CN106279747B - 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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- 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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- 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
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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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- C08J2497/00—Characterised by the use of lignin-containing materials
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
This disclosure relates to a kind of method for preparing automotive upholstery and automotive upholstery, the preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, and nano silver-bamboo fibre compound first is made in the two, then coupling agent and chemical modifier combination are modified processing to nano silver-bamboo fibre compound and resin matrix, and there is significant antibiotic and sterilizing effect by automotive upholstery made from overcritical micro foaming injection moulding, and under the premise of keeping mechanical property to be basically unchanged, the weight of automotive upholstery is obviously reduced.
Description
Technical field
This disclosure relates to composite material and product preparation field, and in particular, to a kind of preparation method of automotive upholstery
And automotive upholstery.
Background technique
In recent years, the development of auto industry has brought great convenience, and the appearance of new-energy automobile is further
The predicament of Current resource shortage is alleviated, while also growing day by day to the requirement of automotive light weight technology.For reply automotive light weight technology
Demand, fibre reinforced composites are as one of main solution, and proportion constantly increases in automotive material.It is fine at present
Dimension enhancing composite material is mainly formed by glass fibre, carbon fiber etc. with plastic composition, and the processing of waste is more difficult, produces ring
Border is severe, and very big burden is brought to environment.As people's environmental protection consciousness constantly enhances, processing performance is excellent, by with
In the plastics pollution on the environment of various industrial products has become general concern the problem of.Therefore, natural fiber is as increasing
Strong material is attracted attention for production environment friendly composite material.
Compound research is carried out with longer history, currently, bio-based materials exist using plant fiber and synthetic resin
Application in terms of automobile has begun, as natural fiber replaces glass fiber reinforcement；Japanese Toyota Company is in the car exhibition of Chicago
Illustrate the I/X plug-in hybrid concept car of flaxen fiber bio-based materials roof；Ford is shown in the model U
The rear baffle and seat foam of soy resins support；And plant fiber enhancing PP material manufacture instrument disc assembly shell is used to have become
Mainstream, a kind of smell is small, non-aging, low-density and the plant fiber enhancing PP material for having better environmental suitability,
It applies on car；The polypropylene automotive component of the 45% wood-fibred enhancing occurred on German market, wood-fibred enhancing subtract
Shake the products such as calendared sheet.The states such as India, Japan are using jute, sisal hemp, flax fiber and hemp as reinforcing material and heat
Thermoplastic polymer is made natural plant fibre polymer composite product and has also started engineer application.Natural fiber increases at home
Strong composite material is at the early-stage, and the research in this field really realizes that the product of volume production goes out not yet still in its infancy
It is existing.
China's bamboo wood yield ranks first in the world, accounts for 30% of the world or more, and cheap, is largely distributed in
The mountain areas such as Hunan, Anhui, Zhejiang.Bamboo fiber has good biodegradable and reproducibility simultaneously, utilizes this fibre
Compound the developed material of thermoplastic resins such as dimension and low-melting point polyester and polypropylene, intensity, specific modulus are relatively high, are suitable for
Make the reinforcement of the composite material of automobile；Reinforced phase can be made mutually to separate with matrix by melt process simultaneously, effectively reached
The purpose of recycling, to embody the feature of environmental protection and sustainable developability of material application.Bamboo fiber reinforcement thermoplastic
Composite processing energy consumption is few, and process equipment loss is small, is conducive to energy saving.The maximum feature of bamboo fibre is the height of cross section
Spend natural hollow.It is covered with ellipse gap on bamboo fibre section, gap is in quincunx arrangement, this makes bamboo fibre and its product
Moisture absorption, moisture releasing, wet transmitting performance are splendid, and expert is referred to as " fiber that can be breathed ".Bamboo has natural antibacterial, fungi-proofing, protection function
Can, free from insect pests, nothing are rotted in its growth course.These antibacterial materials not will receive destruction, day in the process of production and processing
Right antibiotic property will not cause any reaction to human body, and can also health-care and skin-care, the antibacterial agent that effect is added after being much better than.Bamboo
Fiber reinforced thermoplastics composite material has broad application prospects in fields such as automobile, electromechanics, interior decorations.
Nano silver particles partial size has high-specific surface area, unique physico-chemical property, efficiently generally in 25-50 ran
Antibacterial activity, have strong inhibition and killing to the tens of kinds of pathogenic microorganisms such as Escherichia coli, gonococcus, chlamydia trachomatis
Effect.It is found by researches that nano silver can kill 650 various bacterias in several minutes, the cell wall of nano-Ag particles and pathogen/
After film combines, thallus can be directly entered, rapidly with the combination of the sulfydryl (- SH) of oxygen metabolism enzyme, inactivate enzyme, respiratory metabolism is blocked to make
It is choked to death.Unique sterilization mechanism so that nano-Ag particles can kill rapidly pathogenic bacteria in low concentration, and will not produce
Raw drug resistance does not find any stimulate the reaction to skin without any toxic reaction yet.
Vehicle air conditioning outlet is the exhaust apparatus for automotive interior heating, ventilating and air conditioning system, is car room
Outer air intercommunication, the necessary place of circulation also need to guarantee that air is circulating other than meeting the requirements in various mechanical properties
Cleaning is kept in the process, not by the pollution of mould etc., protects the respiratory health of rider.And current most air-conditioner air outlet
The automotive upholsteries such as shell in the biggish situation of air humidity, give to pollute air by generation mould that can be different degrees of
Human health brings hidden danger；Meanwhile the compatibility of bamboo fibre and plastics is bad in existing bamboo fiber composite material, seriously affects
The performance of composite material and its product.
Summary of the invention
Purpose of this disclosure is to provide a kind of preparation method of automotive upholstery, the automotive upholstery of this method preparation can be with
The automotive upholstery for overcoming existing method to prepare is easy to produce mould, and fiber and resin compatible difference influence inside gadget performance
Technical problem.
Another object of the present disclosure is to provide a kind of automotive upholstery, which can solve existing automobile
The technical issues of inside gadget is easy to produce mould, and fiber and resin compatible difference influence composite property.
To achieve the goals above, the disclosure provides a kind of method for preparing automotive upholstery, and this method includes following step
It is rapid:
(1) bamboo filament is carried out to pad processing using the solution containing nano silver material, obtains nano silver-bamboo fibre
Composite fibre；
(2) make the nano silver-bamboo fibre composite fibre after being chopped, contacted with coupling agent and carry out surface coating processing,
Obtain the chopped bamboo fibre composite fibre of the modified nano silver-in surface；
(3) make acrylonitrile-butadiene-styrene copolymer, chemical modifier and the chopped bamboo fibre of the nano silver-compound
Fiber carries out melting extrusion granulation, obtains antimicrobial composite material；
(4) so that the antimicrobial composite material heating plasticizing is obtained melting charge, mix the melting charge with supercritical fluid
Homogeneous phase solution is formed, the homogeneous phase solution is injected in the mold cavity of the automotive upholstery, forms to obtain institute through fretting map
Automotive upholstery is stated, the supercritical fluid is supercritical carbon dioxide and/or supercritical nitrogen.
Through the above technical solutions, the preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, and first will
Nano silver-bamboo fibre compound is made in the two, then by coupling agent and chemical modifier combination to nano silver-bamboo fibre compound
It is modified processing with resin matrix, and there is significant resist by automotive upholstery made from overcritical micro foaming injection moulding
Bacterium bactericidal effect, and under the premise of keeping mechanical property to be basically unchanged, the weight of automotive upholstery is obviously reduced.
The disclosure also provides the automotive upholstery that above-mentioned preparation method is prepared.
The disclosure also provides a kind of automotive upholstery, which contains acrylonitrile-butadiene-styrene (ABS) copolymerization
Object, be 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 the chopped bamboo fibre are 5-60 parts by weight, and the content of the nano silver material is 0.01-2
Parts by weight, the content of the coupling agent are 0.1-10 parts by weight, and the content of the chemical modifier is 0.1-20 parts by weight；It is described
Coupling agent is silane coupling agent and/or titante coupling agent；The chemical modifier is selected from Aluminate, the double fat of ethylene
At least one of sour amide and chromium picolinate.
Contain bamboo fibre and nano silver material in the automotive upholstery of the disclosure, there is significant antibiotic and sterilizing effect；It will
Coupling agent and chemical modifier combination, while bamboo fibre surface and resin matrix are modified, improve automotive upholstery
Mechanical property；It distributed the molding micropore of fretting map in automotive upholstery, the density of automotive upholstery and whole can be substantially reduced
Body weight.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:
Fig. 1 is in automobile used by a kind of specific embodiment of the preparation method of automotive upholstery provided by the invention
The structural schematic diagram of gadget.
Specific embodiment
It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched
The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of method for preparing automotive upholstery, and this method comprises the following steps:
(1) bamboo filament is carried out to pad processing using the solution containing nano silver material, obtains nano silver-bamboo fibre
Composite fibre；
(2) make the nano silver-bamboo fibre composite fibre after being chopped, contacted with coupling agent and carry out surface coating processing,
Obtain the chopped bamboo fibre composite fibre of the modified nano silver-in surface；
(3) make acrylonitrile-butadiene-styrene copolymer, chemical modifier and the chopped bamboo fibre of the nano silver-compound
Fiber carries out melting extrusion granulation, obtains antimicrobial composite material；
(4) so that the antimicrobial composite material heating plasticizing is obtained melting charge, mix the melting charge with supercritical fluid
Homogeneous phase solution is formed, the homogeneous phase solution is injected in the mold cavity of the automotive upholstery, forms to obtain institute through fretting map
Automotive upholstery is stated, the 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 nano silver-bamboo first is made in the two
Then fibre composites change coupling agent and chemical modifier combination to nano silver-bamboo fibre compound and resin matrix
Property processing, and there is significant antibiotic and sterilizing effect by automotive upholstery made from overcritical micro foaming injection moulding, and
Under the premise of keeping mechanical property to be basically unchanged, the weight of automotive upholstery is obviously reduced.
Wherein, the method for padding processing is well known to those skilled in the art, can be with reference to sizing fabric process
Method for sizing is carried out using the cooperation of compregnate roller and sizing roller.Specifically processing method can for second dipping and rolling, it is double leaching three pressure or
Double four pressures of leaching etc., preferably second dipping and rolling method.
In the preparation method according to the disclosure, the dosage of each raw material component can change in very large range, Ke Yiwei
Dosage commonly used by field of compound material technical staff, for example, relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer
Object, the dosage for the bamboo fibre that is chopped can be 5-60 parts by weight, and the dosage of nano silver material can be 0.01-2 parts by weight, coupling agent
Dosage can be 0.1-10 parts by weight, the dosage of chemical modifier can be 0.1-20 parts by weight；Coupling agent can be silane
Class coupling agent and/or titante coupling agent；The chemical modifier is selected from Aluminate, ethylene bis-fatty acid amides and pyridine
At least one of chromic formate.
In order to further increase the antibacterial effect and mechanical property of the automotive upholstery by above method preparation, preferable case
Under, the dosage relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the bamboo fibre that is chopped can be 15-35 weight
Part, the dosage of nano silver material can be 0.05-0.5 parts by weight, and the dosage of coupling agent can be 0.5-5 parts by weight, and chemistry changes
The dosage of property agent can be 0.5-10 parts by weight.
According to the disclosure, the acrylonitrile-butadiene-styrene copolymer (ABS resin) is those skilled in the art institute
Known, the relative amount of acrylonitrile unit therein member, butadiene structural units and styrol structural unit is not important to
It asks, can be the conventional selection of field of compound material, for example, 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).Above-mentioned acrylonitrile-
Butadiene-styrene copolymer can be commercial products, such as can for purchased from Japan Electric chemistry ABS resin GR-4000,
ABS Magnum800 purchased from Si Tailong company, the U.S., ABS resin Terluran KR2883 purchased from BASF Aktiengesellschaft,
KR2885,828P or 846L etc..
In the preparation method according to the disclosure, coupling agent can be used for carrying out surface to chopped bamboo fibre being modified, described
Chemical modifier can be used for being modified resin matrix, and the two is used cooperatively for improving acrylonitrile-butadiene-styrene (ABS)
The interface compatibility of copolymer and chopped bamboo fibre, to improve the interface bond strength of the two.In above-mentioned preparation method each group
Divide in amount ranges, in order to further increase the interface cohesion of acrylonitrile-butadiene-styrene copolymer and chopped bamboo fibre
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, vinyltriethoxysilane, ethylene
Base trimethoxy silane, double-(γ-triethoxy silicon substrate propyl) tetrasulfide, γ-methacryloxypropyl trimethoxy
One or more of silane, triphenyl silicol, wherein in order to make the processed fiberglass surfacing of silane coupling agent with
Active force between cyclic olefin polymer interface is stronger, under preferable case, selects the coupling agent containing olefin group, such as ethylene
Ethyl triethoxy silicane alkane, vinyltrimethoxysilane or γ-methacryloxypropyl trimethoxy silane；Titanate ester
Coupling agent can be for selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy)
Titanate esters, two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters
The chelate of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine and bis- (two octyloxy pyrophosphoric acid ester groups) second
Support at least one of titanate esters.
According to the disclosure, nano silver material can be any form containing nano silver particles, for example, nano silver material can
Think and contain only nano silver particles, can also disperse on the carrier particles, the type and content present invention of carrier granular is not spy
Other requirement, as long as meeting, nano silver particles are evenly distributed in nano silver material and content is suitable for.In order to improve nanometer
The compatibility of silver particles and resin matrix under preferable case, can choose the knot with acrylonitrile-butadiene-styrene copolymer
Structure unit is identical or structure similar in carrier granular of the polymer as nano silver particles, for example, nano silver material can contain
Nano silver particles and polystyrene.
In nano silver material, the relative usage of polystyrene and nano silver particles can change in very large range, preferably
In the case of, the amount ratio of the nano silver particles and polystyrene can be 1:(1-20), in above-mentioned content range, You Bengong
Nano silver particles content in the automotive upholstery that the preparation method opened is prepared is suitable for, and nano silver particles and acrylonitrile-
The compatibility of butadiene-styrene copolymer resin matrix is good, is conducive to the antibacterial effect for improving composite material.
In nano silver material, the carrier granulars such as nano silver particles and polystyrene may be constructed nano particle, the nanometer
The size of grain can change in very large range, wherein in order to improve the antibacterial effect and compatibility of nano silver particles, preferably
Ground, the partial size of nano particle can be 5-100nm in nano silver material.
It can also be changed in very large range according to the length of the disclosure, the bamboo fibre that is chopped, as long as meeting the bamboo fibre that is chopped
Humidification is played, and can be uniformly dispersed in the composite material.Under preferable case, the length for the bamboo fibre that is chopped can
Think 2-5mm.In above-mentioned preferred length range, be chopped bamboo fibre and acrylonitrile butadiene styrene resin base
The compatibility of body is good, and obvious to the humidification of composite material.
In order to further increase chemical modifier to the modified effect of acrylonitrile-butadiene-styrene copolymer, improve altogether
The compatibility of copolymer resin matrix and chopped bamboo fibre, under preferable case, this method comprises: making acrylonitrile-butadiene-styrene (ABS)
Copolymer and chemical modifier carry out melting extrusion with the chopped bamboo fibre composite fibre of the nano silver-again after mixing and make
Grain, obtains the antimicrobial composite material.
It is highly preferred that in order to further increase the comprehensive performance of the automotive upholstery by disclosed method preparation, automobile
The preparation method of inside gadget may include: make at least one of heat stabilizer, processing aid, ultraviolet absorber and antioxidant with
The bamboo fibre that is chopped again with the nano silver-after the acrylonitrile-butadiene-styrene copolymer and chemical modifier mixing is compound
Fiber carries out melting extrusion granulation, obtains the antimicrobial composite material；
Wherein, the specific type of antioxidant, heat stabilizer, ultraviolet absorber and processing aid can be those skilled in the art
Conventional kind known to member, for example, antioxidant can be for selected from β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid positive 18
At least one of double octadecyls of carbon alcohol ester, 2- (1,1- dimethyl ethyl) -6- methyl-phenol, thio-2 acid；Thermostabilization
Agent can be for selected from least one of maleic acid tin octylate or carboxylic acid tin, Methyl stannum mercaptide and sulfydryl ester group tin；UV absorption
Agent can be for selected from 2,4 dihydroxyl benzophenone, ESCALOL 567,2- hydroxyl -4- n-octyloxy hexichol
Ketone, 2- (2 '-hydroxyls -3 ', 5 '-two tertiary phenyl) -5- chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis
(4- t-octyl phenol oxygroup) nickel, (1,2,2,6,6- pempidine base) phosphite ester, 4- benzoyloxy -2,2,6,6- tetramethyl
At least one of piperidines；Processing aid can be for selected from calcium stearate, modified ethylene bis stearamide, polyethylene wax, ethylene
At least one of double stearic amides.
In the another embodiment of the disclosure, in order to improve the compatibility of bamboo fibre Yu copolymer resin matrix, vapour
The preparation method of interior gadget may include: to make the nano silver-bamboo fibre composite fibre after being chopped and the painting of coupling agent surface
After covering processing, with compatilizer and/or dispersant, the modified nano silver-bamboo fibre composite fibre in surface is obtained；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 of branch maleic anhydride；Dispersing agent can be for selected from two polyphosphate sodiums, triethyl group hexyl phosphoric acid sodium, dodecyl sulphur
Sour sodium or at least one of fatty acid and macrogol ester.
As the disclosure, preferably a kind of embodiment, the preparation method of automotive upholstery include: to make the nano silver-bamboo
Fiber composite fiber, with compatilizer and/or dispersant, obtains to surface and changes after being chopped and after the coating processing of coupling agent surface
Nano silver-bamboo fibre composite fibre of property；
Also, make heat stabilizer, processing aid, ultraviolet absorber and antioxidant and the acrylonitrile-butadiene-styrene (ABS)
The bamboo fibre composite fibre that is chopped again with the nano silver-after copolymer and chemical modifier mixing carries out melting extrusion granulation, obtains
To the antimicrobial composite material；
Above-mentioned compatilizer, antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid specific type can be with
As hereinbefore；Compatilizer, antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid amount ranges can be
Variation in very wide range, it is preferable that relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the dosage of compatilizer
It can be 0.5-5 parts by weight, the dosage of antioxidant can be 0.2-2 parts by weight, and the dosage of heat stabilizer can be 0.2-2 weight
Part, the dosage of dispersing agent can be 0.1-2 parts by weight, and the dosage of ultraviolet absorber can be 0.2-2 parts by weight, processing aid
Dosage can be 0.2-4 parts by weight.In this one preferred embodiment, by the anti-oxidant of the automotive upholstery of this method preparation
The comprehensive performances such as property, weatherability and thermal stability are obviously improved.
According to the disclosure, in above-mentioned preparation process, the method that melting extrusion is granulated is well known to those skilled in the art, institute
Stating melting extrusion granulation can carry out on extrusion equipment, such as screw extruder, and the screw extruder can be single screw rod
Extruder or double screw extruder, the present invention do not do special requirement.
Wherein, the reaction condition that melting extrusion is granulated may be as it is known to those skilled in the art that can be according to matrix
The type and property of resin accordingly adjust.Under preferable case, in order to improve the melting mixing effect of each raw material component, melting extrusion
The temperature of granulation can be 210-250 DEG C.
According to the disclosure, nano silver material can be dispersed to obtain by the substance containing nano silver particles, can also be by chemistry
Reaction obtains.In the disclosure preferably a kind of embodiment, polystyrene and nanometer silver granuel can be contained in nano silver material
Son can be obtained by kayexalate with silver nitrate solution progress redox reaction described containing the molten of nano silver material
Liquid, shown in chemical equation such as following formula (1), reaction condition can change in very large range, for example, reaction temperature can be
20-100 DEG C, the reaction time can be 5-60min, it is preferable that reaction temperature can be 50-90 DEG C, and the reaction time can be 10-
40min.The solution that the above-mentioned solution containing nano silver material can be formed for aqueous solution or other suitable solvents.It is excellent at this
In the embodiment of choosing, nano silver particles that redox reaction obtains can with uniform adsorption on granules of polystyrene, thus
The dispersing uniformity of nano silver particles is improved, while by can be further improved a nanometer silver granuel with granules of polystyrene absorption
The compatibility of son and copolymer resin matrix and bamboo fibre.
According to the disclosure, in order to improve the compatibility of chopped bamboo fibre and resin matrix, the above method further includes using even
After joining agent to the nano silver-bamboo fibre composite fibre progress surface coating processing, make surface described in step (2) is modified to receive
Meter Yin-bamboo fibre composite fibre and compatilizer and dispersant are simultaneously reacted, and it is compound to obtain the modified nano silver-bamboo fibre in surface
Fiber.
Coupling agent is used to carry out the method for surface coating processing also for art technology to nano silver-bamboo fibre composite fibre
Known to personnel, for example, nano silver-bamboo fibre composite fibre can be dispersed in containing the anhydrous of 0.2-10% (wt) coupling agent
In ethyl alcohol, HCl is added and adjusts pH value to 4-5, ultrasonic disperse reacts 1-2 hours at 50 DEG C.After reaction, nano silver-is taken out
Bamboo fibre composite fibre, it is extremely neutral wash with distilled water, it is dried 2-5 hours at 100-120 DEG C, obtains the modified nanometer in surface
Silver-bamboo fibre composite fibre.
According to the disclosure, the meaning 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.It is more than usually critical-temperature regardless of whether its pressure and density are more than critical state of value temperature is in
Fluid all return for supercritical fluid.Supercritical fluid have many unique properties, as viscosity is small, density, diffusion coefficient,
The properties such as solvability change very sensitive with temperature and pressure: 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 change in very large range, it is preferable that super
The temperature of critical fluids is 80-130 DEG C, pressure 60-130MPa.Supercritical fluid within the scope of above-mentioned temperature and pressure is advantageous
In forming homogeneous phase solution with melted material, it is convenient for subsequent fretting map forming process.
The melted material that supercritical fluid and heating plasticizing obtain is mixed to form homogeneous phase solution, which can keep
At a higher pressure, the lower mold cavity of temperature and pressure is then injected by switching regulator nozzle, due to temperature and pressure
The unstability for causing molecule is reduced to forming a large amount of nuclei of bubbles in product, these last 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 molding Forming Quality of fretting map, preferably feelings to further increase supercritical fluid
Under condition, the difference of the pressure of the pressure and mold cavity of heating plasticizing can be 50-100MPa, and the temperature of mold can be 50-
80℃。
The dosage of supercritical fluid can change in very large range, in the automobile that density and gas release are suitable in order to obtain
Gadget, it is preferable that relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the dosage of supercritical fluid can be
0.5-10 parts by weight.In above-mentioned preferred amount ranges, the automotive upholstery of the preparation method preparation of the disclosure can be strong
In the case that degree is held essentially constant, the density and overall weight of inside gadget are further decreased.
The disclosure also provides the automotive upholstery that above-mentioned preparation method is prepared.
The disclosure also provides a kind of automotive upholstery, which contains acrylonitrile-butadiene-styrene (ABS) copolymerization
Object, be 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 the chopped bamboo fibre are 5-60 parts by weight, and the content of the nano silver material is 0.01-2
Parts by weight, the content of the coupling agent are 0.1-10 parts by weight, and the content of the chemical modifier is 0.1-20 parts by weight；It is described
Coupling agent is silane coupling agent and/or titante coupling agent；The chemical modifier is selected from Aluminate, the double fat of ethylene
At least one of sour amide and chromium picolinate.
Contain bamboo fibre and nano silver material in the automotive upholstery of the disclosure, there is significant antibiotic and sterilizing effect；It will
Coupling agent and chemical modifier combination, while bamboo fibre surface and resin matrix are modified, improve automotive upholstery
Mechanical property；It distributed the molding micropore of fretting map in automotive upholstery, the density of automotive upholstery and whole can be substantially reduced
Body weight.
According to the disclosure, in order to further increase the antibacterial effect and mechanical property of automotive upholstery, under preferable case, phase
For 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the content for the bamboo fibre that is chopped can be 15-35 parts by weight, receive
The content of rice ag material can be 0.05-0.5 parts by weight, and the content of coupling agent can be 0.5-5 parts by weight, chemical modifier
Content can be 0.5-10 parts by weight.
The acrylonitrile-butadiene-styrene copolymer (ABS resin) is well known to those skilled in the art, therein
The relative amount of acrylonitrile unit member, butadiene structural units and styrol structural unit does not specially require, and can be multiple
The conventional selection in condensation material field, for example, in acrylonitrile-butadiene-styrene copolymer, acrylonitrile unit member, butadiene
The weight ratio of structural unit and styrol structural unit can be 1:(0.15-2): (1-4).Above-mentioned acrylonitrile-butadiene-benzene second
Alkene copolymer can be commercial products, such as can for purchased from Japan Electric chemistry ABS resin GR-4000, be purchased from the U.S. this
ABS Magnum800 of company, ACE Semi, ABS resin Terluran KR2883 purchased from BASF Aktiengesellschaft, KR2885,
828P or 846L etc..
In the automotive upholstery according to the disclosure, coupling agent can be used for carrying out surface to chopped bamboo fibre being modified, institute
Stating chemical modifier can be used for being modified resin matrix, and the two is used cooperatively for improving acrylonitrile-butadiene-benzene second
The interface compatibility of alkene copolymer and chopped bamboo fibre, to improve the interface bond strength of the two.In above-mentioned content range,
In order to further increase the interface binding power of acrylonitrile-butadiene-styrene copolymer and chopped bamboo fibre, coupling agent and chemistry
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, vinyltriethoxysilane, vinyl trimethoxy
Silane, double-(γ-triethoxy silicon substrate propyl) tetrasulfide, γ-methacryloxypropyl trimethoxy silane, triphen
One or more of base silicol, wherein in order to keep the processed fiberglass surfacing of silane coupling agent and cycloolefin poly-
The active force closed between object interface is stronger, under preferable case, selects the coupling agent containing olefin group, such as three ethoxy of vinyl
Base silane, vinyltrimethoxysilane or γ-methacryloxypropyl trimethoxy silane；Titante coupling agent can
Think selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters,
Two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters are bis-, and (two is pungent
Oxygroup pyrophosphoric acid ester group) ethylene titanate esters and triethanolamine chelate and Di(dioctylpyrophosphato) ethylene titanate
At least one of.
Aluminate can be for selected from three isopropyl ester of aluminic acid, three benzyl ester of aluminic acid；Ethylene bis-fatty acid amides can be double for ethylene
The double oleamides of stearic amide, ethylene, ethylene double at least one of palmitamides and ethylene dilaurate amide.
According to the disclosure, nano silver material can be any form containing nano silver particles, for example, nano silver material can
Think and contain only nano silver particles, can also disperse on the carrier particles, the type and content present invention of carrier granular is not spy
Other requirement, as long as meeting, nano silver particles are evenly distributed in nano silver material and content is suitable for.In order to improve nanometer
The compatibility of silver particles and resin matrix under preferable case, can choose the knot with acrylonitrile-butadiene-styrene copolymer
Structure unit is identical or structure similar in carrier granular of the polymer as nano silver particles, for example, nano silver material can contain
Nano silver particles and polystyrene.
In nano silver material, the relative amount of polystyrene and nano silver particles can change in very large range, preferably
In the case of, the weight ratio of the 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 for, and nano silver particles and acrylonitrile butadiene styrene resin matrix
Compatibility is good, is conducive to the antibacterial effect for improving composite material.
In nano silver material, the carrier granulars such as nano silver particles and polystyrene may be constructed nano particle, the nanometer
The size of grain can change in very large range, wherein in order to improve the antibacterial effect and compatibility of nano silver particles, preferably
Ground, the partial size of nano particle can be 10-80nm in nano silver material.
According to the disclosure, the length of the chopped bamboo fibre composite fibre of nano silver-can also change in very large range, as long as
Meet the bamboo fibre that is chopped and play humidification, and can be uniformly dispersed in the composite material.Under preferable case, nanometer
The length of the chopped bamboo fibre composite fibre of silver-can be 2-5mm.In above-mentioned preferred length range, the chopped bamboo of nano silver-is fine
The compatibility for tieing up composite fibre and acrylonitrile butadiene styrene resin matrix is good, and makees to the enhancing of composite material
With obvious.
According to the disclosure, in order to further increase the comprehensive performance of automotive upholstery, under preferable case, above-mentioned automobile interior decoration
Part can also contain at least one of compatilizer, antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid.
Above-mentioned compatilizer, antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid specific type can be with
The conventional kind being well known to those skilled in the art, for example, compatilizer can be for selected from Research of Grafting Malaic Anhydride Onto Polyethylene, benzene second
At least one of 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) propionic acid n-octadecyl alcohol ester, 2- (1,1- dimethyl ethyl) -6- methyl-phenol,
At least one of double octadecyls of thio-2 acid；Heat stabilizer can be for selected from maleic acid tin octylate or carboxylic acid tin, methyl
At least one of tin mercaptides and sulfydryl ester group tin；Dispersing agent can be for selected from two polyphosphate sodiums, triethyl group hexyl phosphoric acid sodium, ten
Sodium dialkyl sulfate or at least one of fatty acid and macrogol ester；Ultraviolet absorber can be for selected from 2,4- dihydroxy two
Benzophenone, ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxyls -3 ', 5 '-two
Tertiary phenyl) -5- chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4- t-octyl phenol oxygroup) nickel, (1,2,
2,6,6- pempidine base) phosphite ester, at least one of 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Processing helps
Agent can be at least one in calcium stearate, modified ethylene bis stearamide, polyethylene wax, ethylene bis stearic acid amide
Kind.
As the disclosure, preferably a kind of specific embodiment, the automotive upholstery further include compatilizer, antioxidant, heat
Stabilizer, dispersing agent, ultraviolet absorber and processing aid；Preferably, the content of above-mentioned auxiliary agent can be with are as follows: relative to 100 weight
The content of part acrylonitrile-butadiene-styrene copolymer, compatilizer can be 0.5-5 parts by weight, and the content of antioxidant can be
0.2-2 parts by weight, the content of heat stabilizer can be 0.2-2 parts by weight, and the content of dispersing agent can be 0.1-2 parts by weight, purple
The content of outer absorbent can be 0.2-2 parts by weight, and the content of processing aid can be 0.2-4 parts by weight.It is above-mentioned preferably to help
The comprehensive performances such as the inoxidizability, weatherability and thermal stability of the automotive upholstery can be improved in agent and content range.
Above-mentioned automotive upholstery may include air-conditioner air outlet shell, compartment partition, door panel, panel assembly and
At least one of handrail.Wherein, in order to play the antibacterial and mouldproof effect of the automotive upholstery, it is preferable that automotive upholstery
It can be air-conditioner air outlet shell.
The disclosure is further illustrated by the following examples, but therefore the disclosure is not any way limited.At this
In disclosed following embodiments, the structure of automotive upholstery as shown in Figure 1, acrylonitrile-butadiene-styrene copolymer be purchased from
The ABS resin Terluran KR2883 of BASF Aktiengesellschaft, bamboo fibre are purchased from Ningbo Qi Zhu company；Other chemical reagent
It is general commercial products；Melting extrusion is prepared in the connection company's T L-55-55-500 type double screw extruder of upper tableland.
Embodiment 1
The present embodiment is used to illustrate the composition of the automotive upholstery of the disclosure.
Contain in the automotive upholstery of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 15 weight
(weight ratio of nano silver particles and polystyrene is 1:3, nano particle for the chopped bamboo fibre of part, 0.01 parts by weight nano silver material
Partial size be 20nm), 0.1 parts by weight Silane coupling agent KH550,15 parts by weight chemical modifier Aluminates.
Embodiment 2
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 60 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:20, the partial size of nano particle to 2 parts by weight nano silver materials
For 100nm), 10 parts by weight coupling agent isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, 0.1 parts by weight chemical modifier
Ethylene bis-fatty acid amides.
Embodiment 3
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 5 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:1, the grain of nano particle to 0.02 parts by weight nano silver material
Diameter is 30nm), 0.1 parts by weight Silane coupling agent KH550,0.2 parts by weight chemical modifier chromium picolinate.
Embodiment 4
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 15 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3, the grain of nano particle to 0.05 parts by weight nano silver material
Diameter is 20nm), 0.5 parts by weight Silane coupling agent KH550,10 parts by weight chemical modifier Aluminates.
Embodiment 5
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 35 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3, the partial size of nano particle to 0.4 parts by weight nano silver material
For 20nm), 5 parts by weight Silane coupling agent KH550s, 0.5 parts by weight chemical modifier Aluminate.
Embodiment 6
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 15 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3, the grain of nano particle to 0.01 parts by weight nano silver material
Diameter is 20nm), 0.1 parts by weight Silane coupling agent KH550,0.1 parts by weight chemical modifier Aluminate.
Embodiment 7
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 30 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3, the partial size of nano particle to 0.2 parts by weight nano silver material
It is connect for 20nm), 1 parts by weight Silane coupling agent KH550,1 parts by weight chemical modifier Aluminate, 1 parts by weight of compatible agent styrene
Branch maleic anhydride, 0.5 parts by weight antioxidant β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, 0.5 weight
Part heat stabilizer maleic acid tin octylate, 0.5 parts per weight dispersing agent macrogol ester, 0.5 parts by weight ultraviolet absorber 2,4- dihydroxy
Base benzophenone and 0.5 parts by weight processing aid calcium stearate.
Comparative example 1
This comparative example is used to illustrate different from the disclosure to be used for automotive upholstery.
Containing ingredient with embodiment 1 in the automotive upholstery, the difference is that nano silver material such as is replaced at the weight
Acrylonitrile-butadiene-styrene copolymer.
Comparative example 2
The automotive upholstery contains the ingredient with embodiment 1, the difference is that chopped bamboo fibre such as is replaced at the weight
Acrylonitrile-butadiene-styrene copolymer.
Comparative example 3
Containing ingredient with embodiment 1 in the automotive upholstery, the difference is that coupling agent KH550 such as is replaced at the weight
The chemical modifier Aluminate of amount.
Comparative example 4
Containing the ingredient with embodiment 1 in the automotive upholstery, the difference is that chemical modifier Aluminate is replaced with
Etc. weight coupling agent KH550.
Prepare embodiment 1
The present embodiment is used to illustrate the preparation method of the automotive upholstery of the disclosure, each in the automotive upholstery of the present embodiment
The dosage of raw material is same as Example 1, includes the following steps:
(1) kayexalate is added in silver nitrate solution and is mixed evenly, in micro-wave oven, 500w heating
30min, centrifuge separation, obtains the aqueous solution containing nano silver material, bamboo fibre is immersed in concentration 1g/L's after drying process
It is compound to obtain nano silver-bamboo fibre for aqueous solution containing nano silver material, second dipping and rolling, heated by microwave fast dewatering, drying
Fiber；
(2) the drying nano silver-bamboo fibre composite fibre obtained (1) is carried out after being chopped with Silane coupling agent KH550
The chopped bamboo fibre composite fibre (length 2-5mm) of the modified nano silver-in surface is obtained after the coating of surface；
(3) by ABS resin and chemical modifier put into heated at high speed mixing machine (2000 turns/min of speed of agitator) into
It is added twin-screw extrude (230 DEG C of temperature) after row mixing dispersion, then will the chopped compound fibre of bamboo fibre of nano silver-in (2)
Dimension is added from the side spout of extruder, carries out melt pelletization, by obtaining antibacterial after outlet mold sizing, water cooling, air-dried, pelletizing
Composite material；
(4) above-mentioned antimicrobial composite material heating plasticizing is made to obtain melting charge, supercritical carbon dioxide heating plasticizing obtains
Melting charge is mixed to form homogeneous phase solution, injects the homogeneous phase solution in the mold cavity of the automotive upholstery, through fretting map
Molding obtains the automotive upholstery of the present embodiment.Relative to 100 parts by weight, the dosage of supercritical fluid is 2 parts by weight；Heating modeling
The difference of the pressure of the pressure and mold cavity of change can be 60 DEG C with 80MPa, the temperature of mold.
Prepare embodiment 2
Using preparation embodiment 1 method, the difference is that in the automotive upholstery of the present embodiment the dosage of each raw material with
Embodiment 2 is identical.
Prepare embodiment 3
Using preparation embodiment 1 method, the difference is that in the automotive upholstery of the present embodiment the dosage of each raw material with
Embodiment 3 is identical.
Prepare embodiment 4
Using preparation embodiment 1 method, the difference is that in the automotive upholstery of the present embodiment the dosage of each raw material with
Embodiment 4 is identical.
Prepare embodiment 5
Using preparation embodiment 1 method, the difference is that in the automotive upholstery of the present embodiment the dosage of each raw material with
Embodiment 5 is identical.
Prepare embodiment 6
Using preparation embodiment 1 method, the difference is that in the automotive upholstery of the present embodiment the dosage of each raw material with
Embodiment 6 is identical.
Prepare embodiment 7
The dosage of each raw material is same as Example 7 in the automotive upholstery of the present embodiment, and preparation method includes the following steps:
(1) kayexalate is added in silver nitrate solution and is mixed evenly, in micro-wave oven, 500w heating
30min, centrifuge separation, obtains the aqueous solution containing nano silver material, bamboo fibre is immersed in concentration 1g/L's after drying process
It is compound to obtain nano silver-bamboo fibre for aqueous solution containing nano silver material, second dipping and rolling, heated by microwave fast dewatering, drying
Fiber；
(2) the drying nano silver-bamboo fibre composite fibre obtained (1) is carried out after being chopped with Silane coupling agent KH550
It is reacted with compatilizer, dispersing agent through heated at high speed mixing machine (2000 turns/min of speed of agitator) after the coating of surface, in compatilizer
Esterification occurs for the hydroxyl (- OH) in maleic anhydride and bamboo fibre, the carboxyl (- COOH) that reaction process generates again with natural fibre
Subsequent esterification occurs for the hydroxyl (- OH) in dimension, and it is (long to obtain the chopped bamboo fibre composite fibre of the modified nano silver-in surface
Degree is 2-5mm)；
(3) ABS resin, chemical modifier, heat stabilizer, processing aid, ultraviolet absorber and antioxidant are put into height
(temperature 230 is added twin-screw extrude after carrying out mixing dispersion (2000 turns/min of speed of agitator) in speed heating mixing machine
DEG C), then the nano silver-in (2) is chopped bamboo fibre composite fibre from the addition of the side spout of extruder, melt pelletization is carried out,
Again by obtaining antimicrobial composite material after outlet mold sizing, water cooling, air-dried, pelletizing；
(4) above-mentioned antimicrobial composite material heating plasticizing is made to obtain melting charge, supercritical carbon dioxide heating plasticizing obtains
Melting charge is mixed to form homogeneous phase solution, injects the homogeneous phase solution in the mold cavity of the automotive upholstery, through fretting map
Molding obtains the automotive upholstery of the present embodiment.Relative to 100 parts by weight, the dosage of supercritical fluid is 2 parts by weight；It is overcritical
The additional amount of carbon dioxide is the pressure of heating plasticizing and the difference of pressure of mold cavity can be with 80MPa, the temperature of mold
60℃。
Prepare comparative example 1-4
Using preparation embodiment 1 method, the difference is that in automotive upholstery the dosage of each raw material respectively with comparative example
1-4 is identical.
Prepare comparative example 5
The dosage and preparation method of each raw material are same as Example 1 in the automotive upholstery of this comparative example, the difference is that
So that antimicrobial composite material obtained in step (3) is carried out injection molding and obtains the automotive upholstery of this comparative example.
Testing example 1
Automotive upholstery obtained in preparation embodiment 1-7 and preparation comparative example 1-5 is performed the following performance tests respectively:
Relative density test is referring to GB4472-2011；Tensile strength is tested according to ASTM D638 standard, stretches speed
50mm/min is spent, bending strength and bending modulus are tested according to ASTM D790 standard, span 56mm, and rate of bending is
2mm/min, test result are listed in table 1
According to light industry of China professional standard QB/T 2591-2003, " antibiotic plastic-anti-microbial property is commented for the test of antibiotic rate
Valence and its test method " standard tests it.Test the strain used: staphylococcus aureus, Escherichia coli, black song
Mould, Aspergillus terreus, test result are listed in table 2.
Table 1
| Tensile strength (MPa) | Bending strength (MPa) | Relative density (g/m3) | |
| Prepare embodiment 1 | 42.6 | 65.8 | 0.98 |
| Prepare embodiment 2 | 33.9 | 56.5 | 1.00 |
| Prepare embodiment 3 | 40.9 | 62.9 | 0.97 |
| Prepare embodiment 4 | 43.8 | 66.4 | 0.95 |
| Prepare embodiment 5 | 48.4 | 69.5 | 0.94 |
| Prepare embodiment 6 | 50.4 | 71.7 | 0.95 |
| Prepare embodiment 7 | 49.6 | 72.9 | 0.93 |
| Prepare comparative example 1 | 41.9 | 64.7 | 0.99 |
| Prepare comparative example 2 | 37.7 | 55.1 | 0.98 |
| Prepare comparative example 3 | 40.1 | 62.9 | 1.00 |
| Prepare comparative example 4 | 39.6 | 62.1 | 0.99 |
| Prepare comparative example 5 | 31.4 | 48.3 | 1.03 |
Table 2
According to Tables 1 and 2 data, can be seen that relatively from preparation embodiment 1 and the data comparison for preparing comparative example 1-2
In the automotive upholstery for containing only 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；It can with the data comparison for preparing comparative example 3-4 from preparation embodiment 1
Out, relative to the automotive upholstery for containing only chemical modifier or coupling agent, the automotive upholstery and preparation method of the disclosure will
Coupling agent and chemical modifier combination, while bamboo fibre surface and resin matrix are modified, improve automotive upholstery
Mechanical property；Preparation embodiment 1 and the data comparison of preparation comparative example 5 can be seen that relative to not using fretting map to be molded into
The automotive upholstery production method of type, the automotive upholstery obtained using the preparation method of the disclosure are keeping mechanical property basic
While constant, hence it is evident that reduce density and overall weight.
The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure
Monotropic type, these simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (20)
1. a kind of method for preparing automotive upholstery, which is characterized in that this method comprises the following steps:
(1) bamboo filament is carried out to pad processing using the solution containing nano silver material, it is compound obtains nano silver-bamboo fibre
Fiber；
(2) make the nano silver-bamboo fibre composite fibre after being chopped, contacted with coupling agent and carry out surface coating processing, obtained
The chopped bamboo fibre composite fibre of the modified nano silver-in surface；
(3) make the chopped bamboo fibre composite fibre of acrylonitrile-butadiene-styrene copolymer, chemical modifier and the nano silver-
Melting extrusion granulation is carried out, antimicrobial composite material is obtained；
(4) so that the antimicrobial composite material heating plasticizing is obtained melting charge, be mixed to form the melting charge with supercritical fluid
Homogeneous phase solution injects the homogeneous phase solution in the mold cavity of the automotive upholstery, forms to obtain the vapour through fretting map
Interior gadget, the supercritical fluid are supercritical carbon dioxide and/or supercritical nitrogen.
2. the method according to claim 1, wherein relative to 100 parts by weight of acrylonitrile-butadiene-styrene
Copolymer, the dosage of the chopped bamboo fibre are 5-60 parts by weight, and the dosage of the nano silver material is 0.01-2 parts by weight, institute
The dosage for stating coupling agent is 0.1-10 parts by weight, and the dosage of the chemical modifier is 0.1-20 parts by weight；The coupling agent is
Silane coupling agent and/or titante coupling agent；The chemical modifier be selected from Aluminate, ethylene bis-fatty acid amides and
At least one of chromium picolinate.
3. the method according to claim 1, wherein the content of the coupling agent and chemical modifier ratio is
1:(0.5-2.5).
4. the method according to claim 1, wherein the nano silver material contains nano silver particles and polyphenyl second
The weight ratio of alkene, the nano silver particles and polystyrene is 1:(1-20), the partial size of nano particle in the nano silver material
For 10-80nm.
5. the method according to claim 1, wherein this method comprises: being total to acrylonitrile-butadiene-styrene (ABS)
Polymers and chemical modifier carry out melting extrusion granulation with the chopped bamboo fibre composite fibre of the nano silver-again after mixing,
Obtain the antimicrobial composite material；The length of the chopped bamboo fibre composite fibre of the nano silver-is 2-5mm.
6. the method according to claim 1, wherein this method comprises: making heat stabilizer, processing aid, ultraviolet
After at least one of absorbent and antioxidant are mixed with the acrylonitrile-butadiene-styrene copolymer and chemical modifier
The bamboo fibre composite fibre that is chopped again with the nano silver-carries out melting extrusion granulation, obtains the antimicrobial composite material；
The antioxidant is selected from β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, 2- (1,1- dimethyl
Ethyl) -6- methyl-phenol, at least one of double octadecyls of thio-2 acid；The heat stabilizer is misery selected from Malaysia
At least one of base tin or carboxylic acid tin, Methyl stannum mercaptide and sulfydryl ester group tin；The ultraviolet absorber is selected from 2,4- dihydroxy
Base benzophenone, ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxyls -3 ',
5 '-two tertiary phenyl) -5- chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4- t-octyl phenol oxygroup) nickel,
At least one of (1,2,2,6,6- pempidine base) phosphite ester, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Institute
Processing aid is stated to be selected from calcium stearate, be modified in ethylene bis stearamide, polyethylene wax and ethylene bis stearic acid amide extremely
Few one kind；
Wherein, relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the dosage of the antioxidant is 0.2-2 weight
Part is measured, the dosage of the heat stabilizer is 0.2-2 parts by weight, and the dosage of the ultraviolet absorber is 0.2-2 parts by weight, described to add
The dosage of work auxiliary agent is 0.2-4 parts by weight.
7. method according to claim 1 or 6, which is characterized in that this method comprises: keeping the nano silver-bamboo fibre multiple
Condensating fiber is chopped with after the coating processing of coupling agent surface, with compatilizer and/or dispersant, obtains the modified nanometer in surface
Silver-bamboo fibre composite fibre；
The compatilizer is selected from Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride
At least one of with ABS grafted maleic anhydride；The dispersing agent is selected from two polyphosphate sodiums, triethyl group hexyl phosphoric acid sodium, ten
Sodium dialkyl sulfate or at least one of fatty acid and macrogol ester；
Wherein, relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the dosage of the compatilizer is 0.5-5 weight
Part is measured, the dosage of the dispersing agent is 0.1-2 parts by weight.
8. method described in any one of -6 according to claim 1, which is characterized in that this method comprises: making polystyrene sulphur
Sour sodium and silver nitrate solution carry out redox reaction and obtain the solution containing nano silver material.
9. method described in any one of -6 according to claim 1, which is characterized in that the temperature that the melting extrusion is granulated is
210-250℃。
10. method described in any one of -6 according to claim 1, which is characterized in that the temperature of the supercritical fluid is
80-130 DEG C, pressure 60-130MPa.
11. method described in any one of -6 according to claim 1, which is characterized in that the pressure of the heating plasticizing and institute
The difference for stating the pressure of mold cavity is 50-100MPa, and the temperature of the mold is 50-80 DEG C.
12. method described in any one of -6 according to claim 1, which is characterized in that relative to 100 parts by weight of acrylonitrile -
Butadiene-styrene copolymer, the dosage of the supercritical fluid are 0.5-10 parts by weight.
13. the automotive upholstery that method described in any one of claim 1-12 is prepared.
14. a kind of automotive upholstery, which is characterized in that the automotive upholstery contain acrylonitrile-butadiene-styrene copolymer,
Be 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 the chopped bamboo fibre are 5-60 parts by weight, and the content of the nano silver material is 0.01-2 weight
Part, the content of the coupling agent is 0.1-10 parts by weight, and the content of the chemical modifier is 0.1-20 parts by weight；The coupling
Agent is silane coupling agent and/or titante coupling agent；The chemical modifier is selected from Aluminate, ethylene bis-fatty acid acyl
At least one of amine and chromium picolinate.
15. automotive upholstery according to claim 14, which is characterized in that the coupling agent and the chemical modifier
Content ratio is 1:(0.5-2.5).
16. automotive upholstery according to claim 14, which is characterized in that the nano silver material contains nano silver particles
And polystyrene, the weight ratio of the nano silver particles and polystyrene are 1:(1-20), nanometer in the nano silver material
The partial size of grain is 10-80nm.
17. automotive upholstery according to claim 14, which is characterized in that the length of the chopped bamboo fibre is 2-5mm.
18. automotive upholstery according to claim 14, which is characterized in that the automotive upholstery also contain compatilizer,
At least one of antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid；
The compatilizer is selected from Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride
At least one of with ABS grafted maleic anhydride；The antioxidant is selected from β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid
At least one of positive octadecanol ester, 2- (1,1- dimethyl ethyl) -6- methyl-phenol, the double octadecyls of thio-2 acid；
The heat stabilizer is selected from least one of maleic acid tin octylate or carboxylic acid tin, Methyl stannum mercaptide and sulfydryl ester group tin；Institute
Stating dispersing agent is selected from two polyphosphate sodiums, triethyl group hexyl phosphoric acid sodium, lauryl sodium sulfate or fatty acid and macrogol ester
At least one of；The ultraviolet absorber be selected from 2,4 dihydroxyl benzophenone, ESCALOL 567,
2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxyls -3 ', 5 '-two tertiary phenyl) -5- chlorination benzotriazole, single benzoic acid
Resorcinol, 2,2 '-thiobis (4- t-octyl phenol oxygroup) nickel, (1,2,2,6,6- pempidine base) phosphite ester, 4- benzene
At least one of formyloxy -2,2,6,6- tetramethyl piperidine；The processing aid is double selected from calcium stearate, modified ethylene
At least one of stearmide, polyethylene wax, ethylene bis stearic acid amide.
19. automotive upholstery according to claim 18, which is characterized in that the automotive upholstery also contain compatilizer,
Antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid, relative to 100 parts by weight of acrylonitrile-butadiene-benzene second
Alkene copolymer, the content of the compatilizer are 0.5-5 parts by weight, and the content of the antioxidant is 0.2-2 parts by weight, and the heat is steady
The content for determining agent is 0.2-2 parts by weight, and the content of the dispersing agent is 0.1-2 parts by weight, and the content of the ultraviolet absorber is
0.2-2 parts by weight, the content of the processing aid are 0.2-4 parts by weight.
20. automotive upholstery described in any one of 4-19 according to claim 1, which is characterized in that the automotive upholstery
For air-conditioner air outlet shell.
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|---|---|---|---|---|
| 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 |
| 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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