CN106279747A - A kind of method preparing automotive upholstery and automotive upholstery - Google Patents
A kind of method preparing automotive upholstery and automotive upholstery Download PDFInfo
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- CN106279747A CN106279747A CN201610656532.XA CN201610656532A CN106279747A CN 106279747 A CN106279747 A CN 106279747A CN 201610656532 A CN201610656532 A CN 201610656532A CN 106279747 A CN106279747 A CN 106279747A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C08J2203/08—Supercritical fluid
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- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/16—Fibres; Fibrils
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Abstract
It relates to a kind of method preparing automotive upholstery and automotive upholstery, the preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, and first the two is made nanometer silver bamboo fibre complex, then coupling agent and chemical modifier are combined and are modified nanometer silver bamboo fibre complex and resin matrix processing, and through the automotive upholstery that supercritical micro foaming injection moulding is prepared, there is significant antibiotic and sterilizing effect, and on the premise of keeping mechanical property to be basically unchanged, the weight of automotive upholstery is obviously reduced.
Description
Technical field
It relates to composite and product preparation field, in particular it relates to the preparation method of a kind of automotive upholstery
And automotive upholstery.
Background technology
In recent years, the development of auto industry has brought great convenience, and the appearance of new-energy automobile is further
Alleviating the predicament of Current resource shortage, the most also the requirement to automotive light weight technology grows with each passing day.For reply automotive light weight technology
Demand, fibre reinforced composites are as one of main solution, and in automotive material, proportion constantly increases.The most fine
Dimension strengthens composite and is mainly formed with plastic composition by glass fibre, carbon fiber etc., and the process of garbage is more difficult, produce ring
Border is severe, brings the biggest burden to environment.Along with people's environmental protection consciousness constantly strengthens, processing characteristics is excellent, by with
In the problem that the plastics pollution on the environment of various industrial products has become general concern.Therefore, natural fiber is as increasing
Strong material attracts attention for production environment friendly composite.
The research utilizing Plant fiber and synthetic resin to carry out being combined has longer history, and at present, bio-based materials exists
Application in terms of automobile has begun to, as natural fiber replaces glass fiber reinforcement；Toyota Company of Japan is in the car exhibition of Chicago
Illustrate the I/X plug-in hybrid concept car of flaxen fiber bio-based materials roof；Ford shows in model U
The backboard of soy resins support and seat foam；And use Plant fiber to strengthen PP material manufacture instrumental panel assembly shell and become
Main flow, a kind of abnormal smells from the patient is little, be difficult to aging, low-density and have the Plant fiber of more preferable environmental suitability to strengthen PP material,
Apply on car；The polypropylene automotive parts that 45% wood fiber occurred on German market strengthens, what the wood fiber strengthened subtracts
The products such as shake calendared sheet.The state such as India, Japan uses Corchorus olitorius L., Folium Agaves Sisalanae, flax fiber and hemp as reinforcing material and heat
Thermoplastic polymer is made natural plant fibre polymer composite product and is also had started to engineer applied.Natural fiber increases at home
Strong composite is at the early-stage, and the research in this field is still in the starting stage and really realizes the product of volume production and the most do not go out
Existing.
China's bamboo wood yield ranks first in the world, accounts for more than the 30% of the world, and cheap, and major part is distributed in
The mountain areas such as Hunan, Anhui, Zhejiang.Bamboo fiber has good biodegradable and recyclability simultaneously, utilizes this fibre
The dimension material developed compound with the thermoplastic resin such as low-melting point polyester and polypropylene, its intensity, specific modulus are of a relatively high, suitably
Make the reinforcement of the composite of automobile；Enhancing can be made to be separated with matrix by melt process simultaneously, effectively reach
The purpose recycled, thus embody the feature of environmental protection and the sustainable developability of materials application.Bamboo fiber reinforcement thermoplastic
Composite processing power consumption is few, and process equipment loss is little, is conducive to saving the energy.The maximum feature of bamboo fibre is the height of cross section
Degree natural hollow.Being covered with ellipse space on bamboo fibre cross section, space is quincunx arrangement, and this makes bamboo fibre and goods thereof
Moisture absorption, moisture releasing, wet transmitting performance are splendid, and expert is referred to as " fiber that can breathe ".Bamboo has natural antibacterial, fungi-proofing, protection merit
Can, free from insect pests in its growth course, nothing are rotted.In process of manufacture, these antibiotic substance will not be destroyed, its sky
So human body will not be caused any reaction by antibiotic property, and can also health-care and skin-care, the antibacterial that its effect adds after being much better than.Bamboo
Fiber reinforced thermoplastics composite has broad application prospects in fields such as automobile, electromechanics, interior decorations.
Nano silver particles particle diameter, typically at 25-50 ran, has high-specific surface area, unique physico-chemical property, efficiently
Antibacterial activity, the tens of kinds of pathogenic microorganism such as escherichia coli, gonococcus, chlamydia trachomatis are had strong suppression and kill
Effect.Finding according to the study, nanometer silver can kill 650 various bacteria in several minutes, and the cell wall of nano-Ag particles and pathogen/
After film combines, can be directly entered thalline, rapid and oxygen metabolism enzyme sulfydryl (-SH) combines, and makes enzyme inactivate, blocks respiratory metabolism and make
It is choked to death.Unique sterilization mechanism so that nano-Ag particles just can kill rapidly pathogenic bacterium at low concentration, and will not produce
Raw drug resistance, without any toxic reaction, does not finds any irritant reaction to skin yet.
Vehicle air conditioning outlet is for automotive interior heating, the exhaust apparatus of ventilating and air conditioning system, is car room
Outer air intercommunication, circulation must be through part, in addition to meeting in various mechanical properties and requiring, also need to ensure that air is in circulation
During keep cleaning, not by the pollution of mycete etc., protection rider respiratory health.And current most air-conditioner air outlet
The automotive upholsteries such as housing in the case of air humidity is relatively big, all can generation mycete in various degree, thus contaminated air, give
Health brings hidden danger；Meanwhile, in existing bamboo fiber composite material, bamboo fibre is bad with the compatibility of plastics, has a strong impact on
The performance of composite and product thereof.
Summary of the invention
The purpose of the disclosure is to provide the preparation method of a kind of automotive upholstery, and automotive upholstery prepared by the method is permissible
The automotive upholstery overcoming existing method to prepare easily produces mycete, and fiber affects inside gadget performance with resin compatible difference
Technical problem.
Another object of the present disclosure is to provide a kind of automotive upholstery, and this automotive upholstery can solve existing automobile
Inside gadget easily produces mycete, and fiber affects the technical problem of composite property with resin compatible difference.
To achieve these goals, the disclosure provides a kind of method preparing automotive upholstery, and the method includes walking as follows
Rapid:
(1) use the solution containing nano silver material that bamboo filament is padded process, obtain nanometer silver-bamboo fibre
Composite fibre；
(2) make described nanometer silver-bamboo fibre composite fibre after chopped, contact with coupling agent and carry out surface-coated process,
Obtain the nanometer silver-chopped bamboo fibre composite fibre of surface modification；
(3) acrylonitrile-butadiene-styrene copolymer, chemical modifier is made to be combined with described nanometer silver-chopped bamboo fibre
Fiber carries out melt extruding pelletize, obtains antimicrobial composite material；
(4) make described antimicrobial composite material heating plasticizing obtain melting charge, make described melting charge mix with supercritical fluid
Form homogeneous phase solution, make described homogeneous phase solution inject in the mold cavity of described automotive upholstery, obtain institute through fretting map molding
Stating automotive upholstery, described supercritical fluid is supercritical carbon dioxide and/or supercritical nitrogen.
By technique scheme, the preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, and first will
The two makes nanometer silver-bamboo fibre complex, is then combined coupling agent and chemical modifier to nanometer silver-bamboo fibre complex
It is modified processing with resin matrix, and the automotive upholstery prepared through supercritical micro foaming injection moulding has the most anti-
Bacterium bactericidal effect, and on the premise of keeping mechanical property to be basically unchanged, the weight of automotive upholstery is obviously reduced.
The disclosure also provides for the automotive upholstery that above-mentioned preparation method prepares.
The disclosure also provides for a kind of automotive upholstery, and this automotive upholstery contains acrylonitrile-butadiene-styrene (ABS) copolymerization
Thing, chopped bamboo fibre, nano silver material, coupling agent and chemical modifier, wherein, relative to 100 parts by weight of acrylonitrile-fourth two
Alkene-styrol copolymer, the content of described chopped bamboo fibre is 5-60 weight portion, and the content of described nano silver material is 0.01-2
Weight portion, the content of described coupling agent is 0.1-10 weight portion, and the content of described chemical modifier is 0.1-20 weight portion；Described
Coupling agent is silane coupling agent and/or titante coupling agent；Described chemical modifier is selected from Aluminate, the double fat of ethylene
At least one in acid amide and chromium picolinate.
Containing bamboo fibre and nano silver material in the automotive upholstery of the disclosure, there is significant antibiotic and sterilizing effect；Will
Coupling agent and chemical modifier combination, be modified bamboo fibre surface and resin matrix simultaneously, improve automotive upholstery
Mechanical property；Automotive upholstery distributed the micropore of fretting map molding, can substantially reduce the density of automotive upholstery and whole
Body weight.
Other feature and advantage of the disclosure will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide further understanding of the disclosure, and constitutes the part of description, with following tool
Body embodiment is used for explaining the disclosure together, but is not intended that restriction of this disclosure.In the accompanying drawings:
In Fig. 1 is the automobile that a kind of detailed description of the invention of the preparation method of the automotive upholstery that the present invention provides is used
The structural representation of gadget.
Detailed description of the invention
It is described in detail below in conjunction with accompanying drawing detailed description of the invention of this disclosure.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the disclosure, is not limited to the disclosure.
The disclosure provides a kind of method preparing automotive upholstery, and the method comprises the steps:
(1) use the solution containing nano silver material that bamboo filament is padded process, obtain nanometer silver-bamboo fibre
Composite fibre；
(2) make described nanometer silver-bamboo fibre composite fibre after chopped, contact with coupling agent and carry out surface-coated process,
Obtain the nanometer silver-chopped bamboo fibre composite fibre of surface modification；
(3) acrylonitrile-butadiene-styrene copolymer, chemical modifier is made to be combined with described nanometer silver-chopped bamboo fibre
Fiber carries out melt extruding pelletize, obtains antimicrobial composite material；
(4) make described antimicrobial composite material heating plasticizing obtain melting charge, make described melting charge mix with supercritical fluid
Form homogeneous phase solution, make described homogeneous phase solution inject in the mold cavity of described automotive upholstery, obtain institute through fretting map molding
Stating automotive upholstery, described supercritical fluid is supercritical carbon dioxide and/or supercritical nitrogen.
The preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, and the two first makes nanometer silver-bamboo
Fibre composites, is then combined coupling agent and chemical modifier and changes nanometer silver-bamboo fibre complex and resin matrix
Property process, and the automotive upholstery prepared through supercritical micro foaming injection moulding has a significant antibiotic and sterilizing effect, and
On the premise of keeping mechanical property to be basically unchanged, the weight of automotive upholstery is obviously reduced.
Wherein, described in pad the method for process and be well known to those skilled in the art, be referred to sizing fabric operation
Method for sizing, utilizes the cooperation of compregnate roller and sizing roller to carry out.Specifically processing method can be two leachings two roll, double leaching three press or
Double leaching four pressures etc., method is rolled in preferably two leachings two.
According in the preparation method of the disclosure, the consumption of each raw material components can in very large range change, Ke Yiwei
The consumption that field of compound material technical staff is commonly used, such as, relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer
Thing, the consumption of chopped bamboo fibre can be 5-60 weight portion, and the consumption of nano silver material can be 0.01-2 weight portion, coupling agent
Consumption can be 0.1-10 weight portion, the consumption of chemical modifier can be 0.1-20 weight portion；Coupling agent can be silane
Class coupling agent and/or titante coupling agent；Described chemical modifier is selected from Aluminate, ethylene bis-fatty acid amides and pyridine
At least one in chromic formate.
In order to improve antibacterial effect and the mechanical property of the automotive upholstery prepared by said method, preferable case further
Under, relative to 100 parts by weight of acrylonitrile-BS, the consumption of chopped bamboo fibre can be 15-35 weight
Part, the consumption of nano silver material can be 0.05-0.5 weight portion, and the consumption of coupling agent can be 0.5-5 weight portion, and chemistry changes
The consumption of property agent can be 0.5-10 weight portion.
According to the disclosure, described acrylonitrile-butadiene-styrene copolymer (ABS resin) is those skilled in the art institutes
Knowing, the relative amount of acrylonitrile unit therein unit, butadiene structural units and styrol structural unit is not important to
Ask, can be the conventional selection of field of compound material, such as, in acrylonitrile-butadiene-styrene copolymer, acrylonitrile structure
The weight ratio of unit, butadiene structural units and styrol structural unit can be 1:(0.15-2): (1-4).Aforesaid propylene nitrile-
BS can be commercial products, can be such as purchased from NEC chemistry ABS resin GR-4000,
ABS Magnum800 purchased from Si Tailong company of the U.S., the ABS resin Terluran KR2883 purchased from BASF Aktiengesellschaft,
KR2885,828P or 846L etc..
According in the preparation method of the disclosure, coupling agent may be used for chopped bamboo fibre is carried out surface modification, described
Chemical modifier may be used for being modified resin matrix, and the two is with the use of being used for improving acrylonitrile-butadiene-styrene (ABS)
Copolymer and the interface compatibility of chopped bamboo fibre, thus improve the interface bond strength of the two.Each group of above-mentioned preparation method
In demultiplexing weight range, in order to improve acrylonitrile-butadiene-styrene copolymer and the interface cohesion of chopped bamboo fibre further
The amount ratio of power, coupling agent and chemical modifier can be preferably 1:(0.5-2.5).
According to the disclosure, coupling agent can be silane coupling agent or titante coupling agent, specifically, silanes coupling
Agent can be selected from γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, VTES, ethylene
Base trimethoxy silane, double-(the silica-based propyl group of γ-triethoxy) tetrasulfide, γ-methacryloxypropyl trimethoxy
One or more in silane, triphenyl silicol, wherein, in order to make fiberglass surfacing that silane coupler processed with
Active force between cyclic olefin polymer interface is higher, under preferable case, selects the coupling agent containing olefin group, such as ethylene
Ethyl triethoxy silicane alkane, vinyltrimethoxy silane or γ-methacryloxypropyl trimethoxy silane；Titanate ester
Coupling agent can be selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy)
Titanate esters, isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters
The chelate of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine and double (two octyloxy pyrophosphoric acid ester groups) second
At least one in support titanate esters.
According to the disclosure, nano silver material can be any form containing nano silver particles, and such as, nano silver material can
Think and comprise only nano silver particles, it is also possible on the carrier particles, kind and the content present invention of carrier granular are not spy in dispersion
Other requirement, if meet nano silver particles be evenly distributed in nano silver material and content suitably.In order to improve nanometer
Silver particles and the compatibility of resin matrix, under preferable case, can select the knot with acrylonitrile-butadiene-styrene copolymer
The polymer that structure unit is identical or structure is close is as the carrier granular of nano silver particles, and such as, nano silver material can contain
Nano silver particles and polystyrene.
In nano silver material, polystyrene can in very large range change, preferably with the relative usage of nano silver particles
In the case of, the amount ratio of described nano silver particles and polystyrene can be 1:(1-20), in above-mentioned content range, by these public affairs
Nano silver particles content in the automotive upholstery that the preparation method opened prepares is suitable, and nano silver particles and acrylonitrile-
The compatibility of BS resin matrix is good, is conducive to improving the antibacterial effect of composite.
In nano silver material, the carrier granular such as nano silver particles and polystyrene may be constructed nano-particle, this nanometer
The size of grain can in very large range change, wherein, in order to improve antibacterial effect and the compatibility of nano silver particles, preferably
Ground, in nano silver material, the particle diameter of nano-particle can be 5-100nm.
According to the disclosure, the length of chopped bamboo fibre can also in very large range change, as long as meeting chopped bamboo fibre
Play potentiation, and can be uniformly dispersed in described composite.Under preferable case, the length of chopped bamboo fibre can
Think 2-5mm.In above-mentioned preferred length range, chopped bamboo fibre and acrylonitrile-butadiene-styrene copolymer resin base
The compatibility of body is good, and obvious to the potentiation of composite.
In order to improve the chemical modifier modified effect to acrylonitrile-butadiene-styrene copolymer further, improve altogether
Copolymer resin matrix and the compatibility of chopped bamboo fibre, under preferable case, the method includes: make acrylonitrile-butadiene-styrene (ABS)
Carry out melt extruding making with described nanometer silver-chopped bamboo fibre composite fibre again after copolymer and chemical modifier mix homogeneously
Grain, obtains described antimicrobial composite material.
It is highly preferred that for the combination property improving the automotive upholstery prepared by disclosed method further, automobile
The preparation method of inside gadget may include that make in heat stabilizer, processing aid, ultraviolet absorber and antioxidant at least one with
It is combined with described nanometer silver-chopped bamboo fibre again after described acrylonitrile-butadiene-styrene copolymer and chemical modifier mixing
Fiber carries out melt extruding pelletize, obtains described antimicrobial composite material；
Wherein, the concrete kind of antioxidant, heat stabilizer, ultraviolet absorber and processing aid can be people in the art
Conventional kind known to Yuan, such as, antioxidant can be selected from β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive 18
At least one in the double octadecyl of carbon alcohol ester, 2-(1,1-dimethyl ethyl)-6-methyl-phenol, thio-2 acid；Thermally-stabilised
Agent can be at least one in maleic acid tin octylate or carboxylic acid stannum, Methyl stannum mercaptide and sulfydryl ester group stannum；Uv absorption
Agent can be selected from 2,4 dihydroxyl benzophenone, ESCALOL 567,2-hydroxyl-4-n-octyloxy hexichol
Ketone, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis
(4-t-octyl phenol epoxide) nickel, (1,2,2,6,6-pempidine base) phosphite ester, 4-benzoyloxy-2,2,6,6-tetramethyl
At least one in piperidines；Processing aid can be selected from calcium stearate, modified ethylene bis stearamide, Tissuemat E, ethylene
At least one in double stearic amides.
In the another embodiment of the disclosure, in order to improve the compatibility of bamboo fibre and copolymer resin matrix, vapour
The preparation method of car inside gadget may include that and makes described nanometer silver-bamboo fibre composite fibre after chopped and the painting of coupling agent surface
After covering process, with compatilizer and/or dispersant, obtain the nanometer silver-bamboo fibre composite fibre of surface modification；Wherein, phase
Holding agent can be to connect selected from Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride and ABS
At least one in branch maleic anhydride；Dispersant can be selected from two polyphosphate sodiums, triethyl group hexyl sodium phosphate, dodecyl sulfur
At least one in acid sodium or fatty acid and macrogol ester.
As preferably a kind of embodiment of the disclosure, the preparation method of automotive upholstery includes: make described nanometer silver-bamboo
Fiber composite fiber, after chopped and after the process of coupling agent surface-coated, with compatilizer and/or dispersant, must arrive surface and change
Nanometer silver-bamboo fibre the composite fibre of property；
Further, heat stabilizer, processing aid, ultraviolet absorber and antioxidant and described acrylonitrile-butadiene-styrene (ABS) are made
Carry out melt extruding pelletize with described nanometer silver-chopped bamboo fibre composite fibre again after copolymer and chemical modifier mixing,
To described antimicrobial composite material；
The concrete kind of above-mentioned compatilizer, antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid is permissible
As hereinbefore；The amount ranges of compatilizer, antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid can be
Change in very wide range, it is preferable that relative to 100 parts by weight of acrylonitrile-BS, the consumption of compatilizer
Can be 0.5-5 weight portion, the consumption of antioxidant can be 0.2-2 weight portion, and the consumption of heat stabilizer can be 0.2-2 weight
Part, the consumption of dispersant can be 0.1-2 weight portion, and the consumption of ultraviolet absorber can be 0.2-2 weight portion, processing aid
Consumption can be 0.2-4 weight portion.In this one preferred embodiment, the method the antioxidation of the automotive upholstery prepared
The combination properties such as property, weatherability and heat stability are all obviously improved.
According to the disclosure, in above-mentioned preparation process, the method melt extruding pelletize is well known to those skilled in the art, institute
Stating and melt extrude pelletize and can carry out on such as screw extruder at extrusion equipment, described screw extruder can be single screw rod
Extruder or double screw extruder, the present invention does not do special requirement.
Wherein, the reaction condition melt extruding pelletize can also be well known to those skilled in the art, can be according to matrix
Kind and the character of resin adjust accordingly.Under preferable case, in order to improve the melting mixing effect of each raw material components, melt extrude
The temperature of pelletize can be 210-250 DEG C.
According to the disclosure, nano silver material can be disperseed to obtain by the material containing nano silver particles, it is also possible to by chemistry
Reaction obtains.In preferably a kind of embodiment of the disclosure, nano silver material can contain polystyrene and nanometer silver granuel
Son, can be carried out redox reaction by kayexalate and silver nitrate solution and obtain described molten containing nano silver material
Liquid, shown in its chemical equation such as following formula (1), reaction condition can in very large range change, and such as, reaction temperature can be
20-100 DEG C, the response time can be 5-60min, it is preferable that reaction temperature can be 50-90 DEG C, and the response time can be 10-
40min.The above-mentioned solution containing nano silver material can be aqueous solution or the solution of other suitable solvent formation.Excellent at this
Choosing embodiment in, the nano silver particles that redox reaction obtains can with uniform adsorption on granules of polystyrene, thus
Improve the dispersing uniformity of nano silver particles, simultaneously by nanometer silver granuel can be improved further with granules of polystyrene absorption
Son and copolymer resin matrix and the compatibility of bamboo fibre.
According to the disclosure, in order to improve the compatibility of chopped bamboo fibre and resin matrix, said method also includes using occasionally
After connection agent carries out surface-coated process to described nanometer silver-bamboo fibre composite fibre, make receiving of the surface modification described in step (2)
Meter Yin-bamboo fibre composite fibre and compatilizer and dispersant are also reacted, and the nanometer silver-bamboo fibre obtaining surface modification is combined
Fiber.
Coupling agent is used nanometer silver-bamboo fibre composite fibre to carry out the method for surface-coated process also for art technology
Known to personnel, for example, it is possible to be scattered in by nanometer silver-bamboo fibre composite fibre containing 0.2-10% (wt) coupling agent is anhydrous
In ethanol, addition HCl regulation pH value is to 4-5, and at 50 DEG C, ultrasonic disperse reacts 1-2 hour.After reaction terminates, taking-up nanometer silver-
Bamboo fibre composite fibre, cleans to neutral with distilled water, dries 2-5 hour, obtain the nanometer of surface modification at 100-120 DEG C
Silver-bamboo fibre composite fibre.
According to the disclosure, the implication of supercritical fluid is well known to those skilled in the art, and refers to that temperature, pressure are higher than it
The fluid of critical state.Generally exceed critical temperature regardless of whether whether its pressure and density exceed marginal value state being in temperature
Fluid all return for supercritical fluid.Supercritical fluid has many unique character, as little in viscosity, density, diffusion coefficient,
The character such as solvability are the most sensitive with temperature and pressure change: viscosity and diffusion coefficient are close to gas, and density and solvent
Change ability is close to liquid.
In disclosed method, the temperature and pressure of supercritical fluid can in very large range change, it is preferable that super
The temperature of critical fluids is 80-130 DEG C, and pressure is 60-130MPa.Supercritical fluid in said temperature and pressure limit is favourable
In forming homogeneous phase solution with melted material, it is simple to carry out follow-up fretting map forming process.
The melted material that supercritical fluid and heating plasticizing obtain is mixed to form homogeneous phase solution, and this homogeneous phase solution can keep
At a higher pressure, then inject, by switching regulator nozzle, the mold cavity that temperature and pressure is relatively low, due to temperature and pressure
Reducing the unstability of trigger molecule thus form substantial amounts of nuclei of bubbles in goods, finally these nuclei of bubbles are gradually grown up generation
Small hole.The pressure of heating plasticizing and the pressure of mold cavity and temperature can be supercritical fluid fretting map moulding process
Normal operating temperatures and pressure, carry out the Forming Quality of fretting map molding, preferably feelings to improve supercritical fluid further
Under condition, the pressure of heating plasticizing can be 50-100MPa with the difference of the pressure of mold cavity, and the temperature of mould can be 50-
80℃。
The consumption of supercritical fluid can in very large range change, in order to obtain in density and the suitable automobile of gas release
Gadget, it is preferable that relative to 100 parts by weight of acrylonitrile-BS, the consumption of supercritical fluid can be
0.5-10 weight portion.In above-mentioned preferred amount ranges, automotive upholstery prepared by the preparation method of the disclosure can be by force
In the case of degree is held essentially constant, reduce density and the overall weight of inside gadget further.
The disclosure also provides for the automotive upholstery that above-mentioned preparation method prepares.
The disclosure also provides for a kind of automotive upholstery, and this automotive upholstery contains acrylonitrile-butadiene-styrene (ABS) copolymerization
Thing, chopped bamboo fibre, nano silver material, coupling agent and chemical modifier, wherein, relative to 100 parts by weight of acrylonitrile-fourth two
Alkene-styrol copolymer, the content of described chopped bamboo fibre is 5-60 weight portion, and the content of described nano silver material is 0.01-2
Weight portion, the content of described coupling agent is 0.1-10 weight portion, and the content of described chemical modifier is 0.1-20 weight portion；Described
Coupling agent is silane coupling agent and/or titante coupling agent；Described chemical modifier is selected from Aluminate, the double fat of ethylene
At least one in acid amide and chromium picolinate.
Containing bamboo fibre and nano silver material in the automotive upholstery of the disclosure, there is significant antibiotic and sterilizing effect；Will
Coupling agent and chemical modifier combination, be modified bamboo fibre surface and resin matrix simultaneously, improve automotive upholstery
Mechanical property；Automotive upholstery distributed the micropore of fretting map molding, can substantially reduce the density of automotive upholstery and whole
Body weight.
According to the disclosure, in order to improve antibacterial effect and the mechanical property of automotive upholstery, under preferable case, phase further
For 100 parts by weight of acrylonitrile-BS, the content of chopped bamboo fibre can be 15-35 weight portion, receives
The content of rice ag material can be 0.05-0.5 weight portion, and the content of coupling agent can be 0.5-5 weight portion, chemical modifier
Content can be 0.5-10 weight portion.
Described acrylonitrile-butadiene-styrene copolymer (ABS resin) is well known to those skilled in the art, therein
The relative amount of acrylonitrile unit unit, butadiene structural units and styrol structural unit does not specially require, and can be multiple
The conventional selection in condensation material field, such as, in acrylonitrile-butadiene-styrene copolymer, acrylonitrile unit unit, butadiene
The weight ratio of construction unit and styrol structural unit can be 1:(0.15-2): (1-4).Aforesaid propylene nitrile-butadiene-benzene second
Alkene copolymer can be commercial products, can be such as purchased from NEC chemistry ABS resin GR-4000, purchased from the U.S. this
The ABS Magnum800 of company of ACE Semi, the ABS resin Terluran KR2883 purchased from BASF Aktiengesellschaft, KR2885,
828P or 846L etc..
According in the automotive upholstery of the disclosure, coupling agent may be used for carrying out chopped bamboo fibre surface modification, institute
Stating chemical modifier to may be used for being modified resin matrix, the two is with the use of being used for improving acrylonitrile-butadiene-benzene second
Alkene copolymer and the interface compatibility of chopped bamboo fibre, thus improve the interface bond strength of the two.In above-mentioned content range,
In order to improve acrylonitrile-butadiene-styrene copolymer and the interface binding power of chopped bamboo fibre, coupling agent and chemistry further
The amount ratio of modifying agent can be preferably 1:(0.5-2.5).
Coupling agent can be silane coupling agent or titante coupling agent, and specifically, silane coupling agent can be selected from
γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, VTES, vinyl trimethoxy
Silane, double-(the silica-based propyl group of γ-triethoxy) tetrasulfide, γ-methacryloxypropyl trimethoxy silane, triphen
One or more in base silicol, wherein, in order to the fiberglass surfacing making silane coupler process gathers with cycloolefin
Active force between compound interface is higher, under preferable case, selects the coupling agent containing olefin group, such as vinyl three ethoxy
Base silane, vinyltrimethoxy silane or γ-methacryloxypropyl trimethoxy silane；Titante coupling agent can
Think selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester,
Isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters are double, and (two is pungent
Epoxide pyrophosphoric acid ester group) ethylene titanate esters and the chelate of triethanolamine and Di(dioctylpyrophosphato) ethylene titanate
In at least one.
Aluminate can be selected from aluminic acid three isopropyl ester, aluminic acid three benzyl ester；Ethylene bis-fatty acid amides can be that ethylene is double
At least one in the double oleamide of stearic amide, ethylene, the double palmitamide of ethylene and ethylene dilaurate amide.
According to the disclosure, nano silver material can be any form containing nano silver particles, and such as, nano silver material can
Think and comprise only nano silver particles, it is also possible on the carrier particles, kind and the content present invention of carrier granular are not spy in dispersion
Other requirement, if meet nano silver particles be evenly distributed in nano silver material and content suitably.In order to improve nanometer
Silver particles and the compatibility of resin matrix, under preferable case, can select the knot with acrylonitrile-butadiene-styrene copolymer
The polymer that structure unit is identical or structure is close is as the carrier granular of nano silver particles, and such as, nano silver material can contain
Nano silver particles and polystyrene.
In nano silver material, polystyrene can in very large range change, preferably with the relative amount of nano silver particles
In the case of, the weight ratio of described nano silver particles and polystyrene can be 1:(1-20), in above-mentioned content range, in automobile
Nano silver particles content in gadget is suitable, and nano silver particles and acrylonitrile-butadiene-styrene copolymer resin matrix
The compatibility is good, is conducive to improving the antibacterial effect of composite.
In nano silver material, the carrier granular such as nano silver particles and polystyrene may be constructed nano-particle, this nanometer
The size of grain can in very large range change, wherein, in order to improve antibacterial effect and the compatibility of nano silver particles, preferably
Ground, in nano silver material, the particle diameter of nano-particle can be 10-80nm.
According to the disclosure, the length of nanometer silver-chopped bamboo fibre composite fibre can also in very large range change, as long as
Meet chopped bamboo fibre and play potentiation, and can be uniformly dispersed in described composite.Under preferable case, nanometer
The length of silver-chopped bamboo fibre composite fibre can be 2-5mm.In above-mentioned preferred length range, nanometer silver-chopped bamboo is fine
Dimension composite fibre is good with the compatibility of acrylonitrile-butadiene-styrene copolymer resin matrix, and the enhancing to composite is made
With substantially.
According to the disclosure, in order to improve the combination property of automotive upholstery further, under preferable case, above-mentioned automotive trim
Part can also contain at least one in compatilizer, antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid.
The concrete kind of above-mentioned compatilizer, antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid is permissible
The conventional kind being well known to those skilled in the art, such as, compatilizer can be selected from Research of Grafting Malaic Anhydride Onto Polyethylene, benzene second
At least one in alkene grafted maleic anhydride, polypropylene grafted maleic anhydride and ABS grafted maleic anhydride；Antioxidant can be choosing
From β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, 2-(1,1-dimethyl ethyl)-6-methyl-phenol,
At least one in the double octadecyl of thio-2 acid；Heat stabilizer can be selected from maleic acid tin octylate or carboxylic acid stannum, methyl
At least one in tin mercaptides and sulfydryl ester group stannum；Dispersant can be selected from two polyphosphate sodiums, triethyl group hexyl sodium phosphate, ten
At least one in sodium dialkyl sulfate or fatty acid and macrogol ester；Ultraviolet absorber can be selected from 2,4-dihydroxy two
Benzophenone, ESCALOL 567, Octabenzone, 2-(2 '-hydroxyl-3 ', 5 '-two
Tertiary phenyl)-5-chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4-t-octyl phenol epoxide) nickel, (1,2,
2,6,6-pempidine base) phosphite ester, at least one in 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Processing helps
Agent can be at least in calcium stearate, modified ethylene bis stearamide, Tissuemat E, ethylene bis stearic acid amide
Kind.
As preferably a kind of detailed description of the invention of the disclosure, described automotive upholstery also includes compatilizer, antioxidant, heat
Stabilizer, dispersant, ultraviolet absorber and processing aid；Preferably, the content of above-mentioned auxiliary agent can be: relative to 100 weight
Part acrylonitrile-butadiene-styrene copolymer, the content of compatilizer can be 0.5-5 weight portion, and the content of antioxidant can be
0.2-2 weight portion, the content of heat stabilizer can be 0.2-2 weight portion, and the content of dispersant can be 0.1-2 weight portion, purple
The content of outer absorbent can be 0.2-2 weight portion, and the content of processing aid can be 0.2-4 weight portion.Above-mentioned preferably help
Agent and content range can improve the combination properties such as the non-oxidizability of described automotive upholstery, weatherability and heat stability.
Above-mentioned automotive upholstery can include air-conditioner air outlet housing, compartment dividing plate, door panel, panel assembly and
At least one in handrail.Wherein, in order to play the antibacterial and mouldproof effect of described automotive upholstery, it is preferable that automotive upholstery
It can be air-conditioner air outlet housing.
Further illustrate the disclosure by the following examples, but the disclosure is the most any way limited.At this
In disclosed following embodiment, the structure of automotive upholstery is as it is shown in figure 1, acrylonitrile-butadiene-styrene copolymer is for being purchased from
The ABS resin Terluran KR2883 of BASF Aktiengesellschaft, bamboo fibre is purchased from Ningbo Qi Zhu company；Other chemical reagent
It is general commercial products；Melt extrude and prepare in the connection company's T L-55-55-500 type double screw extruder of upper tableland.
Embodiment 1
The present embodiment is for illustrating the composition of the automotive upholstery of the disclosure.
The automotive upholstery of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 15 weight
Part chopped bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.01 weight portion nano silver material, nano-particle
Particle diameter be 20nm), 0.1 weight portion Silane coupling agent KH550,15 weight portion chemical modifier Aluminates.
Embodiment 2
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 60 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:20 to 2 weight portion nano silver materials, the particle diameter of nano-particle
For 100nm), 10 weight portion coupling agent isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, 0.1 weight portion chemical modifier
Ethylene bis-fatty acid amides.
Embodiment 3
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 5 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:1 to 0.02 weight portion nano silver material, the grain of nano-particle
Footpath is 30nm), 0.1 weight portion Silane coupling agent KH550,0.2 weight portion chemical modifier chromium picolinate.
Embodiment 4
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 15 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.05 weight portion nano silver material, the grain of nano-particle
Footpath is 20nm), 0.5 weight portion Silane coupling agent KH550,10 weight portion chemical modifier Aluminates.
Embodiment 5
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 35 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.4 weight portion nano silver material, the particle diameter of nano-particle
For 20nm), 5 weight portion Silane coupling agent KH550s, 0.5 weight portion chemical modifier Aluminate.
Embodiment 6
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 15 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.01 weight portion nano silver material, the grain of nano-particle
Footpath is 20nm), 0.1 weight portion Silane coupling agent KH550,0.1 weight portion chemical modifier Aluminate.
Embodiment 7
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 30 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.2 weight portion nano silver material, the particle diameter of nano-particle
For 20nm), 1 weight portion Silane coupling agent KH550,1 weight portion chemical modifier Aluminate, 1 parts by weight of compatible agent styrene connects
Branch maleic anhydride, 0.5 weight portion antioxidant β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, 0.5 weight
Part heat stabilizer maleic acid tin octylate, 0.5 parts per weight dispersing agent macrogol ester, 0.5 weight portion ultraviolet absorber 2,4-dihydroxy
Base benzophenone and 0.5 weight portion processing aid calcium stearate.
Comparative example 1
This comparative example is different from the disclosure for automotive upholstery for explanation.
Containing the composition with embodiment 1 in this automotive upholstery, except that, by weight such as nano silver material replace with
Acrylonitrile-butadiene-styrene copolymer.
Comparative example 2
This automotive upholstery contains and the composition of embodiment 1, except that, by weight such as chopped bamboo fibre replace with
Acrylonitrile-butadiene-styrene copolymer.
Comparative example 3
In this automotive upholstery containing with the composition of embodiment 1, except that, coupling agent KH550 is replaced with and waits heavily
The chemical modifier Aluminate of amount.
Comparative example 4
Containing the composition with embodiment 1 in this automotive upholstery, except that, chemical modifier Aluminate is replaced with
Coupling agent KH550 etc. weight.
Preparation embodiment 1
The present embodiment is for illustrating the preparation method of the automotive upholstery of the disclosure, each in the automotive upholstery of the present embodiment
The consumption of raw material is same as in Example 1, comprises the steps:
(1) kayexalate joining mixing and stirring in silver nitrate solution, in microwave oven, 500w heats
30min, centrifugation, obtain the aqueous solution containing nano silver material after dried, bamboo fibre is immersed in concentration 1g/L
Containing the aqueous solution of nano silver material, two leachings two are rolled, and heated by microwave fast dewatering, are dried, and obtain nanometer silver-bamboo fibre and are combined
Fiber；
(2) the drying nano silver-bamboo fibre composite fibre (1) obtained is carried out with Silane coupling agent KH550 after chopped
Nanometer silver-chopped bamboo fibre the composite fibre (a length of 2-5mm) of surface modification is obtained after surface-coated；
(3) put into ABS resin and chemical modifier in heated at high speed mixer (2000 turns/min of speed of agitator)
Add in double screw extruder (temperature 230 DEG C) after row mixing dispersion, then by compound for the nanometer silver in (2)-chopped bamboo fibre fibre
Tie up and add from the side spout of extruder, carry out melt pelletization, antibacterial by obtaining after outlet mold sizing, water-cooled, air-dried, pelletizing
Composite；
(4) making above-mentioned antimicrobial composite material heating plasticizing obtain melting charge, supercritical carbon dioxide heating plasticizing obtains
Melting charge is mixed to form homogeneous phase solution, makes described homogeneous phase solution inject in the mold cavity of described automotive upholstery, through fretting map
Molding obtains the automotive upholstery of the present embodiment.Relative to 100 weight portions, the consumption of supercritical fluid is 2 weight portions；Add thermoplastic
The pressure changed and the difference of the pressure of mold cavity can be with 80MPa, and the temperature of mould is 60 DEG C.
Preparation embodiment 2
Use preparation embodiment 1 method, except that, in the automotive upholstery of the present embodiment the consumption of each raw material with
Embodiment 2 is identical.
Preparation embodiment 3
Use preparation embodiment 1 method, except that, in the automotive upholstery of the present embodiment the consumption of each raw material with
Embodiment 3 is identical.
Preparation embodiment 4
Use preparation embodiment 1 method, except that, in the automotive upholstery of the present embodiment the consumption of each raw material with
Embodiment 4 is identical.
Preparation embodiment 5
Use preparation embodiment 1 method, except that, in the automotive upholstery of the present embodiment the consumption of each raw material with
Embodiment 5 is identical.
Preparation embodiment 6
Use preparation embodiment 1 method, except that, in the automotive upholstery of the present embodiment the consumption of each raw material with
Embodiment 6 is identical.
Preparation embodiment 7
In the automotive upholstery of the present embodiment, the consumption of each raw material is same as in Example 7, and preparation method comprises the steps:
(1) kayexalate joining mixing and stirring in silver nitrate solution, in microwave oven, 500w heats
30min, centrifugation, obtain the aqueous solution containing nano silver material after dried, bamboo fibre is immersed in concentration 1g/L
Containing the aqueous solution of nano silver material, two leachings two are rolled, and heated by microwave fast dewatering, are dried, and obtain nanometer silver-bamboo fibre and are combined
Fiber；
(2) the drying nano silver-bamboo fibre composite fibre (1) obtained is carried out with Silane coupling agent KH550 after chopped
React through heated at high speed mixer (2000 turns/min of speed of agitator), in compatilizer with compatilizer, dispersant after surface-coated
There is esterification in the hydroxyl (-OH) in maleic anhydride and bamboo fibre, the carboxyl (-COOH) that course of reaction generates again with natural fibre
There is follow-up esterification in the hydroxyl (-OH) in dimension, the nanometer silver-chopped bamboo fibre composite fibre obtaining surface modification is (long
Degree is 2-5mm)；
(3) ABS resin, chemical modifier, heat stabilizer, processing aid, ultraviolet absorber and antioxidant are put into height
Speed adds to carry out in Hot mixer mixing disperses (2000 turns/min of speed of agitator) to add (temperature 230 in double screw extruder afterwards
DEG C), then the nanometer silver in (2)-chopped bamboo fibre composite fibre is added from the side spout of extruder, carry out melt pelletization,
Again by obtaining antimicrobial composite material after outlet mold sizing, water-cooled, air-dried, pelletizing；
(4) making above-mentioned antimicrobial composite material heating plasticizing obtain melting charge, supercritical carbon dioxide heating plasticizing obtains
Melting charge is mixed to form homogeneous phase solution, makes described homogeneous phase solution inject in the mold cavity of described automotive upholstery, through fretting map
Molding obtains the automotive upholstery of the present embodiment.Relative to 100 weight portions, the consumption of supercritical fluid is 2 weight portions；Supercritical
The addition of carbon dioxide is that the difference of the pressure of pressure and the mold cavity of heating plasticizing can be with 80MPa, and the temperature of mould is
60℃。
Preparation comparative example 1-4
Use preparation embodiment 1 method, except that, in automotive upholstery the consumption of each raw material respectively with comparative example
1-4 is identical.
Preparation comparative example 5
In the automotive upholstery of this comparative example, consumption and the preparation method of each raw material are same as in Example 1, except that,
Make the antimicrobial composite material obtained in step (3) carry out injection mo(u)lding and obtain the automotive upholstery of this comparative example.
Testing example 1
The automotive upholstery that obtains in preparation embodiment 1-7 and preparation comparative example 1-5 is carried out respectively following performance test:
Relative density test is with reference to GB4472-2011；Hot strength is tested according to ASTM D638 standard, stretching speed
Spending 50mm/min, bending strength and bending modulus are tested according to ASTM D790 standard, and span 56mm, rate of bending is
2mm/min, test result is listed in table 1
According to light industry of China industry standard QB/T 2591-2003, " antibiotic plastic anti-microbial property is commented in the test of antibiotic rate
Valency and method of testing thereof " it is tested by standard.The strain that experiment uses: staphylococcus aureus, escherichia coli, black fermented preparation
Mould, aspergillus terreus, test result is listed in table 2.
Table 1
| Hot strength (MPa) | Bending strength (MPa) | Relative density (g/m3) | |
| Preparation embodiment 1 | 42.6 | 65.8 | 0.98 |
| Preparation embodiment 2 | 33.9 | 56.5 | 1.00 |
| Preparation embodiment 3 | 40.9 | 62.9 | 0.97 |
| Preparation embodiment 4 | 43.8 | 66.4 | 0.95 |
| Preparation embodiment 5 | 48.4 | 69.5 | 0.94 |
| Preparation embodiment 6 | 50.4 | 71.7 | 0.95 |
| Preparation embodiment 7 | 49.6 | 72.9 | 0.93 |
| Preparation comparative example 1 | 41.9 | 64.7 | 0.99 |
| Preparation comparative example 2 | 37.7 | 55.1 | 0.98 |
| Preparation comparative example 3 | 40.1 | 62.9 | 1.00 |
| Preparation comparative example 4 | 39.6 | 62.1 | 0.99 |
| Preparation comparative example 5 | 31.4 | 48.3 | 1.03 |
Table 2
According to Tables 1 and 2 data, from preparation embodiment 1 with the Data Comparison preparing comparative example 1-2 it can be seen that relative
In comprising only the automotive upholstery of nano silver material or bamboo fibre, the automotive upholstery of the disclosure contain simultaneously nano silver material and
Bamboo fibre, has more significant antibiotic and sterilizing effect；Data Comparison from preparation embodiment 1 with preparation comparative example 3-4 can
Going out, relative to comprising only the automotive upholstery of chemical modifier or coupling agent, the automotive upholstery of the disclosure and preparation method will
Coupling agent and chemical modifier combination, be modified bamboo fibre surface and resin matrix simultaneously, improve automotive upholstery
Mechanical property；Preparation embodiment 1 with prepare the Data Comparison of comparative example 5 it can be seen that relative to not using fretting map to be molded into
The automotive upholstery production method of type, the automotive upholstery using the preparation method of the disclosure to obtain is keeping mechanical property basic
While constant, hence it is evident that reduce density and overall weight.
The preferred implementation of the disclosure is described in detail above in association with accompanying drawing, but, the disclosure is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the disclosure, multiple letter can be carried out with technical scheme of this disclosure
Monotropic type, these simple variant belong to the protection domain of the disclosure.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the disclosure to various can
The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the disclosure, as long as it is without prejudice to this
Disclosed thought, it should be considered as disclosure disclosure of that equally.
Claims (20)
1. the method preparing automotive upholstery, it is characterised in that the method comprises the steps:
(1) use the solution containing nano silver material that bamboo filament is padded process, obtain nanometer silver-bamboo fibre and be combined
Fiber；
(2) make described nanometer silver-bamboo fibre composite fibre after chopped, contact with coupling agent and carry out surface-coated process, obtain
The nanometer silver of surface modification-chopped bamboo fibre composite fibre；
(3) acrylonitrile-butadiene-styrene copolymer, chemical modifier and described nanometer silver-chopped bamboo fibre composite fibre are made
Carry out melt extruding pelletize, obtain antimicrobial composite material；
(4) make described antimicrobial composite material heating plasticizing obtain melting charge, make described melting charge be mixed to form with supercritical fluid
Homogeneous phase solution, makes described homogeneous phase solution inject in the mold cavity of described automotive upholstery, obtains described vapour through fretting map molding
Car inside gadget, described supercritical fluid is supercritical carbon dioxide and/or supercritical nitrogen.
Method the most according to claim 1, it is characterised in that relative to 100 parts by weight of acrylonitrile-butadiene-styrene
Copolymer, the consumption of described chopped bamboo fibre is 5-60 weight portion, and the consumption of described nano silver material is 0.01-2 weight portion, institute
The consumption stating coupling agent is 0.1-10 weight portion, and the consumption of described chemical modifier is 0.1-20 weight portion；Described coupling agent is
Silane coupling agent and/or titante coupling agent；Described chemical modifier be selected from Aluminate, ethylene bis-fatty acid amides and
At least one in chromium picolinate.
Method the most according to claim 1, it is characterised in that the content ratio of described coupling agent and described chemical modifier is
1:(0.5-2.5).
Method the most according to claim 1, it is characterised in that described nano silver material contains nano silver particles and polyphenyl second
Alkene, the weight ratio of described nano silver particles and polystyrene is 1:(1-20), the particle diameter of nano-particle in described nano silver material
For 10-80nm.
Method the most according to claim 1, it is characterised in that the method includes: make acrylonitrile-butadiene-styrene (ABS) altogether
Carry out melt extruding pelletize with described nanometer silver-chopped bamboo fibre composite fibre again after polymers and chemical modifier mix homogeneously,
Obtain described antimicrobial composite material；The a length of 2-5mm of described nanometer silver-chopped bamboo fibre composite fibre.
Method the most according to claim 1, it is characterised in that the method includes: make heat stabilizer, processing aid, ultraviolet
After at least one in absorbent and antioxidant mixes with described acrylonitrile-butadiene-styrene copolymer and chemical modifier
Carry out melt extruding pelletize with described nanometer silver-chopped bamboo fibre composite fibre again, obtain described antimicrobial composite material；
Described antioxidant is selected from β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, 2-(1,1-dimethyl
Ethyl)-6-methyl-phenol, at least one in the double octadecyl of thio-2 acid；Described heat stabilizer is misery selected from Malaysia
At least one in Ji Xi or carboxylic acid stannum, Methyl stannum mercaptide and sulfydryl ester group stannum；Described ultraviolet absorber is selected from 2,4-dihydroxy
Base benzophenone, ESCALOL 567, Octabenzone, 2-(2 '-hydroxyl-3 ',
5 '-two tertiary phenyl)-5-chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4-t-octyl phenol epoxide) nickel,
At least one in (1,2,2,6,6-pempidine base) phosphite ester, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Institute
State processing aid be in calcium stearate, modified ethylene bis stearamide, Tissuemat E and ethylene bis stearic acid amide extremely
Few one；
Wherein, relative to 100 parts by weight of acrylonitrile-BS, the consumption of described antioxidant is 0.2-2 weight
Amount part, the consumption of described heat stabilizer is 0.2-2 weight portion, and the consumption of described ultraviolet absorber is 0.2-2 weight portion, described in add
The consumption of work auxiliary agent is 0.2-4 weight portion.
7. according to the method described in claim 1 or 6, it is characterised in that the method includes: make described nanometer silver-bamboo fibre multiple
Condensating fiber, after chopped and coupling agent surface-coated process, with compatilizer and/or dispersant, obtains the nanometer of surface modification
Silver-bamboo fibre composite fibre；
Described compatilizer is selected from Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride
With at least one in ABS grafted maleic anhydride；Described dispersant be selected from two polyphosphate sodiums, triethyl group hexyl sodium phosphate, ten
At least one in sodium dialkyl sulfate or fatty acid and macrogol ester；
Wherein, relative to 100 parts by weight of acrylonitrile-BS, the consumption of described compatilizer is 0.5-5 weight
Amount part, the consumption of described dispersant is 0.1-2 weight portion.
8. according to the method described in any one in claim 1-6, it is characterised in that the method includes: make polystyrene sulphur
Acid sodium and silver nitrate solution carry out redox reaction and obtain the described solution containing nano silver material.
9. according to the method described in any one in claim 1-6, it is characterised in that described in melt extrude the temperature of pelletize and be
210-250℃。
10. according to the method described in any one in claim 1-6, it is characterised in that the temperature of described supercritical fluid is
80-130 DEG C, pressure is 60-130MPa.
11. according to the method described in any one in claim 1-6, it is characterised in that the pressure of described heating plasticizing and institute
The difference of the pressure stating mold cavity is 50-100MPa, and the temperature of described mould is 50-80 DEG C.
12. according to the method described in any one in claim 1-6, it is characterised in that relative to 100 parts by weight of acrylonitrile-
BS, the consumption of described supercritical fluid is 0.5-10 weight portion.
The automotive upholstery that in 13. claim 1-12, method described in any one prepares.
14. 1 kinds of automotive upholsteries, it is characterised in that this automotive upholstery contain acrylonitrile-butadiene-styrene copolymer,
Chopped bamboo fibre, nano silver material, coupling agent and chemical modifier, wherein, relative to 100 parts by weight of acrylonitrile-butadiene-benzene
Ethylene copolymer, the content of described chopped bamboo fibre is 5-60 weight portion, and the content of described nano silver material is 0.01-2 weight
Part, the content of described coupling agent is 0.1-10 weight portion, and the content of described chemical modifier is 0.1-20 weight portion；Described coupling
Agent is silane coupling agent and/or titante coupling agent；Described chemical modifier is selected from Aluminate, ethylene bis-fatty acid acyl
At least one in amine and chromium picolinate.
15. automotive upholsteries according to claim 14, it is characterised in that described coupling agent and described chemical modifier
Content is than for 1:(0.5-2.5).
16. automotive upholsteries according to claim 14, it is characterised in that described nano silver material contains nano silver particles
And polystyrene, the weight ratio of described nano silver particles and polystyrene is 1:(1-20), nanometer in described nano silver material
The particle diameter of grain is 10-80nm.
17. automotive upholsteries according to claim 14, it is characterised in that a length of 2-5mm of described chopped bamboo fibre.
18. automotive upholsteries according to claim 14, it is characterised in that described automotive upholstery possibly together with compatilizer,
At least one in antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid；
Described compatilizer is selected from Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride
With at least one in ABS grafted maleic anhydride；Described antioxidant is selected from β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid
At least one in the double octadecyl of positive octadecanol ester, 2-(1,1-dimethyl ethyl)-6-methyl-phenol, thio-2 acid；
Described heat stabilizer is at least one in maleic acid tin octylate or carboxylic acid stannum, Methyl stannum mercaptide and sulfydryl ester group stannum；Institute
State dispersant for selected from two polyphosphate sodiums, triethyl group hexyl sodium phosphate, sodium lauryl sulphate or fatty acid and macrogol ester
In at least one；Described ultraviolet absorber be selected from 2,4 dihydroxyl benzophenone, ESCALOL 567,
Octabenzone, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole, single benzoic acid
Resorcinol, 2,2 '-thiobis (4-t-octyl phenol epoxide) nickel, (1,2,2,6,6-pempidine base) phosphite ester, 4-benzene
At least one in formyloxy-2,2,6,6-tetramethyl piperidine；Described processing aid is selected from calcium stearate, modified ethylene pair
At least one in stearmide, Tissuemat E, ethylene bis stearic acid amide.
19. automotive upholsteries according to claim 18, it is characterised in that described automotive upholstery possibly together with compatilizer,
Antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid, relative to 100 parts by weight of acrylonitrile-butadiene-benzene second
Alkene copolymer, the content of described compatilizer is 0.5-5 weight portion, and the content of described antioxidant is 0.2-2 weight portion, and described heat is steady
The content determining agent is 0.2-2 weight portion, and the content of described dispersant is 0.1-2 weight portion, and the content of described ultraviolet absorber is
0.2-2 weight portion, the content of described processing aid is 0.2-4 weight portion.
20. according to the automotive upholstery described in any one in claim 14-19, it is characterised in that described automotive upholstery
For air-conditioner air outlet housing.
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| CN102952337A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Modified bamboo fiber reinforced polypropylene composite material and preparation method thereof |
| CN103374166A (en) * | 2012-04-26 | 2013-10-30 | 上海杰事杰新材料(集团)股份有限公司 | High-strength bamboo-plastic micro-foaming composite material and preparation method thereof |
| CN104419108A (en) * | 2013-08-29 | 2015-03-18 | 合肥杰事杰新材料股份有限公司 | Bamboo powder/acrylonitrile-butadiene-styrene composite material and preparation method thereof |
| CN105038091A (en) * | 2015-07-29 | 2015-11-11 | 苏州天健竹业科技有限公司 | Bamboo fiber/ABS (acrylonitrile butadiene styrene copolymers) composite and preparation method thereof |
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2016
- 2016-08-11 CN CN201610656532.XA patent/CN106279747B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1965032A (en) * | 2004-06-10 | 2007-05-16 | 韩洋素材有限公司 | Sheet composition using bamboo |
| CN102558679A (en) * | 2011-12-28 | 2012-07-11 | 苏州晋圣博高分子材料科技有限公司 | Novel bamboo fiber/polypropylene composite material and method for preparing same |
| CN103374166A (en) * | 2012-04-26 | 2013-10-30 | 上海杰事杰新材料(集团)股份有限公司 | High-strength bamboo-plastic micro-foaming composite material and preparation method thereof |
| CN102952337A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Modified bamboo fiber reinforced polypropylene composite material and preparation method thereof |
| CN104419108A (en) * | 2013-08-29 | 2015-03-18 | 合肥杰事杰新材料股份有限公司 | Bamboo powder/acrylonitrile-butadiene-styrene composite material and preparation method thereof |
| CN105038091A (en) * | 2015-07-29 | 2015-11-11 | 苏州天健竹业科技有限公司 | Bamboo fiber/ABS (acrylonitrile butadiene styrene copolymers) composite and preparation method thereof |
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