CN110418864A - The application of fiber after a kind of surface treatment method of ultra high molecular weight polyethylene fiber and processing - Google Patents

The application of fiber after a kind of surface treatment method of ultra high molecular weight polyethylene fiber and processing Download PDF

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Publication number
CN110418864A
CN110418864A CN201880015301.8A CN201880015301A CN110418864A CN 110418864 A CN110418864 A CN 110418864A CN 201880015301 A CN201880015301 A CN 201880015301A CN 110418864 A CN110418864 A CN 110418864A
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China
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molecular weight
fiber
weight polyethylene
high molecular
ultra high
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Chinese (zh)
Inventor
马俭
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Zhejiang Quantumeta Amt Co ltd
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Zhejiang Quantumeta Amt Co ltd
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Priority claimed from CN201710127280.6A external-priority patent/CN108532286A/en
Priority claimed from CN201710552564.XA external-priority patent/CN109208338B/en
Priority claimed from CN201721810742.6U external-priority patent/CN208198777U/en
Priority claimed from CN201721921518.4U external-priority patent/CN208078152U/en
Application filed by Zhejiang Quantumeta Amt Co ltd filed Critical Zhejiang Quantumeta Amt Co ltd
Publication of CN110418864A publication Critical patent/CN110418864A/en
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    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D06M15/555—Epoxy resins modified by compounds containing phosphorus
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention discloses the application of fiber after a kind of surface treatment method of ultra high molecular weight polyethylene fiber and processing, the surface of the ultra high molecular weight polyethylene fiber can reach 72mN/m or more.Preparation method is characterized in that introducing polar functional group on ultra high molecular weight polyethylene fiber surface with the method chemically and physically combined.Since the introducing of polar functional group enables the surface of fiber to significantly improve, it is significantly improved with the composite performance of other materials, the tensile strength of product containing the ultra high molecular weight polyethylene fiber, tearing strength, bursting strength are big, therefore the ultra high molecular weight polyethylene fiber such as can be widely used for the preparation of film, composite material or fabric and be applied to pneumatic membrane building, air bag, dirigible, radome, protective textile, tent at the hard structures material such as soft compound fabric and the helmet, club/racket, vehicle enclosure.

Description

The application of fiber after a kind of surface treatment method of ultra high molecular weight polyethylene fiber and processing Technical field
The present invention relates to the applications of fiber after a kind of surface treatment method of ultra high molecular weight polyethylene fiber and processing.
Background technique
Ultra-high molecular weight polyethylene (english abbreviation UHMWPE) fiber is a kind of high-intensitive, high modulus fibre prepared as raw material through special process using UHMWPE, with the big high-performance fiber of aramid fiber and carbon fiber and referred to as three.UHMWPE fiber is by simple methylene (- CH 2) composition, the crystallinity of fiber is greater than 90%, and the degree of orientation of segment is close to 100%, and such design feature leads to its excellent in mechanical performance, and fiber surface is very smooth, and cohesive energy is low, has good rub resistance and chemical corrosion resistance.UHMWPE fiber is because having the excellent properties such as density is small, intensity is high, corrosion-resistant, shock resistance, anti-cut, so UHMWPE fiber is used to be modified as substrate, can get the functional fiber material with excellent properties.But since UHMWPE fiber and the adhesive force of other composite materials are very poor, interface cohesion is insecure, is difficult to be directly used as reinforcing fiber to prepare fibre reinforced composites.
The surface energy of ultra high molecular weight polyethylene fiber how is improved for mentioning, scholar both domestic and external has been devoted to the research of the project, also there is many related patents and reference works, wherein cutting both ways.
Summary of the invention
Problem to be solved by this invention is how to improve the surface energy of ultra high molecular weight polyethylene fiber.
The first aspect of the present invention provides a kind of ultra high molecular weight polyethylene fiber, which is characterized in that the surface of the fiber can be 72mN/m or higher, preferably 80mN/m or higher, more preferable 90mN/m or higher, more preferable 100mN/m or higher.
The second aspect of the present invention provides a kind of surface treatment method of ultra high molecular weight polyethylene fiber comprising following steps:
Offer a roll is not less than 1g/d more than a roll of intensity, is preferably not less than 5g/d, more desirably not less than 10g/d, is further much more desirably not less than the virgin ultrahigh molecular weight polyethylene fibre of 15g/d and carries out unwrapping wire acquisition yarn；
Yarn is subjected to corona treatment to obtain processed yarn；
At least part to the yarn of the processing all carries out starching (sizing) using size composition and handles to obtain ultra high molecular weight polyethylene fiber, wherein the size composition contain selected from one of alcohols, epoxy resin, polyurethane and isocyanates or more than one, the surface of the ultra high molecular weight polyethylene fiber can be 72mN/m or higher, preferably 80mN/m or higher, more preferable 90mN/m or higher, more preferable 100mN/m or higher.
Preferably, the stretch processing of the treated yarn is carried out before or after the starching is handled and/or simultaneously.Preferably, the speed of the stretch processing is 1~50m/min, preferably 10~30m/min, more preferably 15~25m/min.
Preferably, the size composition contain one of alcohols, bisphenol-A-(chloropharin) epoxy resin, polyurethane and isocyanates selected from C1~C12 or more than one.
Preferably, the alcohols is propyl alcohol class, and preferably 1- methoxy-2-propanol and/or the bisphenol-A-(chloropharin) epoxy resin are bisphenol-A-(chloropharin) epoxy resin that molecular weight is equal to or less than 700.
Preferably, the size composition contains following component: the water of bisphenol-A-(chloropharin) epoxy resin of a.0~5wt% 1- methoxy-2-propanol, and/or b.0~5wt% molecular weight equal to or less than 700, and/or c.0~5wt% polyurethane, and/or d.0~5wt% isocyanates and 80%~96wt%, total weight based on size composition calculates, and precondition a, b, c, d cannot be 0 simultaneously.
Preferably, the corona treatment carries out under the ionic environment full of inert gas and/or non-inert gas.
Preferably, the gas component that the corona treatment uses is 90% nitrogen and 10% oxygen.
Preferably, power when carrying out the corona treatment is 3~100kw, preferably 20~80kw, most preferably 40~60kw.
Preferably, the method further includes to being dried after the progress starching processing of the treated yarn the step of, it is preferable that the drying temperature is 100 DEG C~160 DEG C, preferably 105 DEG C~140 DEG C, most preferably 120 DEG C.
Preferably, the molecular weight of the virgin ultrahigh molecular weight polyethylene fibre is 50~10000dtex in 100,000 or more, preferably 200,000 or more more preferable 500,000 or more, further preferred 1,000,000 or more and/or its fiber number.
The third aspect of the present invention provides a kind of ultra high molecular weight polyethylene fiber obtained by the above method.
The fourth aspect of the present invention provides one kind containing above-mentioned ultra high molecular weight polyethylene fiber product, and the product can be film, composite material or fabric.
The fifth aspect of the present invention provides the purposes that above-mentioned ultra high molecular weight polyethylene fiber is used to prepare the hard structures material such as the soft compound fabric such as pneumatic membrane building, air bag, dirigible, radome, protective textile, tent and the helmet, club/racket, vehicle enclosure.
The sixth aspect of the present invention provides a kind of size composition, it contains selected from alcohols, epoxy resin, one of polyurethane and isocyanates or more than one, preferably, the size composition contains the alcohols selected from C1~C12, bisphenol-A-(chloropharin) epoxy resin, one of polyurethane and isocyanates or more than one, more preferably, the alcohols is propyl alcohol class, it is preferred that 1- methoxy-2-propanol, and/or bisphenol-A-(chloropharin) epoxy resin is bisphenol-A-(chloropharin) epoxy resin that molecular weight is equal to or less than 700, most preferably, the size composition contains following component: a.0~5wt% 1- methoxy-2-propanol, and/or b.0~5wt% molecular weight is equal to or less than 700 bisphenol-A-(chloropharin) epoxy resin, And/or c.0~5wt% polyurethane, and/or d.0~5wt% isocyanates and e.80%~96wt% water, the total weight based on size composition calculate, precondition a, b, c, d cannot be 0 simultaneously.
Detailed description of the invention
Fig. 1 is the schematic diagram for indicating a kind of apparatus for production line set-up mode of the invention.
Fig. 2 is the schematic diagram of composite membrane of the invention.
Specific embodiment
The present invention passes through the specific embodiments and the drawings technical solution that the present invention is further explained, but those of ordinary skill in the art will appreciate that: following specific embodiments and embodiment are intended to illustrate the present invention, but should not be understood as limiting the invention in any way.
In the present invention, the molecular weight of virgin ultrahigh molecular weight polyethylene fibre is 50~10000dtex in 100,000 or more, preferably 200,000 or more more preferable 500,000 or more, further preferred 1,000,000 or more and/or its fiber number.Also, the intensity of virgin ultrahigh molecular weight polyethylene fibre is not less than 1g/d, preferably not less than 5g/d, more desirably not less than 10g/d, further much more desirably not less than 15g/d.
" virgin ultrahigh molecular weight polyethylene fibre " (or yarn) used herein, from the fiber making step obtained by one or more steps stretching or other means.The process of ideal production fiber is described in United States Patent (USP) 6969553,7344668,7370395,7846363 including obtaining height-oriented fiber by stretching.As described in the patent of above-mentioned reference, virgin ultrahigh molecular weight polyethylene fibre (yarn) is usually to generate from gel spinning process, height-oriented fiber (yarn) is obtained by stretching, it is different from " part orients " fiber (or " partially oriented yarn "), processing after being stretched to height-oriented fiber, to improve its fibre strength.Therefore, height-oriented yarn/fiber has intensity more higher than partially oriented yarn/fiber.Term as used herein " intensity " refers to referring to the maximum tensile stress (gram) that every denier fiber is able to bear, and unit is expressed as g/d, passes through ASTMD2256 and measures.The method according to the invention, the processing to mention high surface energy (such as corona treatment or sided corona treatment) are carried out in exposed fiber surface/surface region.
Surface can be the measurement destroyed when creating material surface to intermolecular chemical bond.In solid-state physics theory, surface atom has more energy than the atom inside substance, and therefore, according to maximum energy criterion, what atom can be spontaneous tends to inside substance rather than surface.
It is the energy that material surface is had more relative to material internal in the definition of Material Field, surface energy.One solid material is resolved into fritter and needs to destroy its internal chemical bond, so requiring the expenditure of energy.Because the surface newly formed be it is highly unstable, they generate absorption by surface atom recombination and mutual reaction, or to other molecules of surrounding or atom, so that surface energy be made to reduce.It is also understood that since the bond energy of superficial layer atom towards outside is not compensated for, so that surface particle has additional potential energy, referred to as surface energy than internal particle.
Generate function made by the new surface of unit area:
Y=dw/ds
The surface of substance has surface tension σ, reversibly increase surface area dA under constant temperature and pressure, then need function σ dA, because required function is equal to the increase of object system free energy, and this increase is therefore referred to as surface free energy or surface energy caused by increasing due to the surface area of object system.Surface tension can be indicated with the unit of N/cm.The surface tension of different materials (liquid) is different, this is related with intermolecular active force (including dispersion, polarity and hydrogen bond) size.The big person's surface tension that interacts is high, and then surface tension is low by the small person that interacts, however, surface tension size, object always tries hard to reduce its surface, drops low-surface-energy, tends to stablize.
" fiber " used herein is a kind of elongated structural body of the draw ratio greater than 1000.Used fiber is preferably a continuous elongated structural body, rather than short, discontinuous " staple fiber ", the cross section for the fiber being used in the present invention may be very different, they can be circular, flat or oval cross section.Therefore, " fiber " word includes silk, band and item etc. with rule or irregular cross section, and preferably fiber has a substantially circular cross section.Term " yarn (yarn) " is defined as a kind of continuous strand being made of multiple long filaments.Yarn can be formed by a kind of long filament or by a variety of long filaments, be known respectively as " monfil " or " multifilament fiber ".
Make fiber by carrying out corona treatment in ionization environment full of inertia or non-inert gas, as gas component used in corona treatment, such as, oxygen, argon, helium, ammonia or other suitable inert gases or non-inert gas can be enumerated, it also include the combination of above-mentioned gas, so that fiber and the combination of neutral molecule, ion, free radical and ultraviolet light be made to contact.Fiber can also be made to pass through the ionization environment not filled with special gas to carry out corona treatment.In fiber surface, kinetic energy and electron exchange etc. as caused by the collision on the surface with charged particle (ion), to improve the surface energy of fiber surface.Collision between fiber surface and free radical will lead to similar chemical rearrangement, and then improve the surface energy of fiber.
The selection of gas is important, because the chemical structure of fiber surface can be carried out to different modifications using different plasma gas, this belongs to well-known technique in this field.It is, for example, possible to use ammonia plasma treatments to be introduced into amine function on fiber surface, and carboxyl and hydroxyl group are introduced on fiber surface with oxygen plasma.
Corona treatment can be used any useful commercial plasma processor and carry out, as the commercial plasma processor, such as it is purchased from the SoftalCorana&Plasma GmbH&Co positioned at Hamburg, Germany, positioned at the 4th State of California Bellmont, positioned at the Plasmatrcat US LP etc. of Illinois Ai Erjin.
As an embodiment, plasma treatment procedure is most preferably carried out in 40~60kw in RF power setting preferably 3~100kw, more preferable 20~80kw.The plasma treatment process is to carry out under vacuum conditions, and vacuum degree is less than 10mbar, and the processing time can be between 0~1000 second.
Fiber/yarn after corona treatment is transported to a post-tensioning device before or after carrying out starching and/or simultaneously, described device includes one or more draw rolls and multiple baking ovens, virgin ultrahigh molecular weight polyethylene fibre is stretched/redraws, drafting process is simultaneously dried the slurry on fiber, is eventually converted into required fiber/yarn.The baking oven is preferably forced convection oven, and temperature is maintained at 100 DEG C to 160 DEG C or so, preferably 105 DEG C~140 DEG C, more preferable 120 DEG C.Multiple adjacent baking ovens in the post-tensioning device can be horizontally arranged, or is arranged vertically in top of each other, or is also possible to horizontally arranged and vertical arrangement combination.Also other means of dry coating described in the prior can be used.
Starching (sizing) composition of the present invention also calls glue composition, contain selected from one of alcohols, epoxy resin, polyurethane and isocyanates or more than one.
The alcohols refers to the compound containing the hydroxyl combined with the carbon on alkyl or benzene ring side chain in molecule.According to the number of hydroxyl, can be divided into can be divided into unitary, binary, ternary or polyalcohol.Common alcohol has C1~C12 alcohols, such as methanol, ethyl alcohol, propyl alcohol, benzyl alcohol, ethylene glycol, glycerine, butanol etc..
The epoxy resin refers to the organic compound in molecule containing two or more epoxy groups, and in addition to individual, their relative molecular mass is not high.
According to molecular structure, epoxy resin can be generally divided into five major class:
1. glycidyl ether type epoxy resin
2. glycidyl ester epoxy resin
3. glycidyl amine epoxy resin
4. linear aliphatic epoxy resin
5. alicyclic based epoxy resin
Polyurethane full name is polyurethanes, is the general designation containing the macromolecular compound for repeating urethano (- NHCOO-) on main chain.It is to be formed by organic diisocyanate or polyisocyanates with dihydroxy or polyol addition polymerization.In polyurethane macromolecular other than carbamate, it can also contain the groups such as ether, ester, urea, biuret, allophanate, vinyl.
Isocyanates is the general name of the various esters of isocyanic acid.If with the quantitative classification of-NCO group, including monoisocyanates R-N=C=O and diisocyanate O=C=N-R-N=C=O and polyisocyanates etc..Isocyanate compound can be divided into following a few classes: (1) alkyl monoisocyanate (2) (substitution) phenyl monoisocyanates (3) alpha-substituted benzyl isocyanate ester (4) polyisocyanates.Current most widely used, maximum yield is that have: toluene di-isocyanate(TDI) (Toluene Diisocyanate, abbreviation TDI)；Methyl diphenylene diisocyanate (MethylenediphenylDiisocyanate, abbreviation MDI).
Size composition of the invention is further preferably selected from the alcohols of C1~C12, bisphenol-A-(chloropharin) epoxy resin, one of polyurethane and isocyanates or more than one, more preferably, the alcohols is propyl alcohol class, it is preferred that 1- methoxy-2-propanol, and/or bisphenol-A-(chloropharin) epoxy resin is bisphenol-A-(chloropharin) epoxy resin that molecular weight is equal to or less than 700, most preferably, the size composition contains following component: a.0~5wt% 1- methoxy-2-propanol, and/or b.0~5wt% molecular weight is equal to or less than 700 bisphenol-A-(chloropharin) epoxy resin, and/or c.0~5wt% polyurethane, and/or d.0~5wt% isocyanates, and e.80%~96wt% water, Total weight based on size composition calculates, and precondition a, b, c, d cannot be 0 simultaneously.Among the ingredient of above-mentioned size composition, it will be understood by those skilled in the art that, a, tetra- kinds of ingredients of b, c, d can be modified on the basis of limited trials, for example, component: a.1- the content of methoxy-2-propanol can between 0~20wt%, the content of bisphenol-A-(chloropharin) epoxy resin of b. molecular weight equal to or less than 700 is between 0~20wt%, the content of c. polyurethane is between 0~20wt%, the content of d. isocyanates is between 0~20wt%.
Those of ordinary skill in the art understand the conventional practices of stretched operation, are all expressly incorporated herein by reference for example including condition described in United States Patent (USP) 6969553, United States Patent (USP) 7344668 or United States Patent (USP) 7370395.Embodiment during one post-tensioning is as shown in Figure 1.Fig. 1 describes a kind of post-tensioning device, including unwinding frame 1, seven roller machines 1, apparatus for processing plasma 3, starching machine 4, baking oven 5, seven roller machines 26, up- coiler 7.It will be appreciated by a person skilled in the art that according to required configuration, as long as the purpose of the present invention can be reached, wherein the quantity of the stretching device repetitive unit is the amount doesn't matter.
In embodiment as shown in Figure 1, volume 1 or volume 1 or more virgin ultrahigh molecular weight polyethylene fibre is placed on unwinding frame 1, the traction through seven roller machines 1 carries out unwrapping wire, obtains yarn.The hauling speed of seven roller machines 1 is 1~50m/min, preferably 5~10m/min.
Yarn passes sequentially through apparatus for processing plasma 3, starching machine 4 and baking oven 5 in the draught line of seven roller machines 26.The speed of seven roller machines 26 is 1~50m/min, preferably 10~30m/min, more preferable 15~25m/min.
The gas component that corona treatment uses is 90% nitrogen and 10% oxygen.
In starching machine 4, starching raw material is preferably the size composition containing alcohols and epoxy resin.
Under the traction of seven roller machines 26, yarn passes through baking oven 5 with certain speed.The length of baking oven 5 can be 3m~30m, preferably 6m~12m.Drying time is 10~150 seconds, preferably 10~90 seconds, more preferable 10~30 seconds.
In up- coiler 7, by starching, treated that ultra high molecular weight polyethylene fiber is wound.Since the hauling speed of seven roller machines 26 and up- coiler 7 is poor, fiber is stretched.In one preferred embodiment, the stretch ratio of ultra high molecular weight polyethylene fiber is 1 ︰ 15, it is preferred that 1 ︰ 3, more preferable 1 ︰ 1, the surface of final fiber can be 50mN/m or higher, preferably 60mN/m or higher, more preferable 70mN/m or higher, more preferable 72mN/m or higher, preferably 80mN/m or higher, more preferable 90mN/m or higher, more preferable 100mN/m or higher.
Various products can be made in obtained ultra high molecular weight polyethylene fiber, for example, can be the film containing above-mentioned ultra high molecular weight polyethylene fiber, composite material, fabric etc..As long as the product contains ultra high molecular weight polyethylene fiber (yarn) of the invention.
Here film refers to the film as made from the material at least containing ultra high molecular weight polyethylene fiber of the invention.
Composite material refers to the fiber combinations referred to containing structural material made of ultra high molecular weight polyethylene fiber of the invention and other basis materials at least with ultra high molecular weight polyethylene fiber of the invention.Thermoplastic polymer layer can also be formed on surface.
Fabric be fiber, long filament and/or yarn by least containing ultra high molecular weight polyethylene fiber of the invention by intersecting, around knot, the relationships such as connect and constitute, including filament yarn fabric and spun fabric.Fabric includes textile fabric and non-woven fabrics.Non-woven fabrics needs not move through weaving to be formed, and is only oriented fiber or long filament or then random alignment, formation fibre net structure are reinforced using the methods of mechanical, hot sticky or chemical.
An application as ultra high molecular weight polyethylene fiber of the invention, composite membrane fiber of the invention includes enhancement layer and polymer coating, wherein, enhancement layer is the fabric containing above-mentioned ultra high molecular weight polyethylene fiber, and polymer coating is coated on the upper surface of enhancement layer and/or below.
In a preferred embodiment, the fabric of the above-mentioned polyethylene fibre containing super high molecular weight as enhancement layer is the base fabric that ultra high molecular weight polyethylene fiber volume content is higher than 10%.
In a preferred embodiment, above-mentioned base fabric is weaved with the fibrous material containing ultra high molecular weight polyethylene fiber.
In a preferred embodiment, the micropore of above-mentioned base fabric is uniformly distributed and is less than or equal to 1000 mesh；Preferably lower than or equal to 100 mesh；More preferably less than or equal to 50 mesh.
In a preferred embodiment, the intensity of above-mentioned ultra high molecular weight polyethylene fiber is not less than 10cN/dtex；Preferably not less than 20cN/dtex；More preferably no less than 30cN/dtex.
In a preferred embodiment, above-mentioned polymer coating is thermoplastic polymer coating, it is preferable that it can be for selected from one of thermoplastic polyurethane elastomer, polytetrafluoroethylene (PTFE), polyethylene, polyvinyl chloride, liquid silastic or a variety of；It is preferably selected from one of thermoplastic polyurethane elastomer, polyethylene, polyvinyl chloride or a variety of；Most preferably thermoplastic polyurethane elastomer；The better Polyether-type thermoplastic polyurethane elastomer of particularly preferred water resistance.
The above-mentioned polymer coating coated on above and below enhancement layer can penetrate through cooling and solidifying by the micropore of enhancement layer and be bonded together.
Above-mentioned solidification refers to that polymer is changed into solid process by molten state.The type of cooling can use natural cooling or water cooling or air-cooled.
Tensile strength, tearing strength and the bursting strength of such composite membrane are improved.Specifically, the tensile strength of the composite membrane is greater than 2000N/5cm, preferably greater than 5000N/5cm, preferably greater than 7000N/5cm, more preferably greater than 10000N/5cm, most preferably greater than 12000N/5cm；Tearing strength is greater than 600N, preferably greater than 900N, more preferably greater than 1200N；Bursting strength is greater than 1000N, preferably greater than 1500N, more preferably greater than 1900N.
The manufacturing method of composite membrane of the invention, comprising the following steps:
By the selected fibrous material woven into fabric containing ultra high molecular weight polyethylene fiber；
By selected polymer coating materials through screw rod melting extrusion；
The molten polymer of melting extrusion is coated in the two sides of fabric.
The manufacturing method of composite membrane of the invention can also include the steps that pressing together multiple base cloth layers or polymeric layer under the action of external pressure and form a film material.
In one preferred embodiment, comprising the following steps:
1. fiber and coating material are selected: selection intensity is not less than the ultra high molecular weight polyethylene fiber of 10cN/dtex；Suitable polymer coating is selected according to requirements, can be selected from thermoplastic polyurethane elastomer, polytetrafluoroethylene (PTFE), polyethylene, polyvinyl chloride or silicon rubber.
2. woven into fabric: according to composite membrane through broadwise intensity requirement, designing suitable line density and carry out woven fabric.
3. applying coating: polymeric aggregate being put into the hopper of screw extruder, dressing melting extrusion will be applied with screw extruder, polymer melting material is from even application after die head extrusion on ultra-high molecular weight polyethylene fabric.
The coating for so carrying out polymer coating respectively in the upper and lower surface of fabric finally obtains the two-sided composite membrane for being all coated with polymer coating.
Product containing ultra high molecular weight polyethylene fiber of the invention, it can be film, composite material or fabric, it can be applied to the soft compound fabric of pneumatic membrane building, air bag, dirigible, radome, protective textile, tent etc., the hard structures materials such as the helmet, club/racket, vehicle enclosure.
The present invention is described with specific embodiment below, it is understood to one skilled in the art that protection scope of the present invention is limited to claim, following embodiments do not limit the invention in any way just to illustrate the purpose of the present invention.
Embodiment
[Examples 1 to 7]
Virgin ultrahigh molecular weight polyethylene fibre used in Examples 1 to 7 is the 1000D ultra high molecular weight polyethylene fiber for being purchased from Qingdao Xin Tai high molecular material Co., Ltd, and molecular weight is 3,000,000, density 0.97g/cm 3。
The virgin ultrahigh molecular weight polyethylene fibre for being 15g/d by the intensity of volume 20 is placed on 1 progress unwrapping wire on unwinding frame.It is 10m/min by speed by seven roller machines 1.
Yarn is divided into 90% nitrogen and 10% oxygen, power 30kw parallel through apparatus for processing plasma 3, corona treatment using gas group, vacuum degree 1mbar, the processing time 500 seconds introduces free radical and a small amount of polar functional group, such as carboxyl, hydroxyl and carbonyl in fiber surface.
For fiber after processing by the coating solution in starching machine 4, size composition solution composition is as shown in table 1.
[table 1]
The fiber for being coated with above-mentioned solution enters the drying of baking oven 5, and drying time is 100 seconds, and the temperature of baking oven is set as 120 DEG C.
The speed of seven roller machines 26 is 11m/min.The winding speed of up- coiler 7 is 11.1m/min.
The treated fiber obtained is for measuring surface energy values.
Surface energy test method and use surface energy tested inks are as follows:
The test of surface energy can tested inks progress using surface.Used surface energy tested inks are Germany's plasmatreat tested inks, and the test scope for the surface energy that can reach is 40~72mN/m, are purchased from upper marine sequence Information technology Co., Ltd.That specifically tests illustrates to see http://www.plasmatreat.cn/surface-determination/test-ink-method .html.
The test method that the present invention carries out fiber are as follows: use plasmatreat tested inks C (ethanol series tested inks) series, fiber is subjected to laying, appropriate surface energy tested inks are picked with a dyne pen, the line for being about 10cm is radially drawn then along fiber, if fiber does not shrink or formed drop in 2 seconds, show that the surface of fiber can be greater than the label surface energy values of surface energy tested inks.
After processing is completed, 20 sites are randomly selected on the fiber obtained in the embodiment of the present invention 1, measure surface energy values, and the results are shown in Table 2, and test dyne value is all at least 72mN/m.
[table 2]
Yarn position number Test dyne value (mN/m)
1 ≥72
2 ≥72
3 ≥72
4 ≥72
5 ≥72
6 ≥72
7 ≥72
8 ≥72
9 ≥72
10 ≥72
11 ≥72
12 ≥72
13 ≥72
14 ≥72
15 ≥72
16 ≥72
17 ≥72
18 ≥72
19 ≥72
20 ≥72
When to fiber obtained in the embodiment of the present invention 1 when handling completion, 24 hours, 48 hours, 96 hours, 168 hours, 6 months after the completion of processing, randomly selecting 20 sites progress surface on surface can test, the results are shown in Table 3, and test average out to is all at least 72mN/m because of value.
[table 3]
Testing time Average out to is tested because of value (mN/m)
When processing is completed ≥72
After processing for 24 hours ≥72
48h after processing ≥72
96h after processing ≥72
168h after processing ≥72
6 months after processing ≥72
Also similarly to Example 1 to fiber obtained in the embodiment of the present invention 2~7, after processing is completed, 20 sites are randomly selected on obtained fiber, measure surface energy values, as a result, test dyne value is all at least 72mN/m.
Also similarly to Example 1 to fiber obtained in the embodiment of the present invention 2~7, when when handling completion, 24 hours, 48 hours, 96 hours, 168 hours, 6 months after the completion of processing, randomly selecting 20 sites progress surface on surface can test, and test average out to is also all at least 72mN/m because being worth.
[comparative example 1]
Virgin ultrahigh molecular weight polyethylene fibre is using the 1000D ultra high molecular weight polyethylene fiber for being purchased from Qingdao Xin Tai high molecular material Co., Ltd, and molecular weight is 3,000,000, density 0.97g/cm 3。
The virgin ultrahigh molecular weight polyethylene fibre for being 15g/d by the intensity of volume 20 is placed on unwinding frame 1 and carries out unwrapping wire.It is 10m/min by speed by seven roller machines 1.
The fiber of not plasma-treated and starching processing enters the drying of baking oven 5, and drying time is 100 seconds, and the temperature of baking oven is set as 120 DEG C.The speed of seven roller machines 26 is 11m/min.The winding speed of up- coiler 7 is 11.1m/min.
The fiber obtained by this processing, which carries out surface with surface energy tested inks, to be tested, and test dyne value is entirely below 42mN/m.
[comparative example 2]
Virgin ultrahigh molecular weight polyethylene fibre is using the 1000D ultra high molecular weight polyethylene fiber for being purchased from Qingdao Xin Tai high molecular material Co., Ltd, and molecular weight is 3,000,000, density 0.97g/cm 3。
The virgin ultrahigh molecular weight polyethylene fibre for being 15g/d by the intensity of volume 20 is placed on unwinding frame 1 and carries out unwrapping wire.It is 10m/min by speed by seven roller machines 1.
Fiber through corona treatment similarly to Example 1 but without starching processing, which enters baking oven 5, dries, and drying time is 100 seconds, and the temperature of baking oven is set as 120 DEG C.The speed of seven roller machines 26 is 11m/min.The winding speed of up- coiler 7 is 11.1m/min.
When to the fiber obtained by this processing when handling completion, 24 hours, 48 hours, 96 hours, 168 hours, 6 months after the completion of processing, randomly selecting 20 sites progress surface on surface can be tested, and test result is as shown in table 4.
[table 4]
Testing time Average out to is tested because of value (mN/m)
When processing is completed 72
After processing for 24 hours 64
48h after processing 52
96h after processing <42
168h after processing <42
6 months after processing <42
[comparative example 3]
Virgin ultrahigh molecular weight polyethylene fibre is using the 1000D ultra high molecular weight polyethylene fiber for being purchased from Qingdao Xin Tai high molecular material Co., Ltd, and molecular weight is 3,000,000, density 0.97g/cm 3。
The virgin ultrahigh molecular weight polyethylene fibre for being 15g/d by the intensity of volume 20 is placed on unwinding frame 1 and carries out unwrapping wire.It is 10m/min by speed by seven roller machines 1.
Fiber not plasma-treated, through starching processing similarly to Example 1, which enters baking oven 5, dries, and drying time is 100 seconds, and the temperature of baking oven is set as 120 DEG C.The speed of seven roller machines 26 is 11m/min.The winding speed of up- coiler 7 is 11.1m/min.
After processing is completed to the fiber obtained by this processing, 20 sites being randomly selected on obtained fiber, measuring surface energy values, test result is as shown in table 5.
[table 5]
Yarn position number Test dyne value (mN/m)
1 50
2 42
3 42
4 62
5 52
6 46
7 50
8 52
9 48
10 42
11 58
12 52
13 62
14 56
15 46
16 42
17 54
18 42
19 58
20 46
Average value 50.1
[embodiment 8]
In embodiment 8, the ultra high molecular weight polyethylene fiber (intensity 20cN/dtex) that is obtained using embodiment 4；As the material of polymer coating, using thermoplastic polyurethane ( 9000TPU, Lubrizol company).
When being made into base fabric, the weaving manner of fabric is plain woven, surface density 630g/m 2。
In applying coating, polyether thermoplastic polyether polyols pellet is put into the hopper of screw extruder, extruder temperature is set as 200 DEG C, pellet is set to flow into screw extruder by gravity, after the heating melting that polyurethane particles pass through screw rod, becomes flowable liquid, formed by mold membranaceous, then it is coated in fabric surface, forms structure of composite membrane.
The coating for so carrying out polymer coating respectively in the upper and lower surface of fabric finally obtains the two-sided composite membrane for being all coated with polymer coating.
[embodiment 9]
In embodiment 9, the ultra high molecular weight polyethylene fiber (intensity 30cN/dtex) obtained in the enhancement layer using embodiment 2, and make surface density 400g/m 2, polyvinyl chloride (PVC is resin dedicated, the super Hua Huagong of Dongguan City) is used in polymer coating, in addition to this, obtains composite membrane similarly to Example 8.
[embodiment 10]
In embodiment 10, the ultra high molecular weight polyethylene fiber (intensity 30cN/dtex) obtained in the enhancement layer using embodiment 1 makes 2 layers of fabric layers, surface density 1600g/m 2, in addition to this, composite membrane is obtained similarly to Example 8.
[embodiment 11]
In embodiment 11, make 1 layer of fabric layers in the enhancement layer, surface density 1000g/m 2, in addition to this, composite membrane is obtained similarly to Example 10.
[comparative example 4]
In a comparative example, terylene (TCS-FDY, Tong Kun group) is used in the enhancement layer, makes surface density 1000g/m 2, in addition to this, composite membrane is obtained similarly to Example 8.
The performance characterization of obtained composite membrane is measured, wherein, measurement standard about each performance standard, surface density is carried out according to the regulation of GB/T 4669-2008, tensile strength is carried out according to the regulation of GB/T 3923.1-2013, peel strength according to the regulation of GB/T 2791-1995 carry out, tearing strength according to the regulation of GB3917.3 carry out, bursting strength according to regulation carry out GB/T14800-2010.
The information and properties of product of embodiment 8~11 and comparative example 4 are shown in Table 6.
[table 6]

Claims (17)

  1. A kind of ultra high molecular weight polyethylene fiber, which is characterized in that the surface of the fiber can be 72mN/m or higher, preferably 80mN/m or higher, more preferable 90mN/m or higher, more preferable 100mN/m or higher.
  2. A kind of surface treatment method of ultra high molecular weight polyethylene fiber comprising following steps:
    Offer a roll is not less than 1g/d more than a roll of intensity, is preferably not less than 5g/d, more desirably not less than 10g/d, is further much more desirably not less than the virgin ultrahigh molecular weight polyethylene fibre of 15g/d and carries out unwrapping wire acquisition yarn；
    Yarn is subjected to corona treatment to obtain processed yarn；
    At least part to the treated yarn all carries out starching using size composition and handles to obtain ultra high molecular weight polyethylene fiber, wherein the size composition contain selected from one of alcohols, epoxy resin, polyurethane and isocyanates or more than one, the surface energy 72mN/m or higher of the ultra high molecular weight polyethylene fiber, preferably 80mN/m or higher, more preferable 90mN/m or higher, more preferable 100mN/m or higher.
  3. According to the method described in claim 2, wherein, the stretch processing of the treated yarn is carried out before or after starching processing and/or simultaneously.
  4. According to the method in claim 2 or 3, wherein the size composition contain one of alcohols, bisphenol-A-(chloropharin) epoxy resin, polyurethane and isocyanates selected from C1~C12 or more than one.
  5. According to the method described in claim 4, wherein, the alcohols is propyl alcohol class, preferably 1- methoxy-2-propanol and/or the bisphenol-A-(chloropharin) epoxy resin are bisphenol-A-(chloropharin) epoxy resin that molecular weight is equal to or less than 700.
  6. According to the method in claim 2 or 3, wherein the size composition contains following component:
    A.0~5wt% 1- methoxy-2-propanol, and/or
    B.0~5wt% molecular weight is equal to or less than 700 bisphenol-A-(chloropharin) epoxy resin, and/or
    C.0~5wt% polyurethane, and/or
    D.0~5wt% isocyanates
    And
    E.80%~96wt% water,
    Total weight based on size composition calculates, and precondition a, b, c, d cannot be 0 simultaneously.
  7. According to the described in any item methods of claim 2 to 6, wherein the corona treatment carries out under the ionic environment full of inert gas and/or non-inert gas.
  8. According to the method described in claim 7, wherein, the gas component that the corona treatment uses is 90% nitrogen and 10% oxygen.
  9. According to the method described in claim 7, wherein, power when carrying out the corona treatment is 3~100kw, preferably 20~80kw, most preferably 40~60kw.
  10. According to the described in any item methods of claim 2 to 9, further comprise the step of drying after carrying out starching processing to the treated yarn, it is preferable that the drying temperature is 100 DEG C~160 DEG C, preferably 105 DEG C~140 DEG C, most preferably 120 DEG C.
  11. According to the method described in claim 3, wherein, the speed of the stretch processing is 1~50m/min, preferably 10~30m/min, more preferably 15~25m/min.
  12. According to the described in any item methods of claim 2 to 11, wherein, the molecular weight of the virgin ultrahigh molecular weight polyethylene fibre is 50~10000dtex in 100,000 or more, preferably 200,000 or more more preferable 500,000 or more, further preferred 1,000,000 or more and/or its fiber number.
  13. The ultra high molecular weight polyethylene fiber that the method according to claim 2~12 obtains.
  14. A kind of product contains ultra high molecular weight polyethylene fiber described in claim 1 or claim 13.
  15. Product according to claim 14, wherein the product is film, composite material or fabric.
  16. Ultra high molecular weight polyethylene fiber described in claim 1 or claim 13 is used to prepare the purposes of the hard structures material such as the soft compound fabric such as pneumatic membrane building, air bag, dirigible, radome, protective textile, tent and the helmet, club/racket, vehicle enclosure.
  17. A kind of size composition, it contains selected from alcohols, epoxy resin, one of polyurethane and isocyanates or more than one, preferably, the size composition contains the alcohols selected from C1~C12, bisphenol-A-(chloropharin) epoxy resin, one of polyurethane and isocyanates or more than one, more preferably, the alcohols is propyl alcohol class, it is preferred that 1- methoxy-2-propanol, and/or bisphenol-A-(chloropharin) epoxy resin is bisphenol-A-(chloropharin) epoxy resin that molecular weight is equal to or less than 700, most preferably, the size composition contains following component:
    A.0~5wt% 1- methoxy-2-propanol, and/or
    B.0~5wt% molecular weight is equal to or less than 700 bisphenol-A-(chloropharin) epoxy resin, and/or
    C.0~5wt% polyurethane, and/or
    D.0~5wt% isocyanates
    And
    E.80%~96wt% water,
    Total weight based on size composition calculates, and precondition a, b, c, d cannot be 0 simultaneously.
CN201880015301.8A 2017-03-06 2018-03-06 The application of fiber after a kind of surface treatment method of ultra high molecular weight polyethylene fiber and processing Pending CN110418864A (en)

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CN201710127280.6A CN108532286A (en) 2017-03-06 2017-03-06 The application of fiber after a kind of surface treatment method of superhigh molecular weight polyethylene fibers and processing
CN2017101272806 2017-03-06
CN201710552564.XA CN109208338B (en) 2017-07-07 2017-07-07 Ultra-light high-strength flexible composite membrane and preparation method thereof
CN201710552564X 2017-07-07
CN201721810742.6U CN208198777U (en) 2017-12-21 2017-12-21 A kind of raising of a wreck air bag
CN2017218107426 2017-12-21
CN2017219215184 2017-12-29
CN201721921518.4U CN208078152U (en) 2017-12-29 2017-12-29 A kind of novel flexible radome
PCT/CN2018/078153 WO2018161897A1 (en) 2017-03-06 2018-03-06 Surface treatment method for ultra-high molecular weight polyethylene fiber and application of treated fiber

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CN114457580A (en) * 2022-01-19 2022-05-10 北京理工艾尔安全科技有限公司 Composite membrane material and preparation method thereof
CN115522386A (en) * 2022-10-25 2022-12-27 重庆国际复合材料股份有限公司 Ultra-high molecular weight polyethylene fiber sizing agent and preparation method and application thereof

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CN104662221A (en) * 2012-07-27 2015-05-27 霍尼韦尔国际公司 Novel UHMWPE fiber and method to produce
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CN113584624A (en) * 2021-08-18 2021-11-02 山东莱威新材料有限公司 Preparation method and application of ultra-high molecular weight and low creep polyethylene fiber
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CN115522386A (en) * 2022-10-25 2022-12-27 重庆国际复合材料股份有限公司 Ultra-high molecular weight polyethylene fiber sizing agent and preparation method and application thereof

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