CN105802008B

CN105802008B - Adhesive-bonded fabric wheel cover and its one-step moulding method

Info

Publication number: CN105802008B
Application number: CN201610177506.9A
Authority: CN
Inventors: 王恩洪
Original assignee: SHANGHAI TIANYUAN GROUP SHENGDE PLASTICS CO Ltd
Current assignee: SHANGHAI TIANYUAN GROUP SHENGDE PLASTICS CO Ltd
Priority date: 2016-03-25
Filing date: 2016-03-25
Publication date: 2018-05-01
Anticipated expiration: 2036-03-25
Also published as: CN105802008A

Abstract

The present invention provides adhesive-bonded fabric wheel cover, and adhesive-bonded fabric wheel cover global shape and the thermoplastic frame of connection bumper bar and vehicle body, and the adhesive-bonded fabric in the thermoplastic frame are kept including at least having；The raw material of the thermoplastic frame, calculates by weight, includes 0.01 5 parts of 100 parts of thermoplastic polyolefin, 0.05 15 parts of inorganic filler, 0.01 5 parts of glass fibre and halloysite nanotubes；The raw material of the adhesive-bonded fabric, calculates by weight, includes 20 45 parts of 100 parts of polyester fiber and polypropylene fibre.The adhesive-bonded fabric wheel cover performance is stable, soundproof effect is good, can not only use in usual cases, and can more meet the characteristic requirements of the bad weathers such as sleet and complex road condition to wheel cover.

Description

Adhesive-bonded fabric wheel cover and its one-step moulding method

Technical field

The present invention relates to a kind of wheel cover and its one-step moulding method, specifically, is related to the plastic wheel-cover with adhesive-bonded fabric And its one-step moulding method.

Background technology

Automobile has become the very universal vehicles, and the family car market share constantly increases, mass consumption Close examination standard of the person for passenger car is also progressively changing, and the indexs such as comfort, hommization, lightweight, oil consumption are low become main Evaluation indicators, influence the emphasis direction that the key components and parts of these indexs also become each main engine plants' technology upgrading and product adjusts.

Wheel cover is mainly used to protect wheel as a kind of key components and parts on automobile, and earliest wheel cover of automobile uses metal Punch forming.Punching press wheel cover belongs to typical covering, compared with general stamping parts, has complicated space curved surface shape, profile The features such as size is big, material is thin, surface quality requirements are high.But in the manufacturing process of wheel cover, to pass through multi-step process It can complete, complex forming technology, product are heavy, of high cost, noise is big, and present metal wheel cover is substituted by plastic wheel-cover, and It is hard plastic part progressively substituted metal part, soft gadget progressively substitutes hard plastic part.Plastic wheel-cover moulding process at present on the market is general It is divided into two kinds：One kind is injection molding, and such wheel cover moulding process is simple, and product size is stablized, and light-weight, noise is low, can be with Applied to most of vehicles currently on the market；Another uses plastic uptake technique, and plastic uptake wheel cover technique is simple, but wall thickness is difficult With control, size is unstable, is generally used on the not high low-end vehicle of required precision.Plastic wheel-cover has compared with metal wheel cover The advantage that technique is simple, cost is low, light-weight, but the effect for reducing noise is still limited, and during the rainy day travels, The water droplet that high-speed rotating tire takes up get to the water mist that backwash behind wheel cover surface goes out the driving safety of vehicle below is brought it is huge Big hidden danger.

The shaping of conventional plastic wheel-cover is to be made with olefin resin through injection molding, if wanting further lightweight, palpus The method for being combined adhesive-bonded fabric using solvent welding, sweat soldering or ultra-sonic welded.But this method is due to can only be by nothing Yarn fabric is combined with wheel cover one by one, if it is necessary to being repeatedly bonded or welded when a product must be combined by polylith adhesive-bonded fabric Step is connect, a product could be completed, it is so i.e. time-consuming and laborious, as fruit product needs more than five adhesive-bonded fabrics, with regard to palpus It could be completed through more than five processes；In addition, the position of welding is different, it is also necessary to has positioning clamping apparatus during welding；Due to being Combine one by one, wheel cover welding surface is in space curved surface again, with reference to intensity because position difference it is unstable, because being pressed from both sides during welding by fixture Clamp force direction is different, and the size of stress is also variant, the limited mechanical strength of the product with reference to after.Adhering method is such as used, is grasped Make personnel to contact with hazardous solvent in bonding agent, solvent volatilization is bad to environment；Decided using the olefines material derived from a wealth of sources Body, bonding agent species is limited, and technique for sticking condition requires high.Wheel cover of automobile can also directly be subject to daylight, wind in use The influence of the unfavorable conditions such as change, greasy dirt, humidity, frost, therefore wheel cover should possess basic strong hardness and weatherability, Neng Goutong When meet growing economical and environmentally friendly demand.Only have with the adhesive-bonded fabric in adhesive-bonded fabric wheel cover and the plastic body of wheel cover The toughness of wheel cover entirety is just can guarantee that under the conditions of combination closely and plays lightweight.

As can be seen here, it is necessary to by improving existing wheel cover formula, with reference to advanced preparation process and equipment, the property developed Energy is stablized, soundproof effect is good, and more environmentally friendly safe wheel cover and wheel cover forming method, make the wheel cover of acquisition can not only be in general case Lower use, and can more meet the characteristic requirements of the bad weathers such as sleet and complex road condition to wheel cover.

The content of the invention

The present invention provides a kind of adhesive-bonded fabric wheel cover, and wheel cover global shape and connection bumper bar are kept including at least having With the thermoplastic frame of vehicle body, and the adhesive-bonded fabric in the thermoplastic frame；The thermoplastic frame The raw material of frame, calculates by weight, includes 100 parts of thermoplastic polyolefin, 0.05-15 parts of inorganic filler, glass fibre 0.01- 5 parts and 0.01-5 parts of halloysite nanotubes；The raw material of the adhesive-bonded fabric, calculates by weight, includes polyester fiber 100 20-45 parts of part and polypropylene fibre.

Be preferably carried out mode as some, the thermoplastic polyolefin include 50-80 wt% Noblens and/ Or propylene copolymer and 10-30 wt% maleic anhydrides-modified polypropene.

Mode is preferably carried out as some, the propylene copolymer is propylene-second that ethylene contents are 30-50 wt% Alkene copolymer, the grafting rate of maleic anhydride acid is 0.05-5.5% in the maleic anhydride-modified polypropene.

Be preferably carried out mode as some, the particle diameter of the inorganic filler is 2-8 μm, the glass fibre it is a diameter of 12-18μm。

Mode is preferably carried out as some, the halloysite nanotubes are amino silicane coupling agent, epoxy radicals silicone hydride idol Join agent, silicon fluoride coupling agent or it is silica modified after halloysite nanotubes.

Mode is preferably carried out as some, the polyester fiber includes but not limited to polyglycolic acid fiber, polylactic acid It is fiber, poly- two ester fiber of hexanedioic acid second, polyhydroxyalkanoatefiber fiber, pet fiber, poly- to benzene two Formic acid butanediol ester fiber, PTT fiber, polyethylene naphthalate fiber.

Mode is preferably carried out as some, the polyester fiber is that the star-like Polycaprolactone modified PET of terminal hydroxy group is fine Dimension, and PET fiber and the weight ratio of the star-like polycaprolactone of terminal hydroxy group are 1：0.001-0.5.

The present invention also provides a kind of one-step moulding method for preparing any one adhesive-bonded fabric wheel cover recited above, comprising There are following steps,

（1）The preparation of thermoplastic frame pellet：Weigh thermoplastic polyolefin, inorganic filler, the glass fibers of parts by weight Peacekeeping halloysite nanotubes, each dry 5-12h at 60-120 DEG C, then above-mentioned raw materials are uniformly mixed, use screw extruder Extrude at 190-230 DEG C, solidified after cooling, obtain thermoplastic frame pellet；

（2）The preparation of adhesive-bonded fabric：The polyester fiber and polypropylene fibre of parts by weight are weighed, by opening for raw fibre Pine and mixing, the thin net that single fiber forms is formed by opener, using four curtain laying modes into the net by its laying networking, It is 400-1500g/m to reuse acupuncture and surface density is made²Adhesive-bonded fabric finished product, and in 150-165 DEG C of temperature, pressure 5- Compression molding 3-8min under conditions of 10MPa, obtains adhesive-bonded fabric；

（3）The pretreatment of adhesive-bonded fabric：By step（2）The adhesive-bonded fabric of acquisition is placed on heating tablet, is protected in nitrogen Under the conditions of carry out contact heating baking, heating-up temperature be 190-210 DEG C, heating time 50-60s；

（4）The preparation of wheel cover：By step（3）The adhesive-bonded fabric of acquisition by manipulator delivers into wheel cover mould after cutting It is interior, adhesive-bonded fabric is fixed by imperforate mode, Guan Bi mould simultaneously keeps 35-75 DEG C of mold temperature, nozzle temperature 190-240 DEG C, the injecting step into mould（1）The thermoplastic frame pellet of acquisition, injection finish excision charging runner, are opened after cooling Mould is opened, obtains adhesive-bonded fabric wheel cover.

Mode, step are preferably carried out as some（4）The imperforate mode is to set to be evacuated on mould Air tube, adhesive-bonded fabric reach designated position when by extracting the gas in air tube out, in a manner of vacuum suction stationary positioned without Yarn fabric.

The present invention also provides the adhesive-bonded fabric wheel cover that a kind of above-mentioned one-step moulding method prepares, the wheel cover is shape Bridge arch shape, has the frame shell that thermoplastic is formed, at least provided with one layer of adhesive-bonded fabric, institute inside the frame shell State adhesive-bonded fabric outer surface directly to contact with the frame shell inner surface, and the thickness of the adhesive-bonded fabric is 2-10mm, face Density is 400-1500g/m²。

Compared with prior art, the beneficial effects of the invention are as follows：Using the raw material of the present invention with adhesive-bonded fabric wheel cover And the wheel cover product crooked radian for preparing of related manufacturing processes is firmly combined with, ensures integral product naturally, connection is smooth Weight declines, and reduces the energy consumption of car, absorbing sound and lowering noise excellent effect；Meanwhile compared to the processing method for needing multiple welding or bonding, Wheel cover shaping of the present invention is to be integrally formed, and improves production efficiency.

Embodiment

Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of fields of the present invention The normally understood identical implication of art personnel.When there is a conflict, the definition in this specification shall prevail.

Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this public affairs can be more easily understood Open content.Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering is non- It is exclusive including.Wanted for example, composition, step, method, product or device comprising listed elements are not necessarily limited to those Element, but can include not expressly listed other key elements or such a composition, step, method, product or device it is intrinsic Key element.

In the description of this specification, reference term " one is preferably carried out scheme ", " some are preferably carried out scheme ", The description of " preferably scheme ", " example " or " some examples " etc. means to combine the specific spy that the embodiment or example describe Sign, structure, material or feature are contained at least one embodiment of the present invention or example.In the present specification, to above-mentioned The schematic representation of term is necessarily directed to identical embodiment or example.Moreover, the specific features of description, structure, material Material or feature may be combined in any suitable manner in any one or more of the embodiments or examples.In addition, not conflicting In the case of, those skilled in the art can be by the different embodiments or example described in this specification and different embodiments Or exemplary feature is combined and combines.

" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term " polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer "." copolymer " means to pass through polymerization Polymer prepared by least two different monomers.Generic term " copolymer " include term " copolymer " (its generally to refer to by Polymer prepared by two kinds of different monomers) (it is generally referring to what is prepared by three kinds of different monomers with term " terpolymer " Polymer).It also includes the polymer for planting monomer by polymerization four or more to manufacture.

It is to be understood that adhesive-bonded fabric wheel cover of the present invention can be applied to all kinds of devices containing wheel-shaped member, can be used for Muddy water, protection wheel are blocked, noise is reduced and decorates, specific described device includes common motor vehicle, it may for example comprise more Functional movement car（SUV）, bus, truck, the car of various commercial vehicles, including the water carrier of various ships and ship, Aircraft etc., and including hybrid electric vehicle, electric car, plug-in hybrid electric vehicles, hydrogen-powered vehicle and other substitute fuels Car（For example, the fuel of the resource beyond oil）.As mentioned in this article, hybrid electric vehicle is that have two or more The vehicle of power source, for example, having petrol power and electrodynamic vehicle.

The present invention provides a kind of adhesive-bonded fabric wheel cover, the adhesive-bonded fabric wheel cover at least by holding wheel cover global shape with And the thermoplastic frame of connection bumper bar and vehicle body, and the adhesive-bonded fabric composition in the thermoplastic frame；

The raw material of the thermoplastic frame, calculates by weight, includes 100 parts of thermoplastic polyolefin, inorganic fills out 0.01-5 parts of 0.05-15 parts of material, 0.01-5 parts of glass fibre and halloysite nanotubes；

The raw material of the adhesive-bonded fabric, calculates by weight, includes 100 parts of polyester fiber and polypropylene fibre 20- 45 parts.

Thermoplastic polyolefin：

Any suitable thermoplastic polyolefin can be used as the thermoplastic frame of adhesive-bonded fabric wheel cover of the present invention Primary raw material.Thermoplastic be typically can at least material softening temperature or melting temperature molding or shaping and again The material of processing.Polyolefin is preferable thermoplastic.Polyolefin is the fundamental building block of polymer science and engineering, because The low cost and high-throughput produced for thermoplastic based on petrochemistry.

Preferably thermoplastic polyolefin, including polythylene resin and polypropylene-based resin.

Polythylene resin includes：High-pressure process low-density polyethylene, high density polyethylene (HDPE), ethene-alpha-olefin copolymer, second The polyethylene-based resins such as alkene-beta-unsaturated esters copolymer.As high-pressure process low-density polyethylene, such as it is 910- that can enumerate density 930 kg/m³High-pressure process low-density polyethylene.In addition, as high density polyethylene (HDPE), such as it is 941-970 that can enumerate density kg/m³High density polyethylene (HDPE).Density is the value that the method according to specified in JIS K6760-1981 measures.

Polypropylene-based resin includes Noblen, propylene-ethylene copolymers and propylene and containing 4 or more carbon atom Alpha-olefin copolymer.Term " alpha-olefin containing 4 or more carbon atoms " is referred to as " alpha-olefin ", and preferably the present invention uses Polypropylene be selected from propylene-ethylene copolymers and the copolymer of propylene and alpha-olefin.

Alpha-olefin in propylene and alpha olefin copolymer is preferably any type alpha-olefin containing 4-20 carbon atom, specifically It is as follows：1- butylene, 2- methyl-1-propylenes, 1- amylenes, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1- hexenes, 2- ethyls -1- Butylene, 2,3- dimethyl -1- butylene, 2- Methyl-1-pentenes, 3- Methyl-1-pentenes, 4-methyl-1-pentene, 3,3- dimethyl - 1- butylene, 1- heptene, 2- methyl isophthalic acids-hexene, 2,3- dimethyl -1- amylenes, 2- ethyl -1- amylenes, 2,3,4- trimethyl -1- fourths Alkene, 2- methyl -3- ethyl -1- butylene, 1- octenes, 5- Methyl-1-pentenes, 2- ethyl -1- hexenes, 3,3- dimethyl -1- hexenes, 2- propyl group -1- heptene, 2- methyl -3- ethyl -1- heptene, 2,3,4- trimethyl -1- amylenes, 2- propyl group -1- amylenes, 2,3- diethyls Base -1- butylene, 1- nonenes, 1- decene, 1- endecatylenes, 1- dodecylenes, 1- tridecylenes, tetradecene, 15 carbon of 1- Alkene, cetene, 1- heptadecenes, 19 carbene of 1- vaccenic acids and 1-.α-alkene preferably containing 4-12 carbon atom Hydrocarbon, its instantiation include 1- butylene, 2- methyl-1-propylenes, 1- amylenes, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1- oneself Alkene, 2- ethyl -1- butylene, 2,3- dimethyl -1- butylene, 2- Methyl-1-pentenes, 3- Methyl-1-pentenes, 4-methyl-1-pentene, 3,3- dimethyl -1- butylene, 1- heptene, 2- methyl isophthalic acids-hexene, 2,3- dimethyl -1- amylenes, 2- ethyl -1- amylenes, 2,3,4- Trimethyl -1- butylene, 2- methyl -3- ethyl -1- butylene, 1- octenes, 5- Methyl-1-pentenes, 2- ethyl -1- hexenes, 3,3- bis- Methyl isophthalic acid-hexene, 2- propyl group -1- heptene, 2- methyl -3- ethyl -1- heptene, 2,3,4- trimethyl -1- amylenes, 2- propyl group -1- Amylene, 2,3- diethyl -1- butylene, 1- nonenes, 1- decene, 1- endecatylenes and 1- dodecylenes.

Polyacrylic fusing point (T_m) it is 150 DEG C -165 DEG C.It is preferred that Tm is not less than 155 DEG C, more desirably not less than 160 ℃.On the other hand, preferably Tm is not higher than 165 DEG C, more preferably no higher than 164 DEG C.If Tm is less than 150 DEG C, polyacrylic T_m At being defined as in the polypropylene fusion curve (DSC curve) with differential scanning calorimetry (DSC) measurement where maximum endothermic peak Temperature (DEG C).

The example of polypropylene manufacture method be included in the presence of known typical polymerization catalyst propylene is polymerized alone or Person is by the method for propylene and ethene or alpha-olefin copolymer.Scheme is preferably carried out as some, the alkene based composition also wraps Containing modified polyolefin, specifically, for example, the polyolefin that acid is modified is common by such as polyethylene, polypropylene, ethene-alpha-olefin Polymers, ethylene-alpha-olefin-nonconjugated diene compound copolymer (for example, EPDM) and ethene-aromatic monovinyl compound thing- The graft copolymerization of the polyolefin such as conjugated diene compound copolymer rubber and the unsaturated carboxylic acid of such as maleic acid or maleic anhydride It is prepared by modification with copolymer.

Graft copolymerization includes using as benzoyl peroxide in appropriate solvent such as polyolefin and unsaturated carboxylic acid Radical initiator reaction.The component of unsaturated carboxylic acid or derivatives thereof can pass through the component and the nothing of polyolefin monomer Rule or block copolymerization and be introduced into polymer chain.For modified unsaturated carboxylic acid example be with polymeric double bond, The compound of carboxyl and functional group such as hydroxyl and amino if necessary；Such as maleic acid, fumaric acid, itaconic acid, acrylic acid and methyl Acrylic acid.The example of the derivative of unsaturated carboxylic acid is acid anhydrides, ester, acid amides, acid imide and the metal salt of above-mentioned unsaturated carboxylic acid. Its instantiation is maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate Ester, ethyl methacrylate, one ethyl ester of maleic acid, diethyl maleate, one methyl esters of fumaric acid, dimethyl fumarate, acryloyl Amine, Methacrylamide, maieamic acid, maleic acid diamides, fumaric acid monamide, maleimide, N- butyl Malaysia Acid imide and Sodium methacrylate.And then preferred maleic anhydride.Highly polar side base, horse are introduced on nonpolar molecular backbone Maleic anhydride grafted polypropylene can become and promote polar material and non-polar material cementability and the bridge of compatibility.

Degree of effect in view of the present invention etc., preferable acid modified polyolefin is maleic anhydride-modified polypropene, is made For the maleic anhydride modified polypropylene used in the present invention（MAH-g-PP）It is not particularly limited, can is that commercially available or experiment is closed Into, the grafting rate preferred 0.05-5.5%, more preferably 0.7-2.2% of maleic anhydride acid.

Scheme is preferably carried out as some, in percentage by weight, it is equal that the thermoplastic polyolefin includes propylene Polymers and/or propylene copolymer 50-80 mass %, maleic anhydride-modified polypropene 10-30 mass %.The propylene copolymer For propylene-ethylene copolymers, ethylene contents are 30-50 mass % in propylene-ethylene copolymers component.

Scheme is preferably carried out as some, it is in percentage by weight, described as the raw material of thermoplastic frame Thermoplastic polyolefin includes Noblen 36-56 mass %, propylene-ethylene copolymers 28-45 mass %, and maleic anhydride- Modified polypropene 10-30 mass %.

Scheme is preferably carried out as one, it is in percentage by weight, described as the raw material of thermoplastic frame Thermoplastic polyolefin includes 42 mass % of Noblen, 33 mass % of propylene-ethylene copolymers, and maleic anhydride-modification gathers 25 mass % of propylene.

Inorganic filler：

Inorganic filler is used to improve heat resistance and rigidity, but is not particularly limited.Specifically, its can be selected from talcum, Potassium carbonate, wollastonite, calcium sulfate, magnesia, calcium stearate, mica, silica, calcium silicates, the one or more of clay and carbon black. Specifically, inorganic filler can be as the increase of its additive amount can make the rigidity and the obvious increased thing of hardness of resin combination Matter.Therefore, more properly, wollastonite or extra fine talc can be used.Specifically, the average grain diameter of inorganic filler can be, e.g., from about 1-30 μm, more properly, such as from about 2-8 μm.For example, if the average grain diameter of inorganic filler is less than 1 μm, heat resistance and rigidity change Kind possible deficiency.And if average grain diameter is more than about 30 μm, during polyolefine resin composition extrusion molding, operation and operating can It can be not easy.

The inorganic filler is in the preferred 0.05-15 parts by weight of content of the raw material of thermoplastic frame, more preferably 0.1-8 Parts by weight, relative to the thermoplastic polyolefin of 100 parts by weight.

Scheme is preferably carried out as one, the inorganic filler is extra fine talc, content preferably 5 parts by weight, relative to The thermoplastic polyolefin of 100 parts by weight.

Glass fibre：

Glass fibre for the present invention can be not particularly limited and use, and be characterized in that the glass fibre in the present invention In the resin combination and formed body of reinforcement, help to show high mechanical properties i.e. high rigidity/high impact and creep resistance Property etc..

Scheme is preferably carried out as some, preferred 3-25 μm of the glass fiber diameter, more preferably 6-22 μm, into one Walk preferred 10-20 μm, particularly preferred 12-18 μm.As described below, fibre diameter and fibre length for example can by using microscope or Slide calliper rule etc. measure pill or the formed body remaining glass after heating is ashed of glass fibre itself to be used or composition Fiber and the value that obtains measure.

The surface of glass fibre can pre-process or without processing.In order to improve in polypropylene-based resin etc. dispersiveness and Adhesion etc., for example, the surface of glass fibre is preferably with organo silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconium Acid esters coupling agent, silicone compounds, higher fatty acids, fatty acid metal salts or fatty acid ester etc. are handled.

The example of organo silane coupling agent is vinyltriethoxysilane, vinyltrimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, N- β-(ammonia Ethyl)-gamma-amino propyl trimethoxy silicane, β-(2,4- epoxycyclohexyls) (ethoxymethyl) oxysilane and γ-(2- ammonia second Base) TSL 8330.Wherein, preferred amino silane coupling agent.The example of higher fatty acids is oleic acid, the last of the ten Heavenly stems Acid, laurate, palmitic acid, stearic acid, montanic acid, gallic acid, linoleic acid, rosin acid, leukotrienes, hendecanoic acid and 11 Carbon enoic acid.The example of fatty acid metal salts is such as the aliphatic acid with the carbon atom of more than 9 of stearic acid and montanic acid Sodium, lithium, calcium, magnesium, zinc and aluminium salt.Wherein, preferably calcium stearate, aluminum stearate, montanic acid calcium or montanic acid sodium.

The glass fibre is in the preferred 0.01-5 parts by weight of content of the raw material of thermoplastic frame, more preferably 0.1-3 Parts by weight, most preferably 2.5 parts by weight, relative to the thermoplastic polyolefin of 100 parts by weight.

Halloysite nanotubes：

Halloysite nanotubes of the present invention（HNTs）It is a kind of natural inorganic nanotube as Nano filling, galapectite Common form mainly has spherical and two kinds of a tubulose, wherein tubular structure be crimped under natural endowment by kaolinic lamella and Into nanotube-shaped galapectite is formed by more than 20 a lamella curlings.Bore is 15~20 nm, and outside diameter is about 50 nm, Length is 100~1500 nm, therefore galapectite usually is known as halloysite nanotubes.Galapectite belongs to the aqueous of monoclinic system Layer silicate mineral, its desirable chemical molecular formula are Al₂Si₂O₅(OH)₄·nH₂O, wherein n=0 and n=2 represent layer respectively Spacing is 7（1 Å=0.1 nm）With 10 HNTs.Due to growing the difference of geographical environment, the constituent of different HNTs It is slightly different.10 HNTs lamellas are formed by the oxygen-octahedron of outer layer and the alumina octahedral regular array of internal layer, piece It is crystalline water molecules among layer.HNTs interlamellar spacings before the crystallization water is sloughed are 10, and the interlamellar spacing after the crystallization water is sloughed It is changed into 7, this dehydration is irreversible.Although HNTs and nano-particle, its tubular structure with certain draw ratio, Be conducive in the polymer scattered；In addition, HNTs surfaces are mainly silicon oxygen bond, the Si-OH hydroxy densities of pipe surface are relatively low, hydrogen Key effect is weaker, and surface charge distribution is more special, is not susceptible to reunite.

Scheme is preferably carried out as some, halloysite nanotubes of the present invention are modified halloysite nanotubes, modified Method can be coupling agent modified, intercalation modifying, loaded modified, radical modification and surfactant-modified.

The coupling agent can be amino silicane coupling agent, epoxy silane coupling or silicon fluoride coupling agent.

By taking amino coupling agent is modified halloysite nanotubes as an example, preparation method can be：60g is added in three-necked flask Toluene and 1g halloysite nanotubes, ultrasonic disperse 30min, is vigorously stirred, and adds 2-5g amino silicane coupling agent KH-590, 100-110 DEG C of back flow reaction 10-15 h, filtering, is washed with absolute ethyl alcohol, extracted three times, 24h is dried in vacuum drying chamber, Obtain aminosilane coupling agent modifying halloysite nanotubes.

Scheme is preferably carried out as some, halloysite nanotubes of the present invention are silica modified galapectite nanometers Pipe, specific preparation method：

（1）Take halloysite nanotubes in distilled water using ultrasonic disperse to forming uniform suspension；

（2）Weigh ethyl orthosilicate, the mass ratio of halloysite nanotubes and ethyl orthosilicate is 1：（2-5）, it is added to nothing The alcoholic solution that ethyl orthosilicate is made is dissolved in water-ethanol；

（3）Will be above-mentioned（2）Solution is slowly dropped to made from step（1）In suspension made from step, strong stirring is extremely Solution is uniform, using ultrasonic disperse to forming uniform suspension；Ammonium hydroxide control ph is added dropwise into suspension in 9.5-10, often Temperature is lower to be stirred to ethyl orthosilicate complete hydrolysis；

（4）After teos hydrolysis, obtained reaction solution is placed in 40 DEG C of baking ovens to drying to constant weight, obtains dioxy SiClx is modified halloysite nanotubes；

（5）By step（4）Obtain silica modified halloysite nanotubes be placed in ethanol water, wherein ethanol and The ratio of water is 1：5, stirring to obtain suspension, then amino silane coupling agent is added dropwise in suspension, and it is silica modified The mass ratio of halloysite nanotubes and amino silane coupling agent is 1：0.8-1.2, stirs 15-24h, after filtering at 30-35 DEG C By the powder of acquisition, drying to constant weight at 40-50 DEG C.

Above-mentioned steps（5）The amino silane coupling agent mentioned is selected from γ aminopropyltriethoxy silane, gamma-amino Propyl trimethoxy silicane, N- β-(aminoethyl)-gamma-amino propyl trimethoxy silicane and γ-(2- aminoethyls) aminopropyl One or more of combinations in trimethoxy silane.

It is preferred that γ-(2- aminoethyls) TSL 8330, and silica modified halloysite nanotubes and γ- The mass ratio of (2- aminoethyls) TSL 8330 is 1：1.

The halloysite nanotubes the raw material of thermoplastic frame the preferred 0.01-5 parts by weight of content, more preferably 0.2-3 parts by weight, relative to the thermoplastic polyolefin of 100 parts by weight.

The halloysite nanotubes are mainly used to improve vehicle cover plastic frame obdurability of the present invention, preferably scheme by its with Silica combines, then has embodied more preferable durability, the silicone hydroxyl and ethyl orthosilicate on the halloysite nanotubes surface Son hydrolysis polycondensation occurs, generation covalent bond is connected to halloysite nanotubes surface, increases the silicone hydroxyl on its surface, then by silicon Alkanisation processing, the product and thermoplastic polyolefin for making acquisition have a more preferable interface bond strength, can preferably bear from The part stress that matrix transfer comes, effectively prevents the extension of crackle.

The thermoplastic polyolefin can also be by compounding other additive components commonly used in the art, with each single Form or as a mixture and to reach its specific purposes convention amount.As addible additive, dosage is normal Dosage is advised, or is adjusted according to the requirement of actual conditions.Additive includes improving the elastomer of plastic frame impact strength, uses In the light stabilizer and ultra-violet absorber that improve plastic frame weatherability, and the colouring agent for coloring.

The example of elastomer is ethylene-propylene copolymer elastomer, ethylene-butene copolymer elastomer, polyethylene-hexene are common Copolymer elastomers, ethylene-octene copolymer elastomer, ethylene-propylene-diene copolymer elastomer, styrene-ethylene-butadiene- Styrene block copolymer and styrene ethylene-propylene-styrene block copolymer.

The example of light stabilizer is hindered amine compound.Instantiation for dimethyl succinate and 1- (2- ethoxys)- The condensation product of 4- hydroxyl -2,2,6,6- tetramethyl piperidines；Poly- [[6- (1,1,3,3- tetramethyl butyls) imino group -1,3,5- three Piperazine -2,4- diyls] [(2,2,6,6- tetramethyl -4- piperidyls) imino group] hexa-methylene [(2,2,6,6- tetramethyl -4- piperidines Base) imino group]]；Four (2,2,6,6- tetramethyl -4- piperidyls) 1,2,3,4- butane tetracarboxylic acid esters；Four (five first of 1,2,2,6,6- Base -4- piperidyls) 1,2,3,4- butane tetracarboxylic acid esters；Double (1,2,2,6,6- pentamethyl -4- piperidyls) sebacates；With it is double- 2,2,6,6- tetramethyl -4- piperidinyl sebacates.

Ultra-violet absorber, the example of Benzotriazole Ultraviolet Stabilizer is 2- (2 '-hydroxyl -3 ', 5 '-di-t-butyl Phenyl) -5- chlorinated benzotriazoles and 2- (2 '-hydroxyl-the 3 '-tert-butyl group -5 '-tolyl) -5- chlorinated benzotriazoles；Benzophenone class The example of ultra-violet absorber is 2- hydroxyl -4- methoxy benzophenones and 2- hydroxyl -4-n- octyloxy Benzophenones；And salicylate The example of class ultra-violet absorber is 4- tert-butylphenyl salicylates acid esters and 2,4- di-t-butyl 3 ', 5 '-di-t-butyl -s of phenyl 4 '-hydroxybenzoate.

The example of inorganic based colorant is titanium oxide, iron oxide (such as red ferric oxide), chromic acid (such as chrome yellow) and carbon black.As Organic based colorant, mentions azo-based colorant such as slightly solubility azo lake/solubility azo lake, phthalocyanine-based colorant such as phthalein Cyanines indigo plant/phthalocyanine green, intellectual circle's based colorant such as anthraquinone/, acridone based colorant and isoindolinone based colorant etc..

The thermoplastic frame will be obtained by injection molding, so needing before the forming by above-mentioned raw materials by weight Part is prepared into powder or pellet, and specifically preparation method can use preparation method commonly used in the art, specifically includes original Material is mixed, dried, screw extruder extruding pelletization.

Adhesive-bonded fabric：

Adhesive-bonded fabric is also known as non-woven fabrics, non-woven cloth, adhesive-bonded fabric, be it is a kind of orient or random alignment fiber by rubbing Wipe, obvolvent or bonding or the combination of these methods and be combined with each other manufactured thin slice, fibre web or batts.Do not include paper and machine Fabric, knitted fabric, tufteds, the stitch bonded fabrics with stitching yarn and wet method fulling milling felted terxture.Fiber can be natural Or chemical process, can be staple fiber, long filament or the threadiness formed on the spot.Adhesive-bonded fabric of the present invention has because of it There are porous loose structure and more fiber interface and there are good sound absorbing capabilities, application flexibility non-woven material or its composite wood Material not only overcomes high density material than the shortcomings that great, of high cost, while the processing forming of this material is good, be easy to and its His structure composite.The parameters such as the non-woven fabric fiber preparation method, material category, fineness, the thickness of material, unit weight can shadow Ring the sound absorbing capabilities of adhesive-bonded fabric and the adhesiveness with outer plastic frame.

The adhesive-bonded fabric is commercially available voluntarily to be synthesized.The preparation method of specific adhesive-bonded fabric can use method The air-laid process of Laroche companies of state, combs and acupuncture moulding process, melt-blown composite molding technique and the dry method of paper-making Composite molding technique prepares.Wherein described combing and acupuncture moulding process flow process are：Opening or cleaning mixing → vibrating cotton box or gas Pressure hopper → carding machine → cross lapping machine → needing machine → cutting winding or plate cut forming machine.

Polyester fiber of the present invention can be selected from any of polyester fiber, and the polyester includes but not limited to Polyglycolic acid（PGA）, polylactic acid（PLA）, poly- hexanedioic acid second diester（PEA）, polyhydroxyalkanoate（PHA）, poly- terephthaldehyde Sour glycol ester（PET）, polybutylene terephthalate (PBT)（PBT）, polypropylene terephthalate（PTT）, poly- naphthalene diformazan Sour glycol ester（PEN）And combinations thereof.

And then preferred pet fiber, it is commonly called as polyester fiber and is also known as polyester fiber.

Scheme is preferably carried out as some, pet fiber of the present invention gathers for modified Ethylene glycol terephthalate fiber, the particularly star-like Polycaprolactone modified PET fiber of terminal hydroxy group.

The preparation method of the star-like polycaprolactone of terminal hydroxy group is：The tripolyphosphazene of ring containing hexahydroxy derivative is synthesized first to make For initiator, then the initiation caprolactone monomer ring-opening polymerisation under the catalytic action of stannous iso caprylate, star-like polycaprolactone is obtained.Tool Body ground preparation method：

（1）In equipped with magnetic agitation, the 250mL three neck round bottom flask of reflux condensing tube add 5g hexachlorocyclotriph,sphazenes and 20g potassium carbonate and 130ml tetrahydrofurans, lead to nitrogen 30min, 7.5g parahydroxyben-zaldehydes are slowly added dropwise under ice-water bath.It is added dropwise After be warmed to room temperature, react 72h, after reaction filter remove white depositions, obtained after the rotated evaporation of filtrate dense molten Liquid.Concentrated solution is added drop-wise in petroleum ether and is precipitated, obtains white solid, then with re-crystallizing in ethyl acetate, obtains six (4- aldehyde radical benzene oxygen Base) three phosphonitrile of ring.

（2）It is 1 that tetrahydrofuran and methanol volume ratio are added in the round-bottomed flask equipped with magnetic agitation：1 mixed solution, Add 7g steps（1）Six (4- aldehyde radicals phenoxy group) rings, three phosphonitrile obtained, 2.5g sodium borohydrides are slowly added under quick stirring Powder, reacts 20h at room temperature, and most of solvent is removed with Rotary Evaporators, adds deionized water stirring 30min, and centrifugation obtains White powder is obtained, obtains six (4- hydroxy methyl phenyloxies) rings, three phosphonitrile three times with ethyl alcohol recrystallization.

（3）Step is added in polymerization pipe（2）Obtain six (4- hydroxy methyl phenyloxies) rings three phosphonitrile 0.65g and ε-oneself in The stannous iso caprylate of ester 10.35g and gross mass 0.1%, depressurize 3h at room temperature, the tube sealing under vacuum state.Then polymerization pipe is soaked Enter in 120 DEG C of oil bath, isothermal reaction 24h, by the product of acquisition as dichloromethane, excessive oil ether is added dropwise, by acquisition Precipitation obtains the star-like polycaprolactone of terminal hydroxy group as being dried in 40 DEG C of vacuum drying chambers to constant weight.

The preparation method of modified PET is：After PET fiber and the star-like polycaprolactone drying of terminal hydroxy group, according to weight ratio 1： 0.001-0.5 is mixed, and the temperature of mixing is 100-120 DEG C, adds to screw extruder and carries out extruding pelletization, each area of screw rod Temperature setting be：One 270 DEG C of area, two 290 DEG C of areas, three 280 DEG C of areas.Obtained modified PET drying will be granulated again to constant weight, Spinning is carried out under the conditions of 270-290 DEG C, spinning speed 1000m/min, stretches fiber under 80-120 DEG C of temperature conditionss, obtains The star-like Polycaprolactone modified PET polyester fibers of terminal hydroxy group.

The PET fiber and the weight ratio of the star-like polycaprolactone of terminal hydroxy group are preferably 1：0.065.

The PP fibers of the preferred low melting point of polypropylene fibre, specific fusing point is 130-200 DEG C, and then preferred 153- 165 DEG C, it can directly select commercially available.

Scheme is preferably carried out as some, the preparation process flow of adhesive-bonded fabric of the present invention may be referred to this area Common preparation method, be specifically exemplified by for：Fibrous raw material → shredding → mixing → combing networking → pre-needling → main acupuncture → patch Face → compression molding.Compression molding is the difference using PP fibers and PET fiber fusing point, at a certain temperature melts PP fibers Melt, above-mentioned PET/PP mixtures are molded into the bonded fabric using PP as matrix.

The shredding and mixing be the PP fibers that will be precisely weighed and PET fiber carry out pre- shredding in pre-opener after give Enter opener and carry out shredding and mixing, make the mixed uniformly purpose of fiber to reach.Fiber passes through shredding after shredding and mixing The discharge port of machine forms the thin net being made of single fiber, using four curtain laying modes into the net by its laying into thin net.Molding 150-165 DEG C of forming temperature, molding pressure 5-10MPa, clamp time 3-8min.

Modified PET in the bonded fabric star-like polycaprolactone because blending adds, greatly improves overall bonded fabric Tensile property, thus it is speculated that be probably because the special structure of the ester type compound and more active group increase PET and divide greatly The chain entanglement and physical crosslinking point of son, enhance intermolecular force.

Scheme is preferably carried out as some, the raw material of the adhesive-bonded fabric, calculates, include modified poly ester by weight 38 parts of 100 parts of fiber and polypropylene fibre.

Present invention also offers a kind of one-step moulding method for preparing adhesive-bonded fabric wheel cover.

Adhesive-bonded fabric wheel cover of the present invention is shape bridge arch shape, and outer working face is thermoplastic frame, Intermediate Gray on-woven The methods of thing, Multi-working-surface one-pass molding is generally inlayed using injection, double-material injection-molding, adhesive-bonded fabric wheel cover of the present invention use The method of embedding and injection molding.First stamping forming adhesive-bonded fabric is carried out to cut into suitable size, is then delivered into by machinery Metal die, and positioned in mold cavity, then be fixed by specific device, mold-closing injection shaping.

The machinery conveys：The adhesive-bonded fabric cut is placed on conveying frame；Periphery has positioning to lean on column, by machinery Route of the hand along setting, captures adhesive-bonded fabric with the mode of machinery, is sent into injecting molding die cavity.

The positioning is：The adhesive-bonded fabric that manipulator is sent into is put in mould, in adhesive-bonded fabric middle part, with not The mechanical system stationary positioned adhesive-bonded fabric of perforation.

The injection moulding is：Guan Bi mould, injects above-mentioned mould, injection molding, cooling by thermoplastic raw material Rear mold is opened, and obtains adhesive-bonded fabric wheel cover.

The main body of the adhesive-bonded fabric wheel cover of acquisition is holding wheel cover global shape and the thermoplastic of connection bumper bar and vehicle body Property plastic frame, and the adhesive-bonded fabric in the thermoplastic frame；Moulded with thermoplasticity on each piece of adhesive-bonded fabric periphery Material frame frame is combined by injection molding, and middle part can be simple layer adhesive-bonded fabric working face.

Preferably, the positioning is in adhesive-bonded fabric middle part, fixed with air tube, vacuum suction mode is fixed fixed Position, mould close the engagement isolation of two components, two working face wheel of injection molding arch liner.As long as restructuring adjustment thermoplastic frame With the isolation mode structure of adhesive-bonded fabric, the position of air tube positioning, you can a variety of wheel arches for possessing two working faces of injection molding.

Preferably, the imperforate mechanical system is the thimble and self-adhesion structure fixation nothing by being set in mould Yarn fabric, after by manipulator, adhesive-bonded fabric is sent to designated position, internal photoelectric sensor perceives the position of adhesive-bonded fabric Change, passes out electric signal and sends the instruction of two steps, ejector pin mechanism oil cylinder is started to work, thimble, which voluntarily ejects, determines adhesive-bonded fabric Position, subsequent manipulator both ends telescoping mechanism pushes at adhesive-bonded fabric both ends inwards, and is bonded in self-adhesion structure, and manipulator moves back Go out, molding shaping.

It should be noted that melting charge is obstructed into glue during injection, and edge connection request has the transition region of 10 mm, melt It cannot pierce into synthesis of non-woven fabric, in order to ensure that adhesive-bonded fabric wheel cover has certain holding shape facility requirement adhesive-bonded fabric Centre has that specifies to run through muscle.Preferably, oil cylinder side core-drawing mechanism can be used by lateral aperture position, passing through among wheel cover Wear muscle to be directly molded on adhesive-bonded fabric, take cover half to be recessed, dynamic model protrusion, the mode that both coordinate carries out.According to above-mentioned spy Seek peace used plastics performance, type is filled using high temperature and high speed.In mold design and manufacture view, to reduce cast system as far as possible The stream material resistance of system, draw taper are big.Pushing-out structure force is balanced steady, and mold cavity surface roughness is small, and notes Meaning exhaust.

Scheme is preferably carried out as some, the one-step moulding method of adhesive-bonded fabric wheel cover of the present invention includes following step Suddenly：

（2）The preparation of adhesive-bonded fabric：The polyester fiber and polypropylene fibre of parts by weight are weighed, by opening for raw fibre Pine and mixing, the thin net that single fiber forms is formed by opener, using four curtain laying modes into the net by its laying networking, It is 400-1500g/m to reuse acupuncture and surface density is made²Adhesive-bonded fabric, and in 150-165 DEG C of temperature, pressure 5-10MPa Under conditions of compression molding 3-8min, obtain adhesive-bonded fabric finished product；

（3）The pretreatment of adhesive-bonded fabric：By step（1）The adhesive-bonded fabric of acquisition is placed on heating tablet, is protected in nitrogen Under the conditions of carry out contact heating baking, heating-up temperature be 190-210 DEG C, heating time 50-60s；

（4）The preparation of wheel cover：By step（3）The adhesive-bonded fabric of acquisition by manipulator delivers into wheel cover mould after cutting It is interior, adhesive-bonded fabric is fixed by way of air tube absorption, Guan Bi mould simultaneously keeps 35-75 DEG C of mold temperature, nozzle temperature 190- 240 DEG C, the injecting step into mould（1）Thermoplastic is obtained, excision charging runner, opening mold after cooling, obtains nonwoven Fabric wheel cover.

Present invention also offers the adhesive-bonded fabric wheel cover prepared according to above-mentioned one-step moulding method, the wheel cover is outer Shape bridge arch shape, has the frame shell that thermoplastic is formed, at least provided with one layer of adhesive-bonded fabric inside the frame shell, The adhesive-bonded fabric outer surface is directly contacted with the frame shell inner surface, and the thickness of the adhesive-bonded fabric is 2-10mm, Surface density is 400-1500g/m²。

The thickness of the adhesive-bonded fabric can be 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm；The surface density can be 400 g/m², 500g/m², 550g/m², 600g/m², 650 g/m², 700 g/m², 750g/m², 800g/m², 900 g/m², 1000 g/m², 1100g/m², 1200g/m², 1300g/m², 1400g/m², 1500g/m²。

The present invention is preferably carried out scheme, and the raw material of the thermoplastic frame includes silica modified galapectite Nanotube, can when the adhesive-bonded fabric raw material includes star-like Polycaprolactone modified pet fiber Obtain and bond close adhesive-bonded fabric wheel cover, there is excellent soundproof effect.Speculate the possible reason is when the thermoplasticity of melting Plastics are contacted in injection phase with adhesive-bonded fabric, and hydroxyl and amino and the modified PET fiber on modified halloysite nanotubes surface are sent out Stronger intermolecular force is given birth to, and the special nanostructured of halloysite nanotubes may have under suitable temperature conditionss Help prevent matrix melt from penetrating into adhesive-bonded fabric, keep non-woven fabric fiber preferable sound-absorbing and soundproof effect in itself.Most Make the adhesive-bonded fabric wheel cover of acquisition can not only use in usual cases eventually, and can more meet the bad weathers such as sleet and answer Characteristic requirements of the miscellaneous road conditions to wheel cover.

Embodiment 1, a kind of adhesive-bonded fabric wheel cover, adhesive-bonded fabric wheel cover global shape and connection are kept including at least having The thermoplastic frame of bumper bar and vehicle body, and the adhesive-bonded fabric in the thermoplastic frame；The thermoplasticity The raw material of plastic frame, calculates by weight, includes 100 parts of thermoplastic polyolefin, 0.05-15 parts of inorganic filler, glass fibers 0.01-5 parts of 0.01-5 parts of dimension and halloysite nanotubes；The raw material of the adhesive-bonded fabric, calculates by weight, includes polyesters 20-45 parts of 100 parts of fiber and polypropylene fibre.

Embodiment 2, identical with embodiment 1, difference lies in the thermoplastic polyolefin includes 50-80 wt% third Polyamino alkenyl thing and/or propylene copolymer and 10-30 wt% maleic anhydrides-modified polypropene.

Embodiment 3, identical with embodiment 1, difference lies in the propylene copolymer is that ethylene contents are 30-50 The propylene-ethylene copolymers of wt%, the grafting rate of maleic anhydride acid is 0.05- in the maleic anhydride-modified polypropene 5.5%.

Embodiment 4, identical with embodiment 1, difference lies in the particle diameter of the inorganic filler is 2-8 μm, the glass A diameter of 12-18 μm of fiber.

Embodiment 5, it is identical with embodiment 1, difference lies in, halloysite nanotubes be amino silicane coupling agent, Epoxy silane coupling, silicon fluoride coupling agent or it is silica modified after halloysite nanotubes.

Embodiment 6, identical with embodiment 1, difference lies in the polyester fiber includes but not limited to polyglycolic acid Fiber, acid fiber by polylactic, poly- two ester fiber of hexanedioic acid second, polyhydroxyalkanoatefiber fiber, polyethylene terephthalate are fine Dimension, polybutylene terephthalate (PBT) fiber, PTT fiber, polyethylene naphthalate fiber.

Embodiment 7, identical with embodiment 1, difference lies in the polyester fiber is the star-like polycaprolactone of terminal hydroxy group Modified PET fiber, and PET fiber and the weight ratio of the star-like polycaprolactone of terminal hydroxy group are 1：0.001-0.5.

Embodiment 8, a kind of one-pass molding side of any one adhesive-bonded fabric wheel cover prepared described in embodiment 1-7 Method, includes following steps,

Embodiment 9, identical with embodiment 8, difference lies in step（4）The imperforate mode is in mould Upper setting can be evacuated air tube, when adhesive-bonded fabric reaches designated position by extracting the gas in air tube out, with the side of vacuum suction Formula stationary positioned adhesive-bonded fabric.

Embodiment 10, the adhesive-bonded fabric wheel cover prepared according to the one-step moulding method of embodiment 8 or 9, institute It is shape bridge arch shape to state wheel cover, the frame shell formed with thermoplastic, at least provided with one inside the frame shell Layer adhesive-bonded fabric, the adhesive-bonded fabric outer surface is directly contacted with the frame shell inner surface, and the thickness of the adhesive-bonded fabric Spend for 2-10mm, surface density 400-1500g/m²。

The present invention is explained in more detail with comparative example below by some embodiments, it should be appreciated that these implementations It is that example only illustrates and nonrestrictive.The raw material that example below is used with comparative example：Noblen is South Korea's Hyosung J800；Propylene-ethylene copolymers and PP fibers are purchased from Taiwan chemical fibre；Maleic anhydride-modified polypropene is purchased from 123 section of Ningbo Change plastic cement Technology Co., Ltd.；Extra fine talc is purchased from Guang Yuan Ultramicro-powders Co., Ltd of Jiangyin City；Glass fibre is sub- purchased from Shenzhen Science and Technology Ltd. of Taida；Halloysite nanotubes are purchased from Lingshou County Nan Yu mineral products processings factory；6-caprolactone is purchased from Shanghai Ou Le Chemical Co., Ltd.；PET polyester fibers are purchased from Dalian Synthetic Fibres Inst.；The experimental raw of other not specified (NS)s is purchased from me Fourth reagent Shanghai Co., Ltd.

A1：55 wt % Noblens, 45wt % propylene-ethylene copolymers（Ethylene contents are 20 wt %）

A2：42 wt % Noblens, 33 wt % propylene-ethylene copolymers（Ethylene contents are 35 wt %）, 25 wt % maleic anhydrides-modified polypropene（The grafting rate of maleic anhydride acid is 1.2%）

B：Extra fine talc, 5-7 μm of average grain diameter

C：Glass fibre, 15-17 μm of average diameter

D1：Halloysite nanotubes

D2：Amino coupling agent is modified halloysite nanotubes, specific preparation method：

The halloysite nanotubes that addition 60g toluene and 1g D1 are used in three-necked flask, ultrasonic disperse 30min, acutely Stirring, adds 2.5g amino silicane coupling agents KH-590,110 DEG C of back flow reaction 13h, filtering, is washed with absolute ethyl alcohol, extracted Three times, 24h is dried in vacuum drying chamber, obtains aminosilane coupling agent modifying halloysite nanotubes.

D3：Silica modified halloysite nanotubes, specific preparation method：

（2）Weigh ethyl orthosilicate, the mass ratio of halloysite nanotubes and ethyl orthosilicate is 1：3.5, it is added to anhydrous The alcoholic solution that ethyl orthosilicate is made is dissolved in ethanol；

（5）By step（4）Obtain silica modified halloysite nanotubes be placed in ethanol water, wherein ethanol and The ratio of water is 1：5, stirring to obtain suspension, then γ-(2- aminoethyls) aminopropyl trimethoxy silicon is added dropwise in suspension Alkane, and the mass ratio of silica modified halloysite nanotubes and γ-(2- aminoethyls) TSL 8330 is 1： 1,20h is stirred at 35 DEG C, drying to constant weight at 45 DEG C by the powder of acquisition after filtering.

E：Light stabilizer Tinuvin 770DF, purchased from BASF

F1：PET polyester fibers

F2：The star-like Polycaprolactone modified PET fiber of terminal hydroxy group, specifically preparation method：

（1）In equipped with magnetic agitation, the 250mL three neck round bottom flask of reflux condensing tube add 5g hexachlorocyclotriph,sphazenes and 20g potassium carbonate and 130ml tetrahydrofurans, lead to nitrogen 30min, 7.5g parahydroxyben-zaldehydes are slowly added dropwise under ice-water bath.It is added dropwise After be warmed to room temperature, react 72h, after reaction filter remove white depositions, obtained after the rotated evaporation of filtrate dense molten Liquid.Concentrated solution is added drop-wise in petroleum ether and is precipitated, obtains white solid, then with re-crystallizing in ethyl acetate, obtains six (4- aldehyde radical benzene oxygen Base) three phosphonitrile of ring；

（2）It is 1 that tetrahydrofuran and methanol volume ratio are added in the round-bottomed flask equipped with magnetic agitation：1 mixed solution, Add 7g steps（1）Six (4- aldehyde radicals phenoxy group) rings, three phosphonitrile obtained, 2.5g sodium borohydrides are slowly added under quick stirring Powder, reacts 20h at room temperature, and most of solvent is removed with Rotary Evaporators, adds deionized water stirring 30min, and centrifugation obtains White powder is obtained, obtains six (4- hydroxy methyl phenyloxies) rings, three phosphonitrile three times with ethyl alcohol recrystallization；

（3）Step is added in polymerization pipe（2）Obtain six (4- hydroxy methyl phenyloxies) rings three phosphonitrile 0.65g and ε-oneself in The stannous iso caprylate of ester 10.35g and gross mass 0.1%, depressurize 3h at room temperature, the tube sealing under vacuum state.Then polymerization pipe is soaked Enter in 120 DEG C of oil bath, isothermal reaction 24h, by the product of acquisition as dichloromethane, excessive oil ether is added dropwise, by acquisition Precipitation obtains the star-like polycaprolactone of terminal hydroxy group as being dried in 40 DEG C of vacuum drying chambers to constant weight；

（4）The PET polyester fibers that F1 is used are cut into pieces and are dried with the star-like polycaprolactone of terminal hydroxy group, according to weight Than 1：0.065 is mixed, and the temperature of mixing is 110 DEG C, adds to screw extruder and carries out extruding pelletization, the temperature in each area of screw rod Degree is arranged to：One 270 DEG C of area, two 290 DEG C of areas, three 280 DEG C of areas.Obtained modified PET drying will be granulated again to constant weight, 280 Spinning is carried out under the conditions of DEG C, spinning speed is 1000 m/min, and fiber is stretched under 105 DEG C of temperature conditionss, obtains terminal hydroxy group star The Polycaprolactone modified PET polyester fibers of type.

F3：Identical with F2 preparation methods, difference lies in PET fiber and the weight ratio 1 of the star-like polycaprolactone of terminal hydroxy group：0.5

G：PP fibers, specific fusing point are 153-165 DEG C

The preparing raw material formula of thermoplastic frame is shown in Table 1.

Table 1

The preparing raw material formula of adhesive-bonded fabric is shown in Table 2.

Table 2

The injection mold that following embodiments and comparative example use is identical, and the wheel cover thickness finally prepared is 10mm, if It is then 6mm bonded fabrics containing a layer thickness comprising bonded fabric.

Embodiment 1：

（1）The preparation of thermoplastic frame pellet：The thermoplastic polyolefin of parts by weight, nothing are weighed according to 1 composition 1 of table Machine filler, glass fibre, halloysite nanotubes and light stabilizer, each dry 7-10h at 75 DEG C, then by above-mentioned raw materials at 90 DEG C It is lower to be uniformly mixed, extruded at 190-230 DEG C using screw extruder, solidified after cooling, obtain thermoplastic frame pellet；

（2）The preparation of adhesive-bonded fabric：The polyester fiber and polypropylene fibre of parts by weight are weighed according to 2 composition 6 of table, is passed through The shredding and mixing of raw fibre are crossed, the thin net of single fiber composition is formed by opener, using four curtain laying sides into the net For formula by its laying networking, it is 1300g/m to reuse acupuncture and surface density is made²Adhesive-bonded fabric, and be in 155 DEG C of temperature, pressure Compression molding 5min under conditions of 8.0MPa, obtains adhesive-bonded fabric；

（3）The pretreatment of adhesive-bonded fabric：By step（2）The adhesive-bonded fabric of acquisition is placed on heating tablet, is protected in nitrogen Under the conditions of carry out contact heating baking, heating-up temperature be 200 DEG C, heating time 55s；

（4）The preparation of wheel cover：By step（3）The adhesive-bonded fabric of acquisition by manipulator delivers into wheel cover mould after cutting It is interior, adhesive-bonded fabric is fixed by way of air tube absorption, Guan Bi mould simultaneously keeps 55 DEG C of mold temperature, 235 DEG C of nozzle temperature, to Injecting step in mould（1）Thermoplastic is obtained, excision charging runner, opening mold after cooling, obtains adhesive-bonded fabric wheel cover.

Embodiment 2：

（1）The preparation of thermoplastic frame pellet：The thermoplastic polyolefin of parts by weight, nothing are weighed according to 1 composition 2 of table Machine filler, glass fibre, halloysite nanotubes and light stabilizer, each dry 7-10h at 80 DEG C, then by above-mentioned raw materials 105 It is uniformly mixed at DEG C, is extruded at 190-230 DEG C using screw extruder, solidified after cooling, obtains thermoplastic frame grain Material；

（2）The preparation of adhesive-bonded fabric：It is same as Example 1；

（3）The pretreatment of adhesive-bonded fabric：It is same as Example 1；

（4）The preparation of wheel cover：By step（3）The adhesive-bonded fabric of acquisition by manipulator delivers into wheel cover mould after cutting It is interior, adhesive-bonded fabric is fixed by way of air tube absorption, Guan Bi mould simultaneously keeps 45 DEG C of mold temperature, 230 DEG C of nozzle temperature, to Injecting step in mould（1）Thermoplastic is obtained, excision charging runner, opening mold after cooling, obtains adhesive-bonded fabric wheel cover.

Embodiment 3：

（1）The preparation of thermoplastic frame pellet：It is same as Example 2.

（2）The preparation of adhesive-bonded fabric：The polyester fiber and polypropylene fibre of parts by weight are weighed according to 2 composition 7 of table, is passed through The shredding and mixing of raw fibre are crossed, the thin net of single fiber composition is formed by opener, using four curtain laying sides into the net For formula by its laying networking, it is 560 g/m to reuse acupuncture and surface density is made²Adhesive-bonded fabric, and be in 150 DEG C of temperature, pressure 6 min of compression molding under conditions of 7.5MPa, obtains adhesive-bonded fabric；

（3）The pretreatment of adhesive-bonded fabric：It is same as Example 1；

（4）The preparation of wheel cover：By step（3）The adhesive-bonded fabric of acquisition by manipulator delivers into wheel cover mould after cutting It is interior, adhesive-bonded fabric is fixed by way of air tube absorption, Guan Bi mould simultaneously keeps 40 DEG C of mold temperature, 240 DEG C of nozzle temperature, to Injecting step in mould（1）Thermoplastic is obtained, excision charging runner, opening mold after cooling, obtains adhesive-bonded fabric wheel cover.

Embodiment 4：

（1）The preparation of thermoplastic frame pellet：The thermoplastic polyolefin of parts by weight, nothing are weighed according to 1 composition 3 of table Machine filler, glass fibre and halloysite nanotubes, each dry 7-10h at 80 DEG C, then above-mentioned raw materials are mixed at 105 DEG C It is even, extruded at 190-230 DEG C using screw extruder, solidified after cooling, obtain thermoplastic frame pellet；

（2）The preparation of adhesive-bonded fabric：The polyester fiber and polypropylene fibre of parts by weight are weighed according to 2 composition 7 of table, is passed through The shredding and mixing of raw fibre are crossed, the thin net of single fiber composition is formed by opener, using four curtain laying sides into the net For formula by its laying networking, it is 550 g/m to reuse acupuncture and surface density is made²Adhesive-bonded fabric, and be in 155 DEG C of temperature, pressure 5 min of compression molding under conditions of 7.5MPa, obtains adhesive-bonded fabric；

（3）The pretreatment of adhesive-bonded fabric：It is same as Example 1；

Comparative example 1：

Same as Example 4, difference lies in step（1）Received in the raw material of thermoplastic frame pellet not comprising galapectite Mitron.

Embodiment 5：

（1）The preparation of thermoplastic frame pellet：The thermoplastic polyolefin of parts by weight, nothing are weighed according to 1 composition 4 of table Machine filler, glass fibre and halloysite nanotubes, each dry 7-10h at 80 DEG C, then above-mentioned raw materials are mixed at 110 DEG C It is even, extruded at 190-230 DEG C using screw extruder, solidified after cooling, obtain thermoplastic frame pellet；

（2）The preparation of adhesive-bonded fabric：It is same as Example 4；

（3）The pretreatment of adhesive-bonded fabric：It is same as Example 1；

（4）The preparation of wheel cover：By step（3）The adhesive-bonded fabric of acquisition by manipulator delivers into wheel cover mould after cutting It is interior, adhesive-bonded fabric is fixed by way of air tube absorption, Guan Bi mould simultaneously keeps 35 DEG C of mold temperature, 220 DEG C of nozzle temperature, The injecting step into mould（1）Thermoplastic is obtained, excision charging runner, opening mold after cooling, obtains adhesive-bonded fabric wheel Cover.

Embodiment 6：

（1）The preparation of thermoplastic frame pellet：The thermoplastic polyolefin of parts by weight, nothing are weighed according to 1 composition 5 of table Machine filler, glass fibre and halloysite nanotubes, each dry 7-10h at 80 DEG C, then above-mentioned raw materials are mixed at 110 DEG C It is even, extruded at 190-230 DEG C using screw extruder, solidified after cooling, obtain thermoplastic frame pellet；

（2）The preparation of adhesive-bonded fabric：It is same as Example 4；

（3）The pretreatment of adhesive-bonded fabric：It is same as Example 1；

（4）The preparation of wheel cover：By step（3）The adhesive-bonded fabric of acquisition by manipulator delivers into wheel cover mould after cutting It is interior, adhesive-bonded fabric is fixed by way of air tube absorption, Guan Bi mould simultaneously keeps 35 DEG C of mold temperature, 220 DEG C of nozzle temperature, to Injecting step in mould（1）Thermoplastic is obtained, excision charging runner, opening mold after cooling, obtains adhesive-bonded fabric wheel cover.

Comparative example 2：

Same as Example 6, difference lies in do not include step（3）The pretreatment of adhesive-bonded fabric, but directly by step（2） The adhesive-bonded fabric of acquisition is sent into mould and is fixed, then carries out follow-up injection molding.

Embodiment 7：

（1）The preparation of thermoplastic frame pellet：It is same as Example 2；

（2）The preparation of adhesive-bonded fabric：The polyester fiber and polypropylene fibre of parts by weight are weighed according to 2 composition 8 of table, is passed through The shredding and mixing of raw fibre are crossed, the thin net of single fiber composition is formed by opener, using four curtain laying sides into the net For formula by its laying networking, it is 550 g/m to reuse acupuncture and surface density is made²Adhesive-bonded fabric, and in 160 DEG C of temperature, pressure 7 5 min of compression molding under conditions of MPa, obtains adhesive-bonded fabric；

（3）The pretreatment of adhesive-bonded fabric：It is same as Example 1；

（4）The preparation of wheel cover：It is same as Example 6, difference lies in Guan Bi mould and mold temperature is kept as 40 DEG C, spray 220 DEG C of mouth temperature.

Embodiment 8：

（1）The preparation of thermoplastic frame pellet：It is same as Example 4；

（2）The preparation of adhesive-bonded fabric：It is same as Example 7；

（3）The pretreatment of adhesive-bonded fabric：It is same as Example 1；

（4）The preparation of wheel cover：It is same as Example 7.

Embodiment 9：

（1）The preparation of thermoplastic frame pellet：It is same as Example 5；

（2）The preparation of adhesive-bonded fabric：It is same as Example 7；

（3）The pretreatment of adhesive-bonded fabric：It is same as Example 1；

（4）The preparation of wheel cover：It is same as Example 7.

Embodiment 10：

（1）The preparation of thermoplastic frame pellet：It is same as Example 6；

（2）The preparation of adhesive-bonded fabric：It is same as Example 7；

（3）The pretreatment of adhesive-bonded fabric：It is same as Example 1；

（4）The preparation of wheel cover：It is same as Example 7.

Comparative example 3：

（2）Adhesive-bonded fabric is blended for commercially available PET/PP in adhesive-bonded fabric（Include the PP fibers of 55wt% and the PET of 45wt% Fiber）, purchased from Shanghai Pu Nate automobile products Co., Ltd；

（3）The preparation of wheel cover：By step（2）Adhesive-bonded fabric cut after delivered into by manipulator in wheel cover mould, Adhesive-bonded fabric is fixed by way of air tube absorption, Guan Bi mould simultaneously keeps 50 DEG C of mold temperature, 220 DEG C of nozzle temperature, Xiang Mo Injecting step in tool（1）Thermoplastic is obtained, excision charging runner, opening mold after cooling, obtains adhesive-bonded fabric wheel cover.

Comparative example 4：

（1）Thermoplastic frame pellet：Purchased from South Korea's Samsung BJ750 polypropylene；

（2）Adhesive-bonded fabric：Adhesive-bonded fabric is blended in PET/PP（Include the PP fibers of 55wt% and the PET fiber of 45wt%）, Purchased from Shanghai Pu Nate automobile products Co., Ltd；

（3）The preparation of wheel cover：By step（2）Adhesive-bonded fabric cut after delivered into by manipulator in wheel cover mould, Adhesive-bonded fabric is fixed by way of air tube absorption, Guan Bi mould simultaneously keeps 55 DEG C of mold temperature, 230 DEG C of nozzle temperature, Xiang Mo Injecting step in tool（1）Thermoplastic is obtained, excision charging runner, opening mold after cooling, obtains adhesive-bonded fabric wheel cover.

Comparative example 5：

（1）Thermoplastic frame pellet：It is same as Example 5.

（2）The preparation of wheel cover：Adhesive-bonded fabric is not placed in mould, direct Guan Bi mould simultaneously keeps mold temperature 40 DEG C, 230 DEG C of nozzle temperature, the injecting step into mould（1）Thermoplastic is obtained, excision charging runner, mould is opened after cooling Tool, the mould is identical with the mould that embodiment 5 uses, and obtains pure plastic wheel-cover.

The wheel cover obtained to above-described embodiment and comparative example carries out following performance test：

（1）Absorbing sound and lowering noise is tested：The noise of wheel cover is tested, specific operating mode is to be carried out on smooth bituminous paving Vehicle at the uniform velocity noise and test, the speed for testing vehicle are 60km/h；Measuring apparatus moves noise-measuring instrument, LMS for LMS Test.Lab8A softwares.Microphone is placed above wheel cover to carry out the collection of test data, sample frequency is 1. 25 Hz, often During secondary test, it is ensured that the position and direction that each microphone is placed are identical.Such as during data acquisition, there are other noises Interference, then the calcellation of this gathered data, re-starts data acquisition.

（2）Weatherability：With reference to the SA methods of JISK6266, senile experiment is carried out to wheel cover.By the outer surface of wheel cover towards Structural carbon arc lamp light source, 63 DEG C of experimental temperature, the continuous irradiation light, and water is sprayed to the outer surface of the flexible water pipe of gasket On, circulate 18 minutes within every 102 minutes.When annealing time is 96 small and when 168 is small.To each wheel cover sample after testing of degenerating 40% is applied to sample with the circulation of 6.7Hz at 20 DEG C and repeats extension strain, is considered as evaluation when the surface of wheel cover is split Terminal, terminate evaluation with 10,000,000 repetition fatigue and cyclics.

The test result of embodiment 1~10 and comparative example 1~5 such as table 3：

Table 3

In addition, the adhesive-bonded fabric wheel cover noise reduction that 1-10 of the embodiment of the present invention is prepared is obvious, and possess certain Weather resistance, finally make the wheel cover of acquisition can not only use in usual cases, and can more meet the bad weathers such as sleet And complex road condition is to the characteristic requirements of wheel cover.

Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention Feature exemplary selectional restriction.And the progress in science and technology will not formed due to the inaccuracy of language performance and not The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case Claim covers.

Claims

1. adhesive-bonded fabric wheel cover, it is characterised in that including at least having

Keep wheel cover global shape and connect the thermoplastic frame of bumper bar and vehicle body, and

Adhesive-bonded fabric in the thermoplastic frame；

The raw material of the thermoplastic frame, calculates by weight, includes 100 parts of thermoplastic polyolefin, inorganic filler 0.01-5 parts of 0.05-15 parts, 0.01-5 parts of glass fibre and halloysite nanotubes；

The raw material of the adhesive-bonded fabric, calculates by weight, includes 20-45 parts of 100 parts of polyester fiber and polypropylene fibre；

The halloysite nanotubes be it is silica modified after halloysite nanotubes；

The polyester fiber is the star-like Polycaprolactone modified PET fiber of terminal hydroxy group, and PET fiber with terminal hydroxy group is star-like gathers oneself The weight ratio of lactone is 1：0.001-0.5.

2. adhesive-bonded fabric wheel cover according to claim 1, it is characterised in that the thermoplastic polyolefin includes 50-80 Wt% Noblens and/or propylene copolymer and 10-30 wt% maleic anhydrides-modified polypropene.

3. adhesive-bonded fabric wheel cover according to claim 2, it is characterised in that the propylene copolymer is that ethylene contents are The propylene-ethylene copolymers of 30-50 wt%, the grafting rate of maleic anhydride acid is in the maleic anhydride-modified polypropene 0.05-5.5%.

4. adhesive-bonded fabric wheel cover according to claim 1, it is characterised in that the particle diameter of the inorganic filler is 2-8 μm, institute State glass fibre a diameter of 12-18 μm.

5. a kind of one-step moulding method for preparing the adhesive-bonded fabric wheel cover in claim 1-4 described in any one, include with Lower step,

（1）The preparation of thermoplastic frame pellet：Weigh the thermoplastic polyolefin of parts by weight, inorganic filler, glass fibre and Halloysite nanotubes, each dry 5-12h at 60-120 DEG C, then above-mentioned raw materials are uniformly mixed, existed using screw extruder Extrude at 190-230 DEG C, solidified after cooling, obtain thermoplastic frame pellet；

（2）The preparation of adhesive-bonded fabric：Weigh the polyester fiber and polypropylene fibre of parts by weight, by raw fibre shredding and Mixing, is formed the thin net of single fiber composition by opener, using four curtain laying modes into the net by its laying networking, then made It is 400-1500g/m that surface density, which is made, with acupuncture²Adhesive-bonded fabric finished product, and in 150-165 DEG C of temperature, pressure 5-10MPa Under conditions of compression molding 3-8min, obtain adhesive-bonded fabric；

（3）The pretreatment of adhesive-bonded fabric：By step（2）The adhesive-bonded fabric of acquisition is placed on heating tablet, in nitrogen protective condition Lower progress contact heating baking, heating-up temperature are 190-210 DEG C, heating time 50-60s；

（4）The preparation of wheel cover：By step（3）The adhesive-bonded fabric of acquisition is delivered into wheel cover mould after cutting by manipulator, Adhesive-bonded fabric is fixed by imperforate mode, Guan Bi mould simultaneously keeps 35-75 DEG C of mold temperature, 190-240 DEG C of nozzle temperature, The injecting step into mould（1）The thermoplastic frame pellet of acquisition, injection finish excision charging runner, mould are opened after cooling Tool, obtains adhesive-bonded fabric wheel cover.

6. one-step moulding method according to claim 5, it is characterised in that step（4）The imperforate mode is Air tube can be evacuated by being set on mould, when adhesive-bonded fabric reaches designated position by extracting the gas in air tube out, be inhaled with vacuum Attached mode stationary positioned adhesive-bonded fabric.

7. the adhesive-bonded fabric wheel cover that the one-step moulding method according to claim 5 or 6 prepares, it is characterised in that institute It is shape bridge arch shape to state adhesive-bonded fabric wheel cover, the frame shell formed with thermoplastic, inside the frame shell at least One layer of adhesive-bonded fabric is provided with, the adhesive-bonded fabric outer surface is directly contacted with the frame shell inner surface, and the nonwoven The thickness of fabric is 2-10mm, surface density 400-1500g/m²。