CN108950852A - A kind of warp-knitted spacer fabric that part is hollow - Google Patents

A kind of warp-knitted spacer fabric that part is hollow Download PDF

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Publication number
CN108950852A
CN108950852A CN201810744017.6A CN201810744017A CN108950852A CN 108950852 A CN108950852 A CN 108950852A CN 201810744017 A CN201810744017 A CN 201810744017A CN 108950852 A CN108950852 A CN 108950852A
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China
Prior art keywords
graphene
folding
raw material
layer
surface layer
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CN201810744017.6A
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Chinese (zh)
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CN108950852B (en
Inventor
苏成喻
柯文新
石建良
杨孝清
黄小欣
任波
邓魏永
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Fujian Jinjiang Huayu Weaving Co Ltd
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Fujian Jinjiang Huayu Weaving Co Ltd
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Priority to CN201810744017.6A priority Critical patent/CN108950852B/en
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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
    • D04B21/16—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/22—Physical properties protective against sunlight or UV radiation
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2403/00—Details of fabric structure established in the fabric forming process
    • D10B2403/02—Cross-sectional features
    • D10B2403/021—Lofty fabric with equidistantly spaced front and back plies, e.g. spacer fabrics
    • D10B2403/0213—Lofty fabric with equidistantly spaced front and back plies, e.g. spacer fabrics with apertures, e.g. with one or more mesh fabric plies
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D10B2501/043—Footwear
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Abstract

The present invention relates to a kind of warp-knitted spacer fabrics that part is hollow, and it includes surface layer, articulamentum and bottom are attached on surface layer and bottom by articulamentum；Articulamentum is part connection, is attached at the both ends of surface layer and bottom by articulamentum, and carries out local connection on surface layer and the middle position of bottom, and the part of connection forms surface layer, three layers of solid construction of articulamentum and bottom；And not connected part just forms the hollow structure in part of surface layer and bottom, i.e., no articulamentum.The hollow structure in the part of the application plays good air permeability effect and good visual stimulus, and especially in surface layer and bottom, there are in the case where color difference.It especially is being used for footwear material technical field, is needing part hollow and local solid, for example vamp needs part is hollow to play airing function, upper of a shoe needs solid construction, plays a supporting role.

Description

A kind of warp-knitted spacer fabric that part is hollow
Technical field
The present invention relates to warp knit screen cloth production technical fields, are a kind of warp-knitted spacer fabrics that part is hollow specifically.
Background technique
Chinese Patent Application No. 201320200037.X is related to a kind of screen cloth, includes inner plexiform layer and outer plexiform layer, described Inner plexiform layer is interwoven by nylon monofilament and polypropylene filament, and the density of nylon monofilament is 15~23 per cm, polypropylene filament Density be 17~21 per cm, therefore the density of the inner plexiform layer is made to keep the state of relative loose, and then makes the net Cloth has ventilative and scattered wet performance well；The outer plexiform layer is interwoven by polyester monofilament and polyethylene monofilament, and terylene The density of monofilament is 32~37 per cm, and the density of polyethylene monofilament is 28~35 per cm, therefore makes the outer plexiform layer Density keep relatively compact state, and then the screen cloth is made to have certain elasticity and intensity, the inner plexiform layer and outer plexiform layer Between by nylon monofilament layer alternately braiding connection, thus make screen cloth provided by the utility model both had well breathe freely and Wet performance is dissipated, but also with certain elasticity and intensity.
Chinese Patent Application No. 201320295187.3 is related to field of textile, and in particular to a kind of screen cloth.This is practical Novel purpose is to provide a kind of unique structure, has good feel, the screen cloth that elasticity is good.The screen cloth, including staggeredly compile The warp and weft knitted, the warp or weft are equipped with surface several protrusions outstanding, and the material of the warp or weft is Complex yarn, the complex yarn include heart yarn and twine yarn outside, and the heart yarn is spandex fibre, and the outer yarn that twines includes tencel fibre Dimension, it is described to twine yarn along the outer circumference surface that the axis direction of heart yarn is wrapped over heart yarn outside.The screen cloth of the utility model is by mutually compiling The warp and weft knitted are constituted, and warp or weft are equipped with the protrusion of Bamboo-shaped, and when application makes product more solid, secured, no Easily cause running and structure novel, it is beautiful and generous, it can satisfy various products or occasion demand.
Chinese Patent Application No. 201320295015.6 is related to a kind of cloth, and in particular to one kind has certain elastic reaction Elastic screen cloth.The technical solution of the utility model is to provide a kind of elastic screen cloth, the elasticity screen cloth be by terylene layer of cloth and Viscose rayon layer of cloth is bonded, and the terylene layer of cloth and viscose rayon cloth layer surface have a fold, the terylene layer of cloth and viscous Flexible silk is equipped between glue fiber layer of cloth, the terylene layer of cloth is the meshed fabric of tool made of polyester fiber warp-knitting, The viscose rayon layer of cloth is the meshed fabric of tool made of viscose rayon warp-knitting.The elastic screen cloth of the utility model exists It is that there is fold up and down under unstretched state, retraction can be stretched, and can cling to the body always, has comfortable well Property, flexible silk are folded between upper layer and lower layer, improve bilevel bonding strength.
Chinese Patent Application No. 201320294900.2 is related to textile technology field, and in particular to a kind of terylene net Cloth.The utility model aim is to provide a kind of antibacterial dacron screen cloth with special elastic structure.The terylene mesh by surface layer, It bottom and is connected to polyester monofilament supporting layer between the two containing antibacterial agent and constitutes, the surface layer and contains antibacterial agent at bottom Polyester monofilament supporting layer the antibacterial three-layer mesh fabric of 3 D stereo is made into a manner of warp knit.The utility model has the beneficial effects that this Utility model terylene mesh is antibacterial three-layer mesh fabric of the polyester monofilament to contain antibacterial agent as supporting layer, has restraining and sterilizing bacteria Function has used viscose rayon and cotton fiber in the table cloth of mesh material, improves whole moisture pick-up properties and the contact of material Performance.This three-layer mesh fabric is the novel kind of a kind of high-quality, environmental protection, can meet the requirements at the higher level of the majority of consumers.
Chinese Patent Application No. 201220031468.3 is related to a kind of screen cloth composite material, and the composite material is by three-layered node The fabric of structure forms, and the outer layer of the composite material is terylene double-sided cloth, and the middle layer of the composite material is TPU membrane, the composite surface The internal layer of material is screen cloth.This kind of composite material uses the sandwich type structure of sandwich, and the terylene of outer layer wind and water preventing is two-sided Cloth, the TPU membrane of middle layer highly efficient gas permeable moisture-permeability waterproof and warmth retention property and frivolous screen cloth are perfectly combined together, can It preventing rainwater from entering again while sweat gas and moisture being allowed to dissipate, there is preferably high radix saposhnikoviae, high waterproof is moisture-penetrable ventilated, it keeps warm, Ageing-resistant, anti-freezing, the multiple functions such as abrasion-resistant make human body keep for a long time dry and comfortable and comfortable.It simultaneously can also be by the fitting Composite material is sewn into various articles, such as back belt, Neck protection belt, knee cap bandage, bracer, mattress with cutting method. 201320675899.8 the utility model relates to Strand Feeding Technique field more particularly to a kind of perspective screen cloth, including top layer screen cloth, institutes State perspective screen cloth further include having bottom screen cloth, be provided between bottom screen cloth and the top layer screen cloth multiple EVA foamed materials or The block of PE foamed material production, multiple blocks are intervally arranged.The perspective screen cloth of the utility model, top layer and bottom Layer is screen cloth structure, and multiple blocks is arranged at intervals between top layer screen cloth and bottom screen cloth, it is ensured that the utility model from Top layer screen cloth, which looks over, can see intermediate block and bottom screen cloth, and the block it can be seen that intermediate is looked over from bottom screen cloth Shape object and top layer screen cloth, transparent effect is good, further promoted cloth permeability, in addition, block be EVA foamed material or PE foamed material is made, and with the excellent and safe and non-toxic performance of material lightweight, physical property, is conducive to improve the additional of cloth product Value.
Chinese Patent Application No. 201310016147.5 is related to a kind of bamboo charcoal fiber mesh fabric, is by face silk, lousiness, bottom silk The molding sandwich structure screen cloth of warp knit, the face silk form the surface layer of screen cloth, and the bottom silk forms the bottom of screen cloth, institute The lousiness stated forms the supporting layer of screen cloth, and the supporting layer is between the surface layer and the bottom, described Face silk or/and bottom silk include at least one bamboo fibre silk, and the surface layer or/and bottom are the bamboo fibre surface layer of soft smooth Or/and bottom.Bamboo charcoal fiber mesh fabric of the present invention is weaved into sandwich structure by face silk, lousiness and bottom silk one, face silk or/and Bottom silk includes bamboo fibre silk, to make the bamboo fibre surface layer or/and bottom of surface layer or/and bottom soft smooth, and then is made This bamboo charcoal fiber mesh fabric has many advantages, such as natural environmental-protective, deodorization, antibacterial, comfortable, softness.
Chinese Patent Application No. 201320294896.X is related to field of textile, and in particular to a kind of composite net cloth. The utility model aim, which is to provide one kind, can not only possess the original ventilation of screen cloth, ventilating performance, also with preferable intensity and outside The composite net cloth of sight.The technical solution adopted in the utility model is to provide a kind of composite net cloth, including screen cloth and resin layer, The screen cloth includes inner layer sheet cloth, middle layer cloth and outer layer table cloth, and the middle layer cloth is uprightly to weave kenel tissue, described interior Layer table cloth, middle layer cloth and outer layer table cloth are integrally made into a manner of warp-knitting, and the resin layer is installed on screen cloth surface It is integrally formed, the resin layer surface is equipped with through-hole.The utility model allows the resin layer to be integrally formed with the screen cloth, resin layer cloth If multiple through-holes, the screen cloth is enabled to possess original ventilation, outside ventilating performance, also with the intensity of the resin layer, and utilized Default through-hole, grain pattern design, can allow screen cloth to have more diversified design on the resin layer.
Chinese Patent Application No. 201320044219.2 is related to a kind of mesh material structure in Strand Feeding Technique field, this is practical Novel mesh material structure includes surface layer, intermediate course and bottom, and intermediate course, which is arranged between surface layer and bottom, forms folder Layered structure, intermediate course are engraved structure, and the mesh material structure of the utility model passes through intermediate course for surface layer and bottom Certain space is separated, and intermediate course is engraved structure, hollow out position forms airflow channel, and air-flow can be directly the bottom of by Layer is pierced by after passing through the airflow channel that engraved structure is formed by surface layer, and air-flow is unobstructed, has good air permeability effect and damping branch Support effect.
Chinese Patent Application No. 201220242408.6 is related to a kind of screen cloth, in particular to a kind of terylene mesh belongs to spinning Knit product.It is interwoven by warp and weft, the warp includes medium line and side line, the two sides difference of the medium line Equipped with side line, two warps between the weft intersect connection, and the medium line wears the intersection for taking over two warps Point, the medium line and two side lines are separately distributed.Terylene mesh is compact-sized, strength enhancing, and service life extends.
Chinese Patent Application No. 201210496733.X is related to a kind of composite elastic material screen cloth, including by top layer, bottom With the warp knit stereo fabric of the articulamentum of connection top layer and bottom composition, top layer, bottom and articulamentum surround cavity, fill out in cavity Filled with curable composite material, reticular fibre fabric of the articulamentum by multilayer along screen cloth length direction parallelly distribute on is formed, often Layer reticular fibre fabric is made of the vimentin filament of multiple alternately braidings, each wave crest of each vimentin filament and first knot Point is affixed, and first node affixed with the wave crest on each vimentin filament is on the same line, each waveform on same straight line The quantity for the first node that adjacent two of fiber are arranged between wave crest is 1~5；Advantage is: it is easy to use, it is convenient artificial Handling and transport, when use the liquid such as need to only water can form the netted complex coagulation soil layer with certain thickness and hardness Special material；Good combination property；It is environmental-friendly；It is flexible in application；It is at low cost, it is easy for construction high-efficient.
Chinese Patent Application No. 201220320157.9 is related to cloth field, provides a kind of permeability good novel ventilated Screen cloth, including ventilative screen cloth ontology, the ventilative screen cloth ontology include the upper layer gas-permeable nets being interwoven by artificial silk and terylene Layer, lower layer's draw textured yarn layer, the upper layer, which is breathed freely, is equipped with fully drawn yarn layer between stratum reticulare and lower layer's draw textured yarn layer.
Chinese Patent Application No. 201210335260.5 is related to a kind of space netted fabric compound material, includes from top to bottom PVC face mask layer, space scrim layer and PVC bottom membrane, space scrim layer includes upper and lower scrim layer disposed in parallel, and is vertically set Set the wire drawing in upper and lower screen cloth interlayer.The preparation method of the space netted fabric compound material comprising following steps: 1) empty Between scrim layer painting scrape paste；2) it preheats；3) it is bonded；4) cooling, trimming and winding.Space netted fabric compound material of the invention, The PVC face mask layer and PVC counterdie interlayer of composite material are provided with space scrim layer, in this way when space netted fabric compound material is applied When in air cushion product, after inflation, air cushion product surfacing, good appearance；It withstands forces, is not easy to pop in gas replenishment process； Intermediate space scrim layer makes air cushion product, and elasticity is good, compressive property is good.
Chinese Patent Application No. 201220191034.X is related to polytetrafluoroethylene fibre fiber mesh cloth, more particularly, to makes The PTFE web cloth of standby perfluorinated sulfonic acid ion exchange membrane, belongs to polytetrafluoroethylene (PTFE) industrial technical field.One kind poly- four Vinyl fluoride fiber mesh cloth, the screen cloth are that latitude and longitude are weaved by polytetrafluoroethylene fibre, and the screen cloth is once two latitude knots Structure, the weft are based on the warp and interlock；The equal single twisting of the latitude and longitude of the screen cloth, the weft fiber width of the screen cloth It is 220~230 μm, warp fiber width is 130~160 μm, and the fineness of the warp fiber and weft fiber is 80~100 Denier.PTFE web cloth provided by the utility model aims at amberplex design, particularly suitable to be used as ion exchange The framework material of film.The copolymer of resin is coated on the screen cloth, and coating uniform, coating is thin, coating and screen cloth skeleton bonding jail Gu；Manufactured amberplex has good proton passage capacity, and no permeability has dimensional stability height, intensity high Advantage.
Chinese Patent Application No. 201220032205.4 is related to screen cloth, refers in particular to a kind of novel sun-shading mesh, the screening Screened postive cloth is cross-woven by reflective material, and upper and lower ends are respectively arranged with support rod, and sunshade is stretched out at the both ends of support rod Screen cloth is outer and is provided with hanging hole, and the both ends of support rod are provided with the clip for clamping sun-shading mesh both ends, is arranged in hanging hole There is the elastic clip of control sun-shading mesh extension elongation and ties the hook or lanyard of support rod, the radial direction or latitude of sun-shading mesh It is arranged at intervals with rows of air hole upwards, is absorbed since above structure feature enables the utility model to take away screen cloth in time Heat, solve the problems, such as that existing sun-shading mesh is ineffective in this way, have many advantages, such as energy conservation.
Chinese Patent Application No. 201220505295.4 is related to a kind of warming three-layer mesh fabric, it is related to a kind of screen cloth.It is wrapped Containing mesh layer, hair high level, bottom plain cloth layer；The upper epidermis of warming three-layer mesh fabric is arranged in mesh layer, and hair high level is arranged in mesh layer Between the plain cloth layer of bottom, the layer of warming three-layer mesh fabric is arranged in bottom plain cloth layer, and mesh layer and hair high level use polyester material It is made, bottom plain cloth layer is made using terylene short fiber；The utility model has good warmth retention property, and beautiful outline form It sees, is suitable on shoes, clothes and luggage, is also applied for making bunting.
Chinese Patent Application No. 201220505322.8 is related to a kind of jacquard seamless three-layer mesh fabric, it is related to a kind of three-layer network Cloth.It includes jacquard layer, hair high level, bottom plain cloth layer, and the upper epidermis of jacquard seamless three-layer mesh fabric is arranged in jacquard layer, and hair high level is set It sets between jacquard layer and bottom plain cloth layer, the layer of jacquard seamless three-layer mesh fabric is arranged in bottom plain cloth layer；Jacquard layer is used and is washed Synthetic fibre material is made by pressure point Jacquard；Hair is high-rise, bottom plain cloth layer is all made of polyester material and is made；The utility model is adopted With piezoelectric jacquard, face is done in jacquard weave, makes jacquard layer there is no gap, and good appearance is suitable on shoes, clothes and luggage, is also suitable In making bunting.
Chinese Patent Application No. 201220505325.1 is related to a kind of transparent three-layer mesh fabric, it is related to a kind of screen cloth.It is wrapped The upper epidermis of transparent three-layer mesh fabric, jacquard weave and hair is arranged in the layer of plain cloth containing face, jacquard weave and hair high level, bottom plain cloth layer, face plain cloth layer High level is arranged between face plain cloth layer and bottom plain cloth layer, and the layer of transparent three-layer mesh fabric, face plain cloth layer is arranged in bottom plain cloth layer It is fabricated to bottom plain cloth layer using terylene transparent wire, jacquard weave and hair high level are made using terylene；The utility model is using saturating Bright silk is made, and transparency is high, good appearance, is suitable on shoes, clothes and luggage, is also applied for making bunting.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of warp-knitted spacer fabrics that part is hollow.
The purpose of the present invention is achieved through the following technical solutions:
A kind of warp-knitted spacer fabric that part is hollow, it includes surface layer, articulamentum and bottom pass through on surface layer and bottom Articulamentum is attached.
Articulamentum is part connection, is attached at the both ends of surface layer and bottom by articulamentum, and on surface layer and bottom Middle position carry out local connection, the part of connection forms surface layer, three layers of solid construction of articulamentum and bottom；And do not connect The part connect just forms the hollow structure in part of surface layer and bottom.
Three layers of solid construction that the part of connection is formed, play a supporting role.
And local hollow structure plays good air permeability effect and good visual stimulus, especially on surface layer and bottom There are in the case where color difference for layer.It especially is being used for footwear material technical field, is needing part hollow and local solid, for example vamp needs Part is hollow to play airing function, and upper of a shoe needs solid construction, plays a supporting role.
Articulamentum is 150D cation low stretch yarn.
Surface layer is folding polyester monofilament.
Bottom is high tenacity polyester fiber monofilament.
High tenacity polyester fiber monofilament, by modifying agent, compatilizer and PET particle pass through melting extrusion and obtain high-intensitive master batch, High tenacity polyester fiber monofilament is obtained by melt spinning by high tenacity polyester fiber master batch again.
Mass fraction of the modifying agent in high-intensitive master batch is 5~10%.
Mass fraction of the compatilizer in high-intensitive master batch is 1~3%.
The preparation method of modifying agent, the specific steps are that:
Superparamagnetism nickel colloidal nanocrystals cluster is dispersed in the ethanol solution of deionized water, dilute sulfuric acid is then added Solution；Continue high-speed stirred and dispersion, speed of agitator is 3000~4500 revs/min, and jitter time is 1~3h；Then in Under fast stirring condition, speed of agitator is 1000~1500 revs/min, and mixing time is 1~3h, and sulfuric acid is slowly added into system Zinc solution, addition finish, then increase reaction temperature to 40~60 DEG C sustained response 1~2 hour, be adsorbed on zinc ion super suitable The surface of Magnetic nickel colloidal nanocrystals cluster, obtains two layers of antibacterial agent after then being separated and be dried in vacuo；In normal temperature condition Under, two layers of antibacterial agent is added in hydrogen peroxide and carries out ultrasonic disperse, jitter time is 2~6h, and sulfuric acid is added after ultrasonic disperse Oxygen titanium aqueous solution carries out stirring at low speed reaction, and speed of agitator is 400~600 revs/min, and mixing time is 1~3h, after filtering Product is being risen to 480 DEG C again under anaerobic or oxygen deprivation atmosphere with the heating rate of 12 DEG C/min, is stopping 3~6 hours to get three Layer antibacterial agent；By three layers of antibacterial agent, high temperature is ground again by first cryogrinding for graphene oxide and hud typed mesoporous aluminoshilicate The mode of mill obtains composite material, the technique of cryogrinding high temperature grinding again are as follows: the control of cryogrinding temperature is 20~30 DEG C, is ground Time consuming is 1~2 hour, and the control of high temperature grinding temperature is 70~85 DEG C, and milling time is 1~3 hour；It is original with composite material Material carries out high-speed stirred and ultrasonic disperse under normal temperature conditions in hexane solution, and mixing speed is 2200~3200 turns/ Minute, jitter time is 1~4h, in nitrogen atmosphere, toluene di-isocyanate(TDI) is added, under 90~110 DEG C of reaction temperatures, instead It answers 1~2 hour, after reaction, then under the conditions of 105~115 DEG C, is evaporated under reduced pressure 1 hour, then to be evaporated under reduced pressure product It is dried in vacuo 50 hours under the conditions of 125 DEG C, modifying agent is prepared；
The mass ratio for controlling the zinc sulfate in superparamagnetism nickel colloidal nanocrystals cluster and solution of zinc sulfate is 5:1~9:1； Mass fraction of the superparamagnetism nickel colloidal nanocrystals cluster in the ethanol solution of deionized water is 5~10%；Deionized water The volume ratio of water and ethyl alcohol in ethanol solution is 1:1；The mass fraction of dilution heat of sulfuric acid is 5~10%, is mainly played pair Superparamagnetism nickel colloidal nanocrystals cluster acidification；It is easy to that zinc ion is made to be adsorbed on superparamagnetism nickel colloidal nanocrystals cluster Surface, the surface that superparamagnetism nickel colloidal nanocrystals cluster is formed in after then smart function separation and vacuum drying form zinc oxide Adsorption layer.
Mass fraction of two layers of antibacterial agent in hydrogen peroxide is 10~20%；
The mass ratio of titanyl sulfate in two layers of antibacterial agent and aqueous solution of titanyle sulfate is 5:1~10:1；
The mass ratio of three layers of antibacterial agent, graphene oxide and hud typed mesoporous aluminoshilicate is 1:2:1；Cryogrinding is again In the technique of high temperature grinding, graphene oxide itself contains polyhydroxy structure, that is, serves as the function of solvent, and itself is also tool There is antibiotic property, therefore graphene oxide has solvent action, antibacterial functions and hydroxylating function, is that other compatilizers do not have Have, one of the characteristics of this is the application；By grind after complex function powder itself be easy to be grafted hydroxyl structure, be easy to Subsequent toluene diisocynate toluene ester reaction；To finally improve the compatibility of its polyester.
Mass concentration of the composite material in n-hexane is 35~50g/L；
The molar ratio of toluene diisocynate toluene ester and composite material is 1:10~1:20.
Superparamagnetism nickel colloidal nanocrystals cluster has biggish porosity due to being nano-scale, simultaneously because its Itself has good antibiotic property, by using the method for solution co-precipitation on the surface of superparamagnetism nickel colloidal nanocrystals cluster Cladding zinc ion is carried out, then by being decomposed to form zinc oxide after separation and drying, there is good antibacterial using zinc oxide Function can provide stable dual anti-microbial property, i.e., internal is that superparamagnetism nickel colloidal nanocrystals cluster has antibacterial functions, And the zinc oxide on surface layer is also with antibacterial functions；Then it is activated, is activated by hydrogen peroxide, is being added Titanyl sulfate solution makes it and combines, then by high-temperature heating reaction, titanyl sulfate resolves into titanium dioxide to be adsorbed on it Surface, so that three-decker is formed, the photocatalysis of titanium dioxide, antibacterial effect, while avoiding conventional be blended and adding titanium dioxide Titanium nano particle problem easy to reunite；The application plays slow-release function, to finally extend its antibacterial functions.
Composite material has excellent uvioresistant, antibacterial effect, but conventional complex function powder in addition use process In, it due to large specific surface area, is easy to reunite and be difficult to disperse, needs to be passivated processing, and single inorganic surfaces are modified, it is right Its dispersibility and binding force in organic matrix are difficult to control, and cause dispersion difficulty big, especially fiber is washing, after sun-proof Long-time stability influence big；The intensity of particle can be improved as medium using hud typed mesoporous aluminoshilicate in the application, Intensity can be improved under the premise of with high antibiotic property simultaneously；And in polyester high temperature polymerization process, composite material not only drops The low uvioresistant antibacterial effect of polyester, while can also cause to break during Direct-spinning of PET Fiber because of the presence of agglomerated particle Situations such as head, the silk that floats, fracture of wire, and make difficulty in spinning, especially melt direct spinning superfine denier high speed spinning polyester filament is difficult, therefore By using the polyhydroxy structure of composite material surface, react composite material surface with isocyanate group, to make multiple Condensation material surface has isocyanate group, and can be reacted with polyester oligomer, so that composite material be made to be grafted on polyester In main chain section, its extinction effect is promoted；Avoid at present using blending form be added composite material prepare polyester fiber when, due to Its bad dispersibility in polyester fondant of composite material, causes uvioresistant antibacterial effect poor, band in especially long-term cleaning process Composite material and cause function to be deteriorated, make its dye and dyeing color fastness reduce, influence the quality and performance of fiber, To further influence the steady production of superfine denier polyester fiber.
Folding polyester monofilament, by folding particle, compatilizer and PET particle pass through melting extrusion and obtain folding master batch, then Folding polyester monofilament is obtained by melt spinning by folding master batch.
Mass fraction of the folding particle in folding master batch is 3~5%；
Mass fraction of the compatilizer in folding master batch is 1~2%.
A kind of preparation method of folding particle, the specific steps are that:
(1) pretreatment of graphene raw material
It takes reed rod to be release-treated, obtains reed straw core material, then reed straw core is carried out again through pickling The pretreatment object of graphene raw material is obtained after alkali washing process pretreatment, then after being pre-processed three times using clear water cleaning；
The acid cleaning process of the reed straw core is Strong oxdiative acidic mixed solution, impregnates 3 under the conditions of 80~90 DEG C ~6h；
The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, wherein the quality of nitric acid solution point Number is 10~15%, and the mass fraction of hydrogen peroxide solution is 10%~15%；
It is acidified and is activated using the acid solution of strong oxidizing property, ensure that cellulose can be adequately acidified And activation, while it is also ensured that metal ion can be invaded out completely cellulose, guarantee the removal of impurities of metal ion；
The alkaline process of the reed straw core is acidification technique treated reed straw core alkaline alcohol solution 3~6h is impregnated under the conditions of 80~90 DEG C；
The alkaline alcohol solution is the mixed solution of the isopropanol of person's potassium hydroxide, wherein potassium hydroxide and isopropanol Molar ratio is 1:05~1:25；
Reed straw itself has fiber content high, is largely used to fibre at present as a kind of biomass fiber cellulosic material Dimension element or paper making pulp；And in the core material in reed straw, it itself is high-content cellulose, carbon element content is abundant, This is as layer material simultaneously, between every layer with a thickness of micron level, therefore by later period charing after, the graphite linings of itself It can be good at being carbonized removing；Simultaneously as the internal material in reed straw, itself has oxidable, the property such as acidificable Can, therefore by carrying out acidification again to the cellulosic material in reed straw, so that its surface is adequately activated, And it is other heavy metal ion removing in cellulose, while carries out the removal of impurities of alkaline solution again, to guarantee reed straw In metal ion content the problems such as reducing, avoiding catalyst deactivation of the later period in charing and graphitizing process.
(2) functionalization of graphene raw material
As raw material, the mixed solution with phytic acid and phytic acid copper is the pretreatment object of the graphene raw material obtained using step (1) Functionalization liquid carries out functionalization load-reaction under strong stirring, and the temperature of functionalization load-reaction is 80~91 DEG C, The functionalization load-reaction time is 20~33h；After functionalization load, using ultracentrifugation, centrifugal sediment is obtained, centrifugation is heavy Starch vacuum drying treatment under the conditions of 82 DEG C again, obtains the function compound of graphene raw material；
Phytic acid mass fraction in the functionalization liquid is 3%；
The mass fraction of phytic acid copper in the functionalization liquid is 8%；
Phytic acid is as a kind of organic acid, itself has six-membered ring structure, while the phosphoric acid structure of phytic acid can be to wooden fibre Dimension element plays good acidification, the effect of catalyzing and carbonizing, and the dominant catalyst currently used for graphene preparation；Pass through cooperation The structure of phytic acid copper passes through the attachment of phytic acid and matter acid copper after absorption using the suction-operated of the reed straw core of activation Effect, so that it is conducive to the catalyzing and carbonizing and graphitization effect of reed straw core, and copper ions are after the charred effect of high temperature, With excellent antibacterial effect, so that graphene can be obtained both with catalyzing and carbonizing by playing, while can also bear on the surface of graphene Load obtains the copper ion of antibacterial functions, to further enhance the anti-microbial property of material.
(3) charing of graphene raw material
Using the function compound of the graphene raw material of step (2) preparation as raw material, first carries out oxidation processes and carry out at charing again Reason obtains the carbide of graphene raw material；
Specifically comprises the processes of: in 185~200 DEG C of oxidizing temperatures, oxygen purity is 10~15%, the volume fraction of ozone To carry out 10~20h of oxidation processes in 1~1.5% oxidizing atmosphere；Then again in helium atmosphere, 500~600 DEG C of conditions Lower carry out charing process；
The oxidation susceptibility of functionalization load reed rod core is improved using the oxidation effectiveness of ozone by the heating of multi-step, The carbonization process in inert gas to be conducive to the later period improves its pre-oxidation charing efficiency.
(4) modification of graphene
Using step (3) preparation graphene raw material carbide and potassium nitrate as raw material, it is agitated after evenly mixing, then The nitrogen mixed gas of material and hypoxemia is continuously conveyed, the carbide of graphene raw material is set to carry out high temperature in hypoxic atmosphere quick-fried Fried graphitization reaction collects the gas of the mixed gas outlet of high temperature explosion graphitization reaction, collects obtain graphite after cooling Alkene modifier；
It is 1:0.08 that the carbide and potassium nitrate of the graphene raw material, which obtain mass ratio,；
Temperature is 1000~2100 DEG C in the high temperature explosion graphitizing process, wherein oxygen in the nitrogen atmosphere of hypoxemia Volume fraction be 3~5%；
The volume ratio of material and mixed gas is 1:1000 in the continuous conveying process；
The feed flow of the mixed gas is 8~21L/min.
Potassium nitrate itself has certain combustion-supporting effect, therefore in a certain range, can play explosion synergist, and Carbide of graphene raw material itself passes through potassium nitrate in the detonation of moment, using the instantaneous force of explosion, to reach To the effect of removing graphene, and using the adjustment effect of potassium nitrate and oxygen concentration, to reach the layer of graphene itself Number control, and after the combustion explosion of potassium nitrate, the gas and product of generation are by the collection in later period, to reach stone The efficient and continuous production operation of black alkene, it is high-efficient and at low cost.There is by load the copper ion of antibacterial simultaneously, there is association The effect of the antibacterial of effect enhancing graphene itself, while graphene is removed by using the combustion explosion of potassium nitrate, utilize control Potassium nitrate content and oxygen concentration reach the material combustion explosion in the confined space, reach removing graphene using explosive force Effect, have many advantages, such as it is high-efficient, it is at low cost.
(5) preparation of folding particle
With step (4) prepare graphene modifier, nano barium sulfate, hud typed mesoporous aluminoshilicate by grinding with Afterwards, ethylene glycol is added and carries out melting extrusion, obtain folding particle；
Mass fraction of the graphene modifier in folding particle is 20~30%.
Nano barium sulfate is 10~25% in the mass fraction in folding particle.
Ethylene glycol is 10~30% in the mass fraction in folding particle.
The application is using hud typed mesoporous aluminoshilicate as function carrier, because its own is micro-sphere structure, microballoon has rule Then spherical morphology, compact silicon dioxide protection superparamagnetism kernel, high opening single layer ordered mesoporous aluminosilicate shell, Regularly arranged duct, and hole wall has high density acidic active sites, aperture is big, and by grinding technics, therefore graphene changes Property object, nano barium sulfate are easy to be adsorbed in the hole of microballoon, play complex function；To realize microballoon and slow-release function, Using nano barium sulfate, hud typed mesoporous aluminoshilicate is mentioned to finally improve the intensity of its product using graphene modifier The antibiotic property of high product, to realize the dual unification of folding and antibacterial.
Compared with prior art, the positive effect of the present invention is:
The hollow structure in the part of the application plays good air permeability effect and good visual stimulus, especially in table There are in the case where color difference with bottom for layer.It especially is being used for footwear material technical field, is needing part hollow and local solid, such as shoes Face needs part is hollow to play airing function, and upper of a shoe needs solid construction, plays a supporting role.
Detailed description of the invention
The structural schematic diagram of Fig. 1 the application；
The Raman spectrum of Fig. 2 graphene modifier；
The scanning electron microscope (SEM) photograph of Fig. 3 graphene modifier；
The transmission electron microscope picture of Fig. 4 graphene modifier；
The label in accompanying drawing is: 11 surface layers, 2 articulamentums, 3 bottoms, the part of 21 connections, 22 not connected parts.
Specific embodiment
A kind of specific embodiment for the warp-knitted spacer fabric that part is hollow of the present invention presented below.
Embodiment 1
A kind of warp-knitted spacer fabric that part is hollow, it includes surface layer 1, articulamentum 2 and bottom 3, on surface layer and bottom It is attached by articulamentum.
Articulamentum is part connection, is attached at the both ends of surface layer and bottom by articulamentum, and on surface layer and bottom Middle position carry out local connection, the part 21 of connection forms surface layer, three layers of solid construction of articulamentum and bottom；And not The part 22 of the connection structure hollow with regard to the part on formation surface layer and bottom.
Three layers of solid construction that the part of connection is formed, play a supporting role.
And local hollow structure plays good air permeability effect and good visual stimulus, especially on surface layer and bottom There are in the case where color difference for layer.It especially is being used for footwear material technical field, is needing part hollow and local solid, for example vamp needs Part is hollow to play airing function, and upper of a shoe needs solid construction, plays a supporting role.
Articulamentum is 150D cation low stretch yarn.
Surface layer is folding polyester monofilament.
Bottom is high tenacity polyester fiber monofilament.
High tenacity polyester fiber monofilament, by modifying agent, compatilizer and PET particle pass through melting extrusion and obtain high-intensitive master batch, High tenacity polyester fiber monofilament is obtained by melt spinning by high tenacity polyester fiber master batch again.
Mass fraction of the modifying agent in high-intensitive master batch is 5%.
Mass fraction of the compatilizer in high-intensitive master batch is 1%.
High tenacity polyester fiber monofilament is greater than 95% to the fungistatic effect of staphylococcus glucose coccus, to the antibacterial effect of Escherichia coli Fruit is greater than 95%.
Superparamagnetism nickel colloidal nanocrystals cluster is dispersed in the ethanol solution of deionized water, dilute sulfuric acid is then added Solution；Continue high-speed stirred and dispersion, speed of agitator is 3000~4500 revs/min, and jitter time is 1~3h；Then in Under fast stirring condition, speed of agitator is 1000~1500 revs/min, and mixing time is 1~3h, and sulfuric acid is slowly added into system Zinc solution, addition finish, then increase reaction temperature to 40~60 DEG C sustained response 1~2 hour, be adsorbed on zinc ion super suitable The surface of Magnetic nickel colloidal nanocrystals cluster, obtains two layers of antibacterial agent after then being separated and be dried in vacuo；In normal temperature condition Under, two layers of antibacterial agent is added in hydrogen peroxide and carries out ultrasonic disperse, jitter time is 2~6h, and sulfuric acid is added after ultrasonic disperse Oxygen titanium aqueous solution carries out stirring at low speed reaction, and speed of agitator is 400~600 revs/min, and mixing time is 1~3h, after filtering Product is being risen to 480 DEG C again under anaerobic or oxygen deprivation atmosphere with the heating rate of 12 DEG C/min, is stopping 3~6 hours to get three Layer antibacterial agent；By three layers of antibacterial agent, high temperature is ground again by first cryogrinding for graphene oxide and hud typed mesoporous aluminoshilicate The mode of mill obtains composite material, the technique of cryogrinding high temperature grinding again are as follows: the control of cryogrinding temperature is 20~30 DEG C, is ground Time consuming is 1~2 hour, and the control of high temperature grinding temperature is 70~85 DEG C, and milling time is 1~3 hour；It is original with composite material Material carries out high-speed stirred and ultrasonic disperse under normal temperature conditions in hexane solution, and mixing speed is 2200~3200 turns/ Minute, jitter time is 1~4h, in nitrogen atmosphere, toluene di-isocyanate(TDI) is added, under 90~110 DEG C of reaction temperatures, instead It answers 1~2 hour, after reaction, then under the conditions of 105~115 DEG C, is evaporated under reduced pressure 1 hour, then to be evaporated under reduced pressure product It is dried in vacuo 50 hours under the conditions of 125 DEG C, modifying agent is prepared；
The mass ratio for controlling the zinc sulfate in superparamagnetism nickel colloidal nanocrystals cluster and solution of zinc sulfate is 5:1；It is super suitable Mass fraction of the Magnetic nickel colloidal nanocrystals cluster in the ethanol solution of deionized water is 5%；The ethanol solution of deionized water In water and ethyl alcohol volume ratio be 1:1；The mass fraction of dilution heat of sulfuric acid is 5%, is mainly played to superparamagnetism nickel glue Body nanocrystal cluster acidification；The surface for being easy to that zinc ion is made to be adsorbed on superparamagnetism nickel colloidal nanocrystals cluster, it is then smart The surface that superparamagnetism nickel colloidal nanocrystals cluster is formed in after function separation and vacuum drying forms zinc oxide adsorption layer.
Mass fraction of two layers of antibacterial agent in hydrogen peroxide is 10%；
The mass ratio of titanyl sulfate in two layers of antibacterial agent and aqueous solution of titanyle sulfate is 5:1；
The mass ratio of three layers of antibacterial agent, graphene oxide and hud typed mesoporous aluminoshilicate is 1:2:1；Cryogrinding is again In the technique of high temperature grinding, graphene oxide itself contains polyhydroxy structure, that is, serves as the function of solvent, and itself is also tool There is antibiotic property, therefore graphene oxide has solvent action, antibacterial functions and hydroxylating function, is that other compatilizers do not have Have, one of the characteristics of this is the application；By grind after complex function powder itself be easy to be grafted hydroxyl structure, be easy to Subsequent toluene diisocynate toluene ester reaction；To finally improve the compatibility of its polyester.
Mass concentration of the composite material in n-hexane is 35g/L；
The molar ratio of toluene diisocynate toluene ester and composite material is 1:10.
Superparamagnetism nickel colloidal nanocrystals cluster has biggish porosity due to being nano-scale, simultaneously because its Itself has good antibiotic property, by using the method for solution co-precipitation on the surface of superparamagnetism nickel colloidal nanocrystals cluster Cladding zinc ion is carried out, then by being decomposed to form zinc oxide after separation and drying, there is good antibacterial using zinc oxide Function can provide stable dual anti-microbial property, i.e., internal is that superparamagnetism nickel colloidal nanocrystals cluster has antibacterial functions, And the zinc oxide on surface layer is also with antibacterial functions；Then it is activated, is activated by hydrogen peroxide, is being added Titanyl sulfate solution makes it and combines, then by high-temperature heating reaction, titanyl sulfate resolves into titanium dioxide to be adsorbed on it Surface, so that three-decker is formed, the photocatalysis of titanium dioxide, antibacterial effect, while avoiding conventional be blended and adding titanium dioxide Titanium nano particle problem easy to reunite；The application plays slow-release function, to finally extend its antibacterial functions.Superparamagnetism nickel glue Body nanocrystal cluster, with good antibacterial and bactericidal effect.Nano nickel particles are initially formed in polarity high-temperature medium, are gone forward side by side And be self-assembled into cluster-glass behaviour and form superparamagnetism nickel colloidal nanocrystals cluster, the raw material of reaction is NaOH and NiCl2.It is specific It can be found in Superparamagnetic nickel colloidal nanocrystal clusters with antibacterial activity and bacteria binding ability(Nat.Nanotech.2018 doi: 10.1038/s41565-018-0108-0)。
Composite material has excellent uvioresistant, antibacterial effect, but conventional complex function powder in addition use process In, it due to large specific surface area, is easy to reunite and be difficult to disperse, needs to be passivated processing, and single inorganic surfaces are modified, it is right Its dispersibility and binding force in organic matrix are difficult to control, and cause dispersion difficulty big, especially fiber is washing, after sun-proof Long-time stability influence big；The intensity of particle can be improved as medium using hud typed mesoporous aluminoshilicate in the application, Intensity can be improved under the premise of with high antibiotic property simultaneously；And in polyester high temperature polymerization process, composite material not only drops The low uvioresistant antibacterial effect of polyester, while can also cause to break during Direct-spinning of PET Fiber because of the presence of agglomerated particle Situations such as head, the silk that floats, fracture of wire, and make difficulty in spinning, especially melt direct spinning superfine denier high speed spinning polyester filament is difficult, therefore By using the polyhydroxy structure of composite material surface, react composite material surface with isocyanate group, to make multiple Condensation material surface has isocyanate group, and can be reacted with polyester oligomer, so that composite material be made to be grafted on polyester In main chain section, its extinction effect is promoted；Avoid at present using blending form be added composite material prepare polyester fiber when, due to Its bad dispersibility in polyester fondant of composite material, causes uvioresistant antibacterial effect poor, band in especially long-term cleaning process Composite material and cause function to be deteriorated, make its dye and dyeing color fastness reduce, influence the quality and performance of fiber, To further influence the steady production of superfine denier polyester fiber.
Folding polyester monofilament, by folding particle, compatilizer and PET particle pass through melting extrusion and obtain folding master batch, then Folding polyester monofilament is obtained by melt spinning by folding master batch.
Mass fraction of the folding particle in folding master batch is 3%；
Mass fraction of the compatilizer in folding master batch is 1%.
Folding polyester monofilament is greater than 94% to the fungistatic effect of staphylococcus glucose coccus, to the fungistatic effect of Escherichia coli Greater than 94%.
A kind of preparation method of folding particle, the specific steps are that:
(1) pretreatment of graphene raw material
It takes reed rod to be release-treated, obtains reed straw core material, then reed straw core is carried out again through pickling The pretreatment object of graphene raw material is obtained after alkali washing process pretreatment, then after being pre-processed three times using clear water cleaning；
The acid cleaning process of the reed straw core is Strong oxdiative acidic mixed solution, impregnates 3 under the conditions of 80~90 DEG C ~6h；
The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, wherein the quality of nitric acid solution point Number is 10~15%, and the mass fraction of hydrogen peroxide solution is 10%~15%；
It is acidified and is activated using the acid solution of strong oxidizing property, ensure that cellulose can be adequately acidified And activation, while it is also ensured that metal ion can be invaded out completely cellulose, guarantee the removal of impurities of metal ion；
The alkaline process of the reed straw core is acidification technique treated reed straw core alkaline alcohol solution 3~6h is impregnated under the conditions of 80~90 DEG C；
The alkaline alcohol solution is the mixed solution of the isopropanol of person's potassium hydroxide, wherein potassium hydroxide and isopropanol Molar ratio is 1:05；
(2) functionalization of graphene raw material
As raw material, the mixed solution with phytic acid and phytic acid copper is the pretreatment object of the graphene raw material obtained using step (1) Functionalization liquid carries out functionalization load-reaction under strong stirring, and the temperature of functionalization load-reaction is 80~91 DEG C, The functionalization load-reaction time is 20~33h；After functionalization load, using ultracentrifugation, centrifugal sediment is obtained, centrifugation is heavy Starch vacuum drying treatment under the conditions of 82 DEG C again, obtains the function compound of graphene raw material；
Phytic acid mass fraction in the functionalization liquid is 3%；
The mass fraction of phytic acid copper in the functionalization liquid is 8%；
(3) charing of graphene raw material
Using the function compound of the graphene raw material of step (2) preparation as raw material, first carries out oxidation processes and carry out at charing again Reason obtains the carbide of graphene raw material；
(4) modification of graphene
Using step (3) preparation graphene raw material carbide and potassium nitrate as raw material, it is agitated after evenly mixing, then The nitrogen mixed gas of material and hypoxemia is continuously conveyed, the carbide of graphene raw material is set to carry out high temperature in hypoxic atmosphere quick-fried Fried graphitization reaction collects the gas of the mixed gas outlet of high temperature explosion graphitization reaction, collects obtain graphite after cooling Alkene modifier；Shown in Fig. 2, in the map of graphene modifier 1595cm-1 it is corresponding be degree of graphitization characteristic peak, 1350cm-1 corresponding is carbon-coating structure unordered in graphene, and the intensity rate at peak is 16.3, therefore prepared by explanation Material degree of graphitization is high, while the distinctive peak 2D of grapheme material can be significantly found out in map, and 2D peak height, therefore institute The biomass quality of graphene of preparation is good.The scanning electron microscope (SEM) photograph of Fig. 3 graphene modifier；The transmission of Fig. 4 graphene modifier Electron microscope；Graphene is in lamellar structure, and in electromicroscopic photograph, can clearly tell the lamella of graphene, and graphite Functional particulate material comprising load in alkene.
It is 1:0.08 that the carbide and potassium nitrate of the graphene raw material, which obtain mass ratio,；
Temperature is 1000~2100 DEG C in the high temperature explosion graphitizing process, wherein oxygen in the nitrogen atmosphere of hypoxemia Volume fraction be 3~5%；
The volume ratio of material and mixed gas is 1:1000 in the continuous conveying process；
The feed flow of the mixed gas is 8~21L/min.
(5) preparation of folding particle
With step (4) prepare graphene modifier, nano barium sulfate, hud typed mesoporous aluminoshilicate by grinding with Afterwards, ethylene glycol is added and carries out melting extrusion, obtain folding particle；
Mass fraction of the graphene modifier in folding particle is 20%.
Nano barium sulfate is 10% in the mass fraction in folding particle.
Ethylene glycol is 10% in the mass fraction in folding particle.
The application is using hud typed mesoporous aluminoshilicate as function carrier, because its own is micro-sphere structure, microballoon has rule Then spherical morphology, compact silicon dioxide protection superparamagnetism kernel, high opening single layer ordered mesoporous aluminosilicate shell, Regularly arranged duct, and hole wall has high density acidic active sites, aperture is big, and by grinding technics, therefore graphene changes Property object, nano barium sulfate are easy to be adsorbed in the hole of microballoon, play complex function；To realize microballoon and slow-release function, Using nano barium sulfate, hud typed mesoporous aluminoshilicate is mentioned to finally improve the intensity of its product using graphene modifier The antibiotic property of high product, to realize the dual unification of folding and antibacterial.
Hud typed mesoporous aluminoshilicate: (1) by stober method, ferroso-ferric oxide disperses in ethyl alcohol, is then added In TEOS and ammonium hydroxide, ferroso-ferric oxide@silicon dioxide composite material is prepared；It is poly- with amphiphilic block copolymer polystyrene-b- 4-vinylpridine (Ps-b-P4VP) is used as directed agents, and aluminium hydroxide is added and ferroso-ferric oxide@is prepared in TEOS reaction Silica-Ps-b-P4VP/ aluminium hydroxide/silica；Calcination processing is finally carried out, amphiphilic block copolymer Ps-b- is removed P4VP obtains hud typed mesoporous aluminoshilicate.Detailed preparation process is shown in Amphiphilic Block Copolymers Directed Interface Coassembly to Construct Multifunctional Microspheres with Magnetic Core and Monolayer Mesoporous Aluminosilicate Shell(Adv.Mater.,2018, DOI:10.1002/adma.201800345)。
Embodiment 2
A kind of warp-knitted spacer fabric that part is hollow, it includes surface layer, articulamentum and bottom pass through on surface layer and bottom Articulamentum is attached.
Articulamentum is part connection, is attached at the both ends of surface layer and bottom by articulamentum, and on surface layer and bottom Middle position carry out local connection, the part of connection forms surface layer, three layers of solid construction of articulamentum and bottom；And do not connect The part connect just forms the hollow structure in part of surface layer and bottom.
Three layers of solid construction that the part of connection is formed, play a supporting role.
And local hollow structure plays good air permeability effect and good visual stimulus, especially on surface layer and bottom There are in the case where color difference for layer.It especially is being used for footwear material technical field, is needing part hollow and local solid, for example vamp needs Part is hollow to play airing function, and upper of a shoe needs solid construction, plays a supporting role.
Articulamentum is 150D cation low stretch yarn.
Surface layer is folding polyester monofilament.
Bottom is high tenacity polyester fiber monofilament.
High tenacity polyester fiber monofilament, by modifying agent, compatilizer and PET particle pass through melting extrusion and obtain high-intensitive master batch, High tenacity polyester fiber monofilament is obtained by melt spinning by high tenacity polyester fiber master batch again.
Mass fraction of the modifying agent in high-intensitive master batch is 10%.
Mass fraction of the compatilizer in high-intensitive master batch is 3%.
High tenacity polyester fiber monofilament is greater than 94% to the fungistatic effect of staphylococcus glucose coccus, to the antibacterial effect of Escherichia coli Fruit is greater than 94%.
Superparamagnetism nickel colloidal nanocrystals cluster is dispersed in the ethanol solution of deionized water, dilute sulfuric acid is then added Solution；Continue high-speed stirred and dispersion, speed of agitator is 3000~4500 revs/min, and jitter time is 1~3h；Then in Under fast stirring condition, speed of agitator is 1000~1500 revs/min, and mixing time is 1~3h, and sulfuric acid is slowly added into system Zinc solution, addition finish, then increase reaction temperature to 40~60 DEG C sustained response 1~2 hour, be adsorbed on zinc ion super suitable The surface of Magnetic nickel colloidal nanocrystals cluster, obtains two layers of antibacterial agent after then being separated and be dried in vacuo；In normal temperature condition Under, two layers of antibacterial agent is added in hydrogen peroxide and carries out ultrasonic disperse, jitter time is 2~6h, and sulfuric acid is added after ultrasonic disperse Oxygen titanium aqueous solution carries out stirring at low speed reaction, and speed of agitator is 400~600 revs/min, and mixing time is 1~3h, after filtering Product is being risen to 480 DEG C again under anaerobic or oxygen deprivation atmosphere with the heating rate of 12 DEG C/min, is stopping 3~6 hours to get three Layer antibacterial agent；By three layers of antibacterial agent, high temperature is ground again by first cryogrinding for graphene oxide and hud typed mesoporous aluminoshilicate The mode of mill obtains composite material, the technique of cryogrinding high temperature grinding again are as follows: the control of cryogrinding temperature is 20~30 DEG C, is ground Time consuming is 1~2 hour, and the control of high temperature grinding temperature is 70~85 DEG C, and milling time is 1~3 hour；It is original with composite material Material carries out high-speed stirred and ultrasonic disperse under normal temperature conditions in hexane solution, and mixing speed is 2200~3200 turns/ Minute, jitter time is 1~4h, in nitrogen atmosphere, toluene di-isocyanate(TDI) is added, under 90~110 DEG C of reaction temperatures, instead It answers 1~2 hour, after reaction, then under the conditions of 105~115 DEG C, is evaporated under reduced pressure 1 hour, then to be evaporated under reduced pressure product It is dried in vacuo 50 hours under the conditions of 125 DEG C, modifying agent is prepared；
The mass ratio for controlling the zinc sulfate in superparamagnetism nickel colloidal nanocrystals cluster and solution of zinc sulfate is 9:1；It is super suitable Mass fraction of the Magnetic nickel colloidal nanocrystals cluster in the ethanol solution of deionized water is 10%；The ethanol solution of deionized water In water and ethyl alcohol volume ratio be 1:1；The mass fraction of dilution heat of sulfuric acid is 5~10%, is mainly played to superparamagnetism Nickel colloidal nanocrystals cluster acidification；The surface for being easy to that zinc ion is made to be adsorbed on superparamagnetism nickel colloidal nanocrystals cluster, and The surface that smart function separation and vacuum drying are formed in superparamagnetism nickel colloidal nanocrystals cluster later afterwards forms zinc oxide adsorption layer.
Mass fraction of two layers of antibacterial agent in hydrogen peroxide is 20%；
The mass ratio of titanyl sulfate in two layers of antibacterial agent and aqueous solution of titanyle sulfate is 10:1；
Mass concentration of the composite material in n-hexane is 35~50g/L；
The molar ratio of toluene diisocynate toluene ester and composite material is 1:20.
Folding polyester monofilament, by folding particle, compatilizer and PET particle pass through melting extrusion and obtain folding master batch, then Folding polyester monofilament is obtained by melt spinning by folding master batch.
Mass fraction of the folding particle in folding master batch is 5%；
Mass fraction of the compatilizer in folding master batch is 2%.
Folding polyester monofilament is greater than 94% to the fungistatic effect of staphylococcus glucose coccus, to the fungistatic effect of Escherichia coli Greater than 94%.
A kind of preparation method of folding particle, the specific steps are that:
(1) pretreatment of graphene raw material
It takes reed rod to be release-treated, obtains reed straw core material, then reed straw core is carried out again through pickling The pretreatment object of graphene raw material is obtained after alkali washing process pretreatment, then after being pre-processed three times using clear water cleaning；
The acid cleaning process of the reed straw core is Strong oxdiative acidic mixed solution, impregnates 3 under the conditions of 80~90 DEG C ~6h；
The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, wherein the quality of nitric acid solution point Number is 10~15%, and the mass fraction of hydrogen peroxide solution is 10%~15%；
It is acidified and is activated using the acid solution of strong oxidizing property, ensure that cellulose can be adequately acidified And activation, while it is also ensured that metal ion can be invaded out completely cellulose, guarantee the removal of impurities of metal ion；
The alkaline process of the reed straw core is acidification technique treated reed straw core alkaline alcohol solution 3~6h is impregnated under the conditions of 80~90 DEG C；
The alkaline alcohol solution is the mixed solution of the isopropanol of person's potassium hydroxide, wherein potassium hydroxide and isopropanol Molar ratio is 1:25；
(2) functionalization of graphene raw material
As raw material, the mixed solution with phytic acid and phytic acid copper is the pretreatment object of the graphene raw material obtained using step (1) Functionalization liquid carries out functionalization load-reaction under strong stirring, and the temperature of functionalization load-reaction is 80~91 DEG C, The functionalization load-reaction time is 20~33h；After functionalization load, using ultracentrifugation, centrifugal sediment is obtained, centrifugation is heavy Starch vacuum drying treatment under the conditions of 82 DEG C again, obtains the function compound of graphene raw material；
Phytic acid mass fraction in the functionalization liquid is 3%；
The mass fraction of phytic acid copper in the functionalization liquid is 8%；
(3) charing of graphene raw material
Using the function compound of the graphene raw material of step (2) preparation as raw material, first carries out oxidation processes and carry out at charing again Reason obtains the carbide of graphene raw material；
(4) modification of graphene
Using step (3) preparation graphene raw material carbide and potassium nitrate as raw material, it is agitated after evenly mixing, then The nitrogen mixed gas of material and hypoxemia is continuously conveyed, the carbide of graphene raw material is set to carry out high temperature in hypoxic atmosphere quick-fried Fried graphitization reaction collects the gas of the mixed gas outlet of high temperature explosion graphitization reaction, collects obtain graphite after cooling Alkene modifier；
It is 1:0.08 that the carbide and potassium nitrate of the graphene raw material, which obtain mass ratio,；
Temperature is 1000~2100 DEG C in the high temperature explosion graphitizing process, wherein oxygen in the nitrogen atmosphere of hypoxemia Volume fraction be 3~5%；
The volume ratio of material and mixed gas is 1:1000 in the continuous conveying process；
The feed flow of the mixed gas is 8~21L/min.
(5) preparation of folding particle
With step (4) prepare graphene modifier, nano barium sulfate, hud typed mesoporous aluminoshilicate by grinding with Afterwards, ethylene glycol is added and carries out melting extrusion, obtain folding particle；
Mass fraction of the graphene modifier in folding particle is 30%.
Nano barium sulfate is 25% in the mass fraction in folding particle.
Ethylene glycol is 30% in the mass fraction in folding particle.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as In protection scope of the present invention.

Claims (9)

1. a kind of warp-knitted spacer fabric that part is hollow, which is characterized in that it includes surface layer, articulamentum and bottom, on surface layer It is attached with bottom by articulamentum.
2. a kind of hollow warp-knitted spacer fabric in part according to claim 1, which is characterized in that articulamentum is that part connects It connects, is attached at the both ends of surface layer and bottom by articulamentum, and carry out local connection on surface layer and the middle position of bottom, The part of connection forms surface layer, three layers of solid construction of articulamentum and bottom；And not connected part just forms surface layer and bottom The hollow structure in the part of layer.
3. a kind of hollow warp-knitted spacer fabric in part according to claim 1, which is characterized in that
Articulamentum is 150D cation low stretch yarn.
Surface layer is folding polyester monofilament；
Bottom is high tenacity polyester fiber monofilament.
4. a kind of hollow warp-knitted spacer fabric in part according to claim 3, which is characterized in that high tenacity polyester fiber list Silk, by modifying agent, compatilizer and PET particle pass through melting extrusion and obtain high-intensitive master batch, then are passed through by high tenacity polyester fiber master batch It crosses melt spinning and obtains high tenacity polyester fiber monofilament.
5. a kind of hollow warp-knitted spacer fabric in part according to claim 4, which is characterized in that modifying agent is in high intensity Mass fraction in master batch is 5~10%.
6. a kind of hollow warp-knitted spacer fabric in part according to claim 4, which is characterized in that the preparation side of modifying agent Method, the specific steps are that:
Superparamagnetism nickel colloidal nanocrystals cluster is dispersed in the ethanol solution of deionized water, it is molten then to add dilute sulfuric acid Liquid；Continue high-speed stirred and dispersion, speed of agitator is 3000~4500 revs/min, and jitter time is 1~3h；Then in middling speed Under stirring condition, speed of agitator is 1000~1500 revs/min, and mixing time is 1~3h, and zinc sulfate is slowly added into system Solution, addition finish, then increase reaction temperature to 40~60 DEG C sustained response 1~2 hour, so that zinc ion is adsorbed on superparamagnetic The surface of property nickel colloidal nanocrystals cluster, obtains two layers of antibacterial agent after then being separated and be dried in vacuo；Under normal temperature conditions, Two layers of antibacterial agent is added in hydrogen peroxide and carries out ultrasonic disperse, jitter time is 2~6h, and titanyl sulfate is added after ultrasonic disperse Aqueous solution carries out stirring at low speed reaction, and speed of agitator is 400~600 revs/min, and mixing time is 1~3h, will be produced after filtering Object is rising to 480 DEG C again under anaerobic or oxygen deprivation atmosphere with the heating rate of 12 DEG C/min, stops 3~6 hours and resists to get three layers Microbial inoculum；By three layers of antibacterial agent, graphene oxide and hud typed mesoporous aluminoshilicate pass through first cryogrinding high temperature grinding again Mode obtains composite material, the technique of cryogrinding high temperature grinding again are as follows: the control of cryogrinding temperature is 20~30 DEG C, when grinding Between be 1~2 hour, high temperature grinding temperature control be 70~85 DEG C, milling time be 1~3 hour；Using composite material as raw material, Under normal temperature conditions, high-speed stirred and ultrasonic disperse are carried out in hexane solution, mixing speed is 2200~3200 revs/min Clock, jitter time is 1~4h, and in nitrogen atmosphere, toluene di-isocyanate(TDI) is added, under 90~110 DEG C of reaction temperatures, reaction It 1~2 hour, after reaction, then under the conditions of 105~115 DEG C, is evaporated under reduced pressure 1 hour, is then existed with being evaporated under reduced pressure product It is dried in vacuo 50 hours under the conditions of 125 DEG C, modifying agent is prepared.
7. a kind of hollow warp-knitted spacer fabric in part according to claim 3, which is characterized in that folding polyester monofilament, By folding particle, compatilizer and PET particle pass through melting extrusion and obtain folding master batch, then pass through melt spinning by folding master batch Obtain folding polyester monofilament.
8. a kind of hollow warp-knitted spacer fabric in part according to claim 7, which is characterized in that folding particle is in folding Mass fraction in master batch is 3~5%.
9. a kind of hollow warp-knitted spacer fabric in part according to claim 7, which is characterized in that a kind of folding particle Preparation method, the specific steps are that:
(1) pretreatment of graphene raw material
(2) functionalization of graphene raw material
The pretreatment object of the graphene raw material obtained using step (1) is raw material, using the mixed solution of phytic acid and phytic acid copper as function Change treatment fluid, under strong stirring, carries out functionalization load-reaction, the temperature of functionalization load-reaction is 80~91 DEG C, function The change load-reaction time is 20~33h；After functionalization load, using ultracentrifugation, centrifugal sediment, centrifugal sediment are obtained Vacuum drying treatment under the conditions of 82 DEG C again, obtains the function compound of graphene raw material；
(3) charing of graphene raw material
Using the function compound of the graphene raw material of step (2) preparation as raw material, first progress oxidation processes carry out charing process again and obtain To the carbide of graphene raw material；
(4) modification of graphene
Using step (3) preparation graphene raw material carbide and potassium nitrate as raw material, it is agitated after evenly mixing, then with company The nitrogen mixed gas of continuous conveying material and hypoxemia makes the carbide of graphene raw material carry out high temperature explosion stone in hypoxic atmosphere Inkization reaction collects the gas of the mixed gas outlet of high temperature explosion graphitization reaction, collects after cooling and obtain graphene and change Property object；
(5) preparation of folding particle
With graphene modifier prepared by step (4), nano barium sulfate adds after hud typed mesoporous aluminoshilicate is by grinding Enter ethylene glycol and carry out melting extrusion, obtains folding particle；
Mass fraction of the graphene modifier in folding particle is 20~30%.
Nano barium sulfate is 10~25% in the mass fraction in folding particle.
Ethylene glycol is 10~30% in the mass fraction in folding particle.
CN201810744017.6A 2018-07-09 2018-07-09 Warp knitted spacer fabric with partial hollows Active CN108950852B (en)

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CN111379070A (en) * 2018-12-31 2020-07-07 泉州汇成针织有限公司 Discontinuous 3D spacer fabric and preparation method and special equipment thereof
CN112313372A (en) * 2019-01-11 2021-02-02 伊斯克纺织品有限公司 Antibacterial multilayer knitted fabric with air layer and preparation method thereof
CN113119541A (en) * 2021-04-15 2021-07-16 福建凤竹纺织科技股份有限公司 Vamp fabric convenient to waterproof heat dissipation
CN113832593A (en) * 2021-07-19 2021-12-24 信泰(福建)科技有限公司 Multilayer knitted vamp

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CN113832593A (en) * 2021-07-19 2021-12-24 信泰(福建)科技有限公司 Multilayer knitted vamp

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