso Ding Mi-in, and azobiscyano valeric acid;
optionally, the solvent comprises a mixed solution of water and an alcohol comprising at least one of methanol, ethanol, isopropanol, and n-propanol.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116653398A (en) * 2023-07-27 2023-08-29 山东联欣环保科技有限公司 Barrier composite film and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116653398A (en) * 2023-07-27 2023-08-29 山东联欣环保科技有限公司 Barrier composite film and application thereof
CN116653398B (en) * 2023-07-27 2023-10-20 山东联欣环保科技有限公司 Barrier composite film and application thereof

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