CN1467075A - Plastic-wood-metal composite structure material and method for producing the same - Google Patents
Plastic-wood-metal composite structure material and method for producing the same Download PDFInfo
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Abstract
A structural plastics-wood-metal composition is prepared from waste or used thermoplastic plastics, reinforcing particles, metallic structural member and modifier. Its advantages are high compression strength and bending strength, and environmental friendlinezz.
Description
Technical field
The present invention relates to a kind of sandwich, especially a kind of Plastic-wood-metal compound material and its preparation method.
Background technology
Wood plastic composite is the new chemical materials that develops rapidly in recent years.Worldwide, because the forest reserves are not enough day by day, cause water and soil to run off in a large number, it is more and more in short supply that wood supply becomes, therefore comparatively desirable as the substitute of timber with plastic-wood material, and have broad application prospects.The exploitation of Wood plastic composite has driven the revolution that new material is used; timber is in short supply for alleviating, and protects forest resources conscientiously, eliminates serious day by day " white pollution "; a kind of solution of comprehensively achieving many things at one stroke is provided, great social benefit and economic benefit have been arranged.
At present, plastic-wood material has application in a big way in the world as a kind of new green environment protection product.Existing production technology generally adopts mixes waste and old thermoplastic and waste and old wood fibre in certain proportion, again to wherein adding adhesive and additive, use traditional extruder and mould, adopt extrusion moulding, through high temperature, height is pressed into the high density structures section bar, and the polyolefin plastics of one of used extrusion molding raw material need be through strict grading, classification and letter sorting, require the dispersion of its molecular weight little, the more consistent polyolefin of molecular weight and the wood fibre that uses coupling agent modified processing are (as wood chip like this, plant stalk and rice husk etc.) powder heat the pressurization condition under, by screw extrusion molding, obtain to mould wooden composite article.There is following major defect in the Wood plastic composite that adopts existing extrusion moulding to make: 1. because the class requirement strictness of waste or used plastics, the high polyolefin of molecular weight dispersion is difficult to processing, therefore existing extruding-out process limits to some extent to needed raw material, and used polyolefin raw material is limited in the narrow scope; 2. extrusion efficiency is low, only is 0.1～0.3 meter/minute, certainly will cause the cost of product higher like this; 3. the resistance to compression of resulting product, flexural strength are poor.
Chinese patent CN1096730A discloses a kind of plastic-steel wood composite material and manufacture method thereof, to be rolled into sheet except that the timber bark, tree root, the treetop, inject resin, can add materials such as nylon fiber as reinforcement, carry out the plastic-steel wood section that multilayer stack, compression molding and cure under pressure are made difformity, specification.The manufacture method that this invention is adopted comprises following processing step: a. timber preprocessing moulding; B. timber preliminary treatment; C. resin injects; D. just molded; E. resin solidification.Wherein the first molded employing of steps d is preliminary compression-moulding methods, shape according to required section bar, requirements such as size and thickness, the still uncured sheet timber multilayer superposition of resin will be injected, in order to strengthen its intensity, can also between sheet timber, add fiber as reinforcement (as nylon fiber, nylon mesh sheet, carbon fiber etc.), be individually fixed on the die fixture according to the made mould of required section bar again, adjust relative position, the still uncured sheet timber of resin that enters that to repeatedly put well is again put into mould as the blank material, pressurization then, the vibration that in pressure process, keeps certain frequency, play the effect of vibrating, last preliminary compression molding.The used raw material of this invention is a timber, thus still can't resolve the problem serious in short supply of present timber resources, and also the cost of product is also than higher; In addition, it has added the fiber as reinforcement in order to strengthen its intensity, and the intensity of products obtained therefrom neither be very desirable.
Chinese patent CN2269954Y discloses a kind of hard plastic-steel composite that strengthens in wire, the reinforced net that has, and this utility model adopts inserts several layers wire, reinforced net section bar in plastic material, to solve the comprehensive mechanical performance of common plastics goods.The technical scheme of this utility model is: will make metallic mesh material after wire, the crooked splicing of muscle, again metallic mesh material is made the grid section bar, then this grid section bar is inserted extrusion molding, injection moulding or the pool and mould etc. in the particular manufacturing craft, uniting two into one with plastic material becomes hard plastic-steel composite.Chinese patent CN1036982C also discloses a kind of manufacturing technology of hard plastics-steel products of expanded metal lath enhancing, do skeleton by in the plastic material of plastic product, having added, with rigidity, reduction amount of deflection, the withstand voltage and cracking resistance of raising that improves original plastic product once the expanded metal lath specification section bar of self-reinforcing processing (cold drawn, cold rolling, clod wash).Because in the recombination process of structural material, there is bigger difference between the hot property of metal material and plastics, will inevitably cause its brittle cracking owing to the effect of stress after the goods cooling, but all unexposed again any technological means that solves this technical problem in above two pieces of patents, therefore prepared plastic-steel is moulded the easily curling and cracking phenomena of generation of wooden metal composite structure material, so that causes shorten dramatically the service life of product.
Summary of the invention
Defective at the prior art existence, main purpose of the present invention is to provide a kind of wooden metal composite structure material and manufacture method thereof of moulding, thereby realized matrix material and strengthened the polynary compound of powder, hardware, produced have high resistance to compression, high bending intensity mould wooden metal composite structure material.
Of the present inventionly mould wooden metal composite structure material and comprise: matrix material, strengthen powder, modifier and hardware, wherein the part by weight of matrix material and enhancing powder is between 90: 10～40: 60, and hardware weight accounts for 5～15% of sandwich gross weight.
The matrix used material of the present invention is thermoplastic plastics, waste plastics or its mixture, and used enhancing powder is wood fibre and/or mixture of fly ash.Used modifier is selected from the group of being made up of modifier A, modifier B, modifier C, modifier D and modifier E, and wherein modifier A is selected from the group of being made up of faintly acid salt and alkalescent salt; Modifier B is selected from the group by titante coupling agent, aluminium titanium compound coupling agent, dispersant and coupling material solvent composition; Modifier C is selected from the group of being made up of rare earth material and nano material; Modifier D is selected from the group of being made up of antioxidant, optothermal stabilizer, nucleator, crosslinking agent and fire retardant; Modifier E is a matal deactivator.
Of the present inventionly mould wooden metal composite structure manufacture of materials method, may further comprise the steps:
A. matrix material is mixed with the enhancing powder, add modifier A, wherein matrix material is thermoplastic plastics, waste plastics or its mixture, strengthening powder is wood fibre and/or trade waste flyash, matrix material is 90: 10～40: 60 with the part by weight that strengthens the powder addition, and modifier A is selected from the group of being made up of faintly acid salt and alkalescent salt;
B. step a gained mixed material is put into high mixer and stir, when temperature rises to 80～140 ℃, add modifier B, wherein modifier B is selected from the group by titante coupling agent, aluminium titanium compound coupling agent, dispersant and coupling material solvent composition;
C. when temperature rises to 120～160 ℃, step b gained material is put into the low machine that mixes, between 30～60 ℃ of temperature, cool off, stir, and adding modifier C, modifier D and modifier E, wherein modifier C is selected from the group of being made up of rare earth material and nano material, modifier D is selected from the group of being made up of antioxidant, optothermal stabilizer, crosslinking agent, nucleator and fire retardant, and modifier E is a matal deactivator;
D. with the resulting modified mixture of step c, put into extruder, the extruded material that between 100～200 ℃, heats, pressurizes, this extruded material is elastico-viscous body behind fusion plastification;
E. with the prefabricated hardware that is fixed to of metal material, this hardware weight accounts for 5～15% of sandwich gross weight, then described hardware is carried out surface treatment, at component surface compacting groove, then described hardware is inserted in the core rod of molding die or injection molding, as the reinforcement of product;
F. the resulting elastico-viscous body of steps d is put into described core rod, then primer fluid press or syringe pump, matched moulds, pressurization, cooling and shaping taking-up product then.
Of the present invention another mould wooden metal composite structure manufacture of materials method, may further comprise the steps:
A. will strengthen powder puts into high mixer and stirs, add modifier A and modifier B simultaneously, wherein said enhancing powder is wood fibre and/or trade waste flyash, this modifier A is selected from the group of being made up of weak acid salt and alkalescent salt, and modifier B is selected from the group by titante coupling agent, aluminium titanium compound coupling agent, dispersant and coupling material solvent composition;
B. in matrix material, add modifier C, modifier D and modifier E, mix with step a gained material then, wherein matrix material is thermoplastic plastics, waste plastics or its mixture, this matrix material is 90: 10～40: 60 with the part by weight that strengthens the powder addition, modifier C is selected from the group of being made up of rare earth material and nano material, modifier D is selected from the group of being made up of antioxidant, optothermal stabilizer, crosslinking agent, nucleator and fire retardant, and modifier E is a matal deactivator;
C. with the resulting modified mixture of step b, put into extruder, the extruded material that between 100～200 ℃, heats, pressurizes, extruded material is elastico-viscous body behind fusion plastification;
D. with the prefabricated hardware that is fixed to of metal material, this hardware weight accounts for 5～15% of sandwich gross weight, then this hardware is carried out surface treatment, at component surface compacting groove, then this hardware is inserted in the core rod of molding die or injection molding, as the reinforcement of product;
E. the resulting elastico-viscous body of step c is put into described core rod, then primer fluid press or syringe pump, matched moulds, pressurization, cooling and shaping taking-up product then.
Plastic-wood-metal compound material and its preparation method of the present invention compared with prior art has following characteristics and advantage:
1. realized the polynary compound of thermoplastic waste plastic and wood fibre and/or trade waste flyash, metal material, produced have high resistance to compression, the environment protective plastic-wood metal composite structure material of high bending intensity.
2. wood fibre that the process modification of adopting is handled and/or trade waste flyash and metallic material components have formed the enhancing system jointly, make the resistance to compression of moulding wooden metal composite structure material, the flexural strength produced improve 2～5 times.
3. adopt the mould pressing process once-through method to produce and mould wooden metal composite structure material, under the effect of modifier, with thermoplastic waste plastic and wood fibre and/or the blend of trade waste flyash, directly fusion is a resilient materials, after this technical process does not need granulation, heating and melting again, thus the degraded of high polymer reduced, saved production cost.
4. improve thermoplastic waste plastic's the degree of utilizing, solved the white pollution that waste or used plastics causes, had the remarkable environmental benefit.
5. the waste product of sandwich of the present invention, through after the fragmentation, the recyclable utilization of hardware, matrix resin and strengthen the filler that powder can be done vistanex processing, waste product can 100% be recycled, and can not produce new environomental pollution source.
The specific embodiment
Composite element of the present invention is polynary compound system, adopt thermoplastic plastics, waste plastics or its mixture as matrix material, wood fibre and/or flyash are as strengthening powder, constructed the enhancing network jointly with hardware, wherein strengthening powder is decentralized photo, be evenly dispersed in the matrix material, hardware is fixing phase, places the concentrated position of stress of structural material.The foundation of this enhancing network makes the mechanical property of structural material realize designability and controllability.
When the thermoplastic waste plastic is carried out the modification processing with the enhancing powder, because it is nonconforming reclaiming polyolefin kind, specification and the molecular weight of waste or used plastics, the low molecule of partial impurities or the segment of high polymer easy fracture enter macromolecular chain, formed " weak bond ", although the number of these weak bonds is less, seriously influence the structural behaviour of whole system.Simultaneously, owing to have very big-difference between matrix resin and the enhancing powder, bonding effect each other is poor, so in so polynary compound interface, exist complicated, changeable physical reactions and chemical reaction, only adopt single technical measures to be difficult to reach the mechanical property of multi-element composite material, therefore the present invention has adopted compound and technology blend, thermoplastic waste plastic and enhancing powder are carried out modification processing multi-faceted, the progress journey, so that comprehensively improve the rigidity and the toughness of structural material.The comprehensive effect of modifier will fully take into account factors such as chemical property coupling, acid-base balance, hot property and the crystallisation by cooling of moulding the polynary compound interface of wooden metal, physical geometry, optimizes the structural behaviour of polynary compound interface.
In making the polynary recombination process of moulding wooden metal composite structure material of the present invention, because the hot property of hardware and elastico-viscous body storeroom there are differences, cause that the curling of goods, cracking phenomena are serious, therefore the modification processing of material being combined with the correct method for posting of hardware, it is important to cause the pass, have only both organically combinations, can eliminate the stress of compound interface, improve the structural strength of whole system all sidedly.
To achieve these goals, there is technical problem in the present invention by adopting following technical measures to solve in the prior art:
1. in moulding wooden metal composite structure material system, form interpenetrating networks.Adopt titanate esters and aluminium titanium compound coupling agent hybrid modification material handling, impel as the raw materials used enhancing powder surface of the present invention and form and the same or analogous group of thermoplastic waste plastic, to increase the compatibility of whole system, coupling agent one end is with chemical bond and enhancing powder bonding, the other end is spread among the thermoplastic waste plastic, form high polymer interpenetrating networks (IPN) with macromolecular chain, realized the thermoplastic waste plastic and strengthened infiltration and adhered to one another mutually better between the powder.
2. regulate the acid-base balance of moulding in the wooden metal composite structure material system.Because wood fibre shows faintly acid, also residual certain acid and alkali substances such as the polyolefin antioxidant of Jia Ruing, optothermal stabilizer simultaneously, therefore in modification processing procedure of the present invention, the an amount of superfines that adds faintly acid or alkalescent salt, to regulate the acid-base balance of compound interface, make the gravitation of scolding of whole system electronic or ion reach good coupling.
3. in moulding wooden metal composite structure material system, introduced chemical bond.Because it is not enough that the bonding of compound interface only has molecular separating force, also need introduce chemical bond to strengthen bonding effect, by adding the proper amount of rare-earth material as the oxide of neodymium or praseodymium, because the surface active of rare-earth oxide can be low, has coordinate bond, can improve the infiltration degree at interface, accelerate the stress transmission speed at interface.
4. in moulding wooden metal composite structure material system, formed " core-shell particles ".Because the modifier that adopts among the present invention contains polyolefin-wax and coupling material solvent, impel coupling agent to improve degree of scatter, the coupling agent of polymolecularity will be coated on and strengthen the powder surface like this, thereby in system, form core-shell particles, make whole system not reduce rigidity, strengthened toughness simultaneously again.
5. but in moulding wooden metal composite structure material system, introduce the thermoplasticity boundary layer.Because inserting of hardware, the rigidity of whole system strengthens significantly, but because the hot property of hardware and high polymer is inconsistent, after this moulds wooden metal composite structure material product cooling, stress can cause its brittle cracking, so the present invention adopted the nano material with quantum effect, and is compound to form molecular level, can thermoplastic boundary layer thereby between hardware and viscoelastic material, introduced, the brittle fracture that eliminates stress and cause.Nano material is by stearic acid modified dose of processing.The limited passivation in surface reduces nano material self reunion tendency.Take to reduce the technical measures of elastico-viscous body material cooling velocity in core rod simultaneously, reduce the generation of stress.
In addition, hardware plays very important humidification of the present invention moulding in the wooden metal composite structure material.Be elastico-viscous body through modification processing back thermoplastic waste plastic and after strengthening the powder blended melting, this elastico-viscous body material is under the high shear forces of mold pressing, formed compound interface at the hardware borderline region of inserting core rod, be subjected to stretch orientation under the shearing force effect at this regional macromolecular chain; When crystallisation by cooling, the tangible strand of stretch orientation flocks together, form the fiber crystallization, and strand folding on the nuclei of crystallization of stretch orientation degree difference is gathered into wafer, wafer is arranged vertical with the Flow of Goods and Materials direction, Here it is so-called " mutton cubes roasted on a skewer " structural form, hardware can the performance superelevation in such structural form strengthen the property.
Therefore, there is double action in hardware in compound interface: the one, and the orderly arrangement of supporting wafers, thus promptly transmit and dispersive stress; The 2nd, the free electron passivation of metal, initiation thermoplastic waste plastic's degraded and aging, thereby the present invention has added matal deactivator in used modifier.
Owing to there is the effect of high shear force in mould pressing process, hardware slides in core rod relatively, cause tearing of compound interface, so the present invention has taked following technical measures to be overcome this technical barrier:
1. hardware is carried out surface treatment.Adopt mechanical force, at component surface compacting groove, with the contact area of increase hardware and viscoelastic storeroom, thereby between produces bigger frictional force.
2. the used metals such as metal material chosen from Fe, copper and aluminium of hardware are preferably metallic iron, and the hardware shape can be made into wire, stratiform, netted or helical form.
3. hardware is moulded wooden metal composite structure material product meta and is changed to limit in the product, angle and stress and concentrates the position of the present invention, and the geometric center at described position is placed axisymmetricly, balance inconsistent the and internal stress that causes of metal material and plastic-wood material shrinkage factor, eliminated the curling phenomenon of multi-element composite material.
4. mould in the core rod of mould of wooden metal composite structure material in production, be provided with the fixture and the flush mounting of metallic material components.Wherein fixture is inserted the inside of elastico-viscous body material, its coupling mechanism force and hardware to hardware can slidable thrust be balanced each other, although thereby can produce high shear force during mold pressing, the position of hardware in core rod still is metastable, do not take place floating or mobile.And after the material cooling, flush mounting then can be eliminated this coupling mechanism force, so that hardware can place the present invention to mould the design position of wooden metal composite structure material product.
Adopt and of the present inventionly mould wooden metal composite structure material and can be used to make carrier pallet, container bottom board, glassware packaging material, ammunition packing material, big shape wood gardens flowerpot and seabeach leisure chaise longue or the like.
Of the present inventionly mould wooden metal composite structure material and comprise: matrix material, strengthen powder, modifier and hardware, wherein matrix material and the part by weight of enhancing powder are between 90: 10～40: 60.
The matrix used material of the present invention is thermoplastic plastics, waste plastics or its mixture, and more preferably polyolefin is preferably polyethylene and/or polypropylene.
The used enhancing powder of the present invention is wood fibre and/or trade waste flyash, is preferably wood chip, plant stalk or the rice husk powder of granularity between 60～200 orders.
The used modifier of the present invention is selected from the group of being made up of modifier A, modifier B, modifier C, modifier D and modifier E.This modifier A is selected from the group of being made up of faintly acid salt and alkalescent salt, and the faintly acid salt is preferably ammonium chloride, and the alkalescent salt is preferably sodium acid carbonate or sodium acetate; This modifier B is selected from the group by titante coupling agent, aluminium titanium compound coupling agent, dispersant and coupling material solvent composition, wherein titante coupling agent is preferably monoalkoxy pyrophosphate class titante coupling agent or chelating titanate class coupling agent, dispersant is preferably polyolefin-wax, and coupling material solvent is preferably mineral oil; This modifier C is selected from the group of being made up of rare earth material and nano material, wherein rare earth material is preferably the oxide of neodymium or praseodymium, nano material is preferably the nano-calcium carbonate of average grain diameter between 40nm～100nm, and this nano-calcium carbonate can be through the limited Passivation Treatment in perstearic acid surface; This modifier D is selected from the group of being made up of antioxidant, optothermal stabilizer, nucleator, crosslinking agent and fire retardant; This modifier E is a matal deactivator.
The used metal material of the present invention is iron, copper or aluminium, is preferably iron.
Of the present inventionly mould wooden metal composite structure manufacture of materials method, may further comprise the steps:
A. will strengthen powder and carry out dry preliminary treatment, used baking temperature is between 40～100 ℃, be preferably between 60～80 ℃, dry 5～60 minutes, be preferably 10～30 minutes, moisture is controlled between the percentage by weight 1～10%, is preferably between 3～5%, wherein this enhancing powder is wood fibre and/or trade waste flyash, and wood fibre is preferably wood chip, plant stalk or the rice husk powder of granularity between 60～200 orders;
B. matrix material is mixed with the enhancing powder that step a obtains, add modifier A simultaneously, regulate acid-base balance, wherein this matrix material is 90: 10～40: 60 with the part by weight that strengthens the powder addition, matrix material is thermoplastic plastics, waste plastics or its mixture, polyolefin more preferably, be preferably polyethylene and/or polypropylene, modifier A is selected from the group of being made up of faintly acid salt and alkalescent salt, the faintly acid salt is preferably ammonium chloride, and the alkalescent salt is preferably sodium acid carbonate or sodium acetate;
C. step b gained mixed material being put into high mixer stirs, when temperature rises to 80～140 ℃, add modifier B, wherein modifier B is selected from the group by titante coupling agent, aluminium titanium compound coupling agent, dispersant and coupling material solvent composition, wherein titante coupling agent is preferably monoalkoxy pyrophosphate class titante coupling agent or chelating titanate class coupling agent, dispersant is preferably polyolefin-wax, and coupling material solvent is preferably mineral oil;
D. when temperature rises to 120～160 ℃, step b gained material is put into the low machine that mixes, between 30～60 ℃ of temperature, cool off, stir, and adding modifier C, modifier D and modifier E, wherein modifier C is selected from the group of being made up of rare earth material and nano material, rare earth material is preferably the oxide of neodymium or praseodymium, and nano material is preferably the nano-calcium carbonate of average grain diameter between 40nm～100nm, and this nano-calcium carbonate can carry out the limited Passivation Treatment in stearic acid surface; This modifier D is selected from the group of being made up of antioxidant, optothermal stabilizer, nucleator, crosslinking agent and fire retardant; This modifier E is a matal deactivator;
E. with the resulting modified mixture of steps d, put into and mould wooden special-purpose extruder, between 100～200 ℃, be preferably in the extruded material that heats, pressurizes between 140～180 ℃, extruded material is elastico-viscous body behind fusion plastification;
F. with the prefabricated hardware that is fixed to of metal material, then this hardware is carried out surface treatment, at component surface compacting groove, then this hardware is inserted in the core rod of molding die or injection molding, as the reinforcement of product, wherein in core rod, be provided with fixture and flush mounting, this metal material is iron, copper or aluminium, be preferably iron, the groove of being suppressed is three-dimensional thread or helical thread;
G. the resulting elastico-viscous body of step e is put into core rod, then primer fluid press or syringe pump, matched moulds, pressurization, cooling and shaping taking-up product then, wherein pressure is between 5～50Mpa, be preferably between 10～30MP, chilling temperature preferably is controlled between 30～40 ℃ between 20～60 ℃;
H. the product with the step g gained moves back mould, ejects, deburring and arrangement obtain finished product.
Of the present invention another mould wooden metal composite structure manufacture of materials method, may further comprise the steps:
A. will strengthen powder puts into high mixer and stirs, add modifier A and modifier B simultaneously, wherein this enhancing powder is wood fibre and/or trade waste flyash, and wood fibre is preferably wood chip, plant stalk or the rice husk powder of granularity between 60～200 orders; This modifier A is selected from the group of being made up of weak acid salt and alkalescent salt, and the faintly acid salt is preferably ammonium chloride, and the alkalescent salt is preferably sodium acid carbonate or sodium acetate; This modifier B is selected from the group by titante coupling agent, aluminium titanium compound coupling agent, dispersant and coupling material solvent composition, wherein titante coupling agent is preferably monoalkoxy pyrophosphate class titante coupling agent or chelating titanate class coupling agent, dispersant is preferably polyolefin-wax, and coupling material solvent is preferably mineral oil;
B. in matrix material, add modifier C, modifier D and modifier E, mix with step a gained material then, wherein matrix material is thermoplastic plastics, waste plastics or its mixture, and the part by weight of matrix material and described enhancing powder addition is 90: 10～40: 60; This modifier C is selected from the group of being made up of rare earth material and nano material, rare earth material is preferably the oxide of neodymium or praseodymium, nano material is preferably the nano-calcium carbonate of average grain diameter between 40nm～100nm, and this nano-calcium carbonate can carry out the limited Passivation Treatment in stearic acid surface; This modifier D is selected from the group of being made up of antioxidant, optothermal stabilizer, nucleator, crosslinking agent and fire retardant; This modifier E is a matal deactivator;
C. with the resulting modified mixture of step b, put into and mould wooden special-purpose extruder, between 100～200 ℃, be preferably between 140～180 ℃, extruded material heats, pressurizes, wherein mouthful molding pressure is between 10～30Mpa, and screw speed is between 30～50 rev/mins, and extruded material is elastico-viscous body behind fusion plastification;
D. with the prefabricated hardware that is fixed to of metal material, this hardware weight accounts for 5～15% of sandwich gross weight, then this hardware is carried out surface treatment, adopt mechanical force to suppress groove in component surface, then this hardware is inserted in the core rod of molding die or injection molding, reinforcement as product, wherein be provided with fixture and flush mounting in this core rod, this metal material is iron, copper or aluminium, be preferably iron, the groove of being suppressed is three-dimensional thread or helical thread;
E. the resulting elastico-viscous body of step c is put into described core rod, follow primer fluid press or syringe pump, matched moulds, pressurization, cooling and shaping take out product then, wherein pressure is between 5～50MPa, be preferably between 10～30MPa, chilling temperature is preferably between 30～40 ℃ between 20～60 ℃;
F. the product with step e gained moves back mould, ejects, deburring and arrangement obtain finished product.
Below in conjunction with embodiment, the present invention is further set forth, and can therefore not limit protection scope of the present invention.
Take the method for the following example to produce and mould wooden metal composite structure materials A, B, C, D, E and F.
Embodiment 1
A. be that 80 purpose wood chip powders carry out dry preliminary treatment with granularity, under 80 ℃ of temperature, dry 10 minutes, it was 4% that moisture is controlled at percentage by weight;
B. the waste and old refuse bag of polyethylene is cleaned broken back and mix with step a gained material, add ammonium chloride simultaneously, wherein the addition part by weight of polyethylene waste plastics and wood chip is 70: 30;
C. step b gained mixed material is put into high mixer and stir, when temperature rises to 90 ℃, add monoalkoxy pyrophosphate class titante coupling agent, aluminium titanium compound coupling agent, Tissuemat E and the frivolous oil of HK;
D. when temperature rises to 120 ℃, step c gained material is put into the low machine that mixes, under 30 ℃ of temperature, cool off, and to add antioxidant 1010, light stabilizer-744, crosslinking agent tert-butyl peroxide isopropylbenzene, fire retardant triphenyl phosphate, the two phenyl oxalamide acid diamides of metal passivator, granularity be the oxide of 400 purpose neodymiums, be the 40nm nano-calcium carbonate through stearic acid modified average particle size, stirred 8 minutes;
E. with the resulting modified mixture of steps d, put into and mould wooden special-purpose extruder, extruded material heats, pressurizes under 120 ℃, this extruded material is elastico-viscous body behind fusion plastification, wherein the draw ratio of this extruder is 1: 32, the compression section temperature is 140 ℃, and die temperature is 165 ℃, and screw speed is 32 rev/mins;
F. with the prefabricated hardware that is fixed to of metallic iron, hardware weight accounts for 10% of goods gross weight, then this hardware is carried out surface treatment, adopt the groove of mechanical force component surface compacting three-dimensional thread shape, then this hardware is inserted in the core rod of molding die, as the reinforcement of product, wherein in this core rod, be provided with fixture and flush mounting;
G. the resulting elastico-viscous body of step e is put into core rod, follow the primer fluid press, matched moulds, pressurization, cooling and shaping take out product then, and pressure is 20MPa, and chilling temperature is 30 ℃;
H. the product with the step g gained moves back mould, ejects, deburring and arrangement obtain finished product.
Made by above step and to mould wooden metal composite structure materials A, it is 1100 * 100 * 60mm I-beam, stacking test (1200kg, 24 hours): bending strength deflection degree value is that 1.9mm, deflection degree residual value are 0.76mm.
In addition, mould wooden metal composite structure materials A through waste and old after long-term the use, available alligator fragmentation after the iron member separates, is recycled, and residue can be used as the filler of PE Processing.
Embodiment 2
A. be that 150 purpose plant stalk powders carry out dry preliminary treatment with granularity, under 60 ℃ of temperature, dry 50 minutes, it was 3% that moisture is controlled at percentage by weight;
B. the useless plastic sheeting for farm use fragment of polyethylene is mixed with step a gained material, add sodium acid carbonate simultaneously, wherein the addition part by weight of polyethylene waste plastics and plant stalk powder is 80: 20;
C. step b gained mixed material is put into high mixer and stir, when temperature rises to 95 ℃, add chelating titanate coupling agent, aluminium titanium compound coupling agent, Tissuemat E, cycloalkyl YT-10 mineral oil;
D. when temperature rises to 140 ℃, step c gained material is put into the low machine that mixes, under 40 ℃ of temperature, cool off, and to add antioxidant 2246, auxiliary antioxidant 168, optothermal stabilizer 770, fire retardant TPP, metallic copper passivator N-salicyloyl-N '-acethydrazide, granularity be the oxide of 400 purpose praseodymiums, and be the nano-calcium carbonate of 80nm through the granularity of stearic acid modified processing, stirred 15 minutes;
E. with the resulting modified mixture of steps d, put into and mould wooden special-purpose extruder, the extruded material that under 160 ℃, heats, pressurizes, described extruded material is elastico-viscous body behind fusion plastification, the draw ratio of wherein said extruder is 1: 32, and screw speed is 35 rev/mins;
F. with the prefabricated hardware that is fixed to of metallic copper, this copper construction weight accounts for 12% of goods gross weight.Then described hardware is carried out surface treatment, adopt mechanical force to suppress spiral groove in component surface, then described hardware is inserted in the core rod of molding die,, wherein in this core rod, be provided with fixture and flush mounting as the reinforcement of product;
G. the resulting elastico-viscous body of step e is put into described core rod, follow the primer fluid press, matched moulds, pressurization, cooling and shaping take out product then, and pressure is 15MPa, and chilling temperature is 32 ℃;
H. the product with the step g gained moves back mould, ejects, deburring and arrangement obtain finished product.
Made by above step and to mould wooden metal composite structure material B, it is 1100 * 100 * 60 I-beams, and stacking test (1200kg, 24 hours): bending strength deflection degree value is 2.3mm, and the deflection degree residual value is 0.36mm.
In addition, mould wooden metal composite structure material B through waste and old after long-term the use, available alligator fragmentation after the copper member separates, is recycled, and residue can be used as the filler of PE Processing.
Embodiment 3
A. be that 200 purpose rice husk powders carry out dry preliminary treatment with granularity, under 60 ℃ of temperature, dry 20 minutes, it was 7% that moisture is controlled at percentage by weight;
B. the useless packaging bag broken material of polypropylene is mixed with step a gained material, add sodium acetate simultaneously, the addition part by weight of polypropylene waste plastics and rice husk powder is 50: 50;
C. step b gained mixed material is put into high mixer and stir, when temperature rises to 140 ℃, add chelating titanate coupling agent, aluminium titanium compound coupling agent, polypropylene wax and cycloalkyl YT-10 mineral oil;
D. when temperature rises to 160 ℃, step c gained material is put into the low machine that mixes, between 60 ℃ of temperature, cool off, and add antioxidant 1010, auxiliary antioxidant 618, nucleator EDBS, fire retardant TPP, matal deactivator DNP, granularity are the oxide of 400 purpose neodymiums, particle mean size through the limited Passivation Treatment in stearic acid surface is the nano-calcium carbonate of 100nm, stirs 45 minutes;
E. with the resulting modified mixture of steps d, put into and mould wooden special-purpose extruder, at 180 ℃ of extruded materials that heat, pressurize, described extruded material is elastico-viscous body behind fusion plastification, and wherein the compression ratio of extruder is 1: 32, and screw speed is 32 rev/mins;
F. with the prefabricated hardware that is fixed to of metallic aluminium, al member weight accounts for 6% of goods gross weight, then described al member is carried out surface treatment, adopt mechanical force to suppress spiral groove in component surface, then described al member is inserted in the core rod of injection molding, as the reinforcement of product, wherein in this core rod, be provided with fixture and flush mounting;
G. the resulting elastico-viscous body of step e is put into core rod, then start syringe pump, matched moulds, pressurization, cooling and shaping take out product then, and wherein pressure is 10MPa, and chilling temperature is 45 ℃;
H. the product with the step g gained moves back mould, ejects, deburring and arrangement obtain finished product.
Made by above step and to mould wooden metal composite structure material C, it is 1100 * 100 * 60 I-beams, and stacking test (1200kg, 24 hours): bending strength deflection degree value is 2.2mm, and the deflection degree residual value is 0.9mm.
In addition, mould wooden metal composite structure material C through waste and old after long-term the use, available alligator fragmentation after al member separates, is recycled, and residue can be used as the filler of polypropylene processing.
Embodiment 4
A. be that 80 purpose wood chip powders are after 200 purpose calcium bicarbonate powders mix with granularity with granularity, putting into high mixer stirs, add monoalkoxy pyrophosphate class titante coupling agent, aluminium titanium compound DL-1618 coupling agent, Tissuemat E and the frivolous oil of HK simultaneously, stirred 10 minutes;
B. clean that to add anti-agent 1010, optothermal stabilizer-770, crosslink agent DCP, fire retardant TPP, matal deactivator MD-1024, granularity in the fragment be 400 purpose neodymia, be the nano-calcium carbonate of 40nm to the useless refuse bag of polyethylene through the average particle size of the limited Passivation Treatment in stearic acid surface, then itself and step a gained material are mixed, wherein the addition part by weight of polyethylene waste plastics and wood chip powder is 70: 30;
C. with the resulting modified mixture of step b, put into and mould wooden special-purpose extruder, extruded material heats, pressurizes under 120 ℃, described extruded material is elastico-viscous body behind fusion plastification, the draw ratio of wherein said extruder is 1: 32, and screw speed is 32 rev/mins, and die temperature is 150 ℃;
D. with the prefabricated hardware that is fixed to of metallic iron, the iron construction weight is 12% of a goods gross weight, then described iron member is carried out surface treatment, adopt mechanical force at component surface compacting three-dimensional thread shape groove, then described iron member is inserted in the core rod of molding die, as the reinforcement of product, wherein in this core rod, be provided with fixture and flush mounting;
E. the resulting elastico-viscous body of step c is put into core rod, follow the primer fluid press, matched moulds, pressurization, cooling and shaping take out product then, and wherein pressure is 20MPa, and chilling temperature is 40 ℃;
F. the product with step e gained moves back mould, ejects, deburring and arrangement obtain finished product.
Made by above step and to mould wooden metal composite structure material D, it is 1100 * 200 * 30mm panel, and stacking test (300kg, 24 hours): the bending strength deflection value is 1.8mm, and the deflection value residual value is 0.12mm.
In addition, mould wooden metal composite structure material D through waste and old after long-term the use, available alligator fragmentation after the iron member separates, is recycled, and residue can be used as the filler of PE Processing.
Embodiment 5
A. be that 150 purpose plant stalk powders, flyash are after 100 purpose sodium acid carbonate powders mix with granularity with granularity, putting into high mixer stirs, plant stalk powder and flyash weight ratio are 50: 50, add integrated phosphate titanium coupling agent TMC-200S, titanium compound coupling agent DL-1618, Tissuemat E and cycloalkyl YT-10 mineral oil simultaneously, stirred 20 minutes;
B. adding antioxidant 1010, auxiliary antioxidant 618, optothermal stabilizer 770, fire retardant TPP, metallic copper passivator N-salicyloyl-N '-acethydrazide, granularity in polyethylene cable waste skin broken material is that 400 purpose praseodymium oxides, granularity are 80 purpose nano-calcium carbonates (through the limited Passivation Treatment in stearic acid surface), then itself and step a gained material are mixed, wherein the polyethylene waste plastics is 40: 60 with the addition part by weight that strengthens powder;
C. with the resulting modified mixture of step b, put into and mould wooden special-purpose extruder, extruded material heats, pressurizes under 160 ℃, extruded material is elastico-viscous body behind fusion plastification, wherein the draw ratio of extruder is 1: 32, and screw speed is 35 rev/mins, and die temperature is 150 ℃;
D. with the prefabricated hardware that is fixed to of metallic copper, construction weight is 12% of a goods gross weight, then this copper member is carried out surface treatment, adopt mechanical force to suppress spiral groove in component surface, then this copper member is inserted in the core rod of molding die, as the reinforcement of product, wherein in core rod, be provided with fixture and flush mounting;
E. the resulting elastico-viscous body of step c is put into core rod, follow the primer fluid press, matched moulds, pressurization, cooling and shaping take out product then, and wherein pressure is 20MPa, and chilling temperature is 35 ℃;
F. the product with step e gained moves back mould, ejects, deburring and arrangement obtain finished product.
Made by above step and to mould wooden metal composite structure material E, it is 1100 * 200 * 30 panels, and stacking test (300kg, 24 hours): bending strength deflection degree value is 2.1mm, and the deflection degree residual value is 0.1mm.
In addition, mould wooden metal composite structure material E through waste and old after long-term the use, available alligator fragmentation after the copper member separates, is recycled, and residue can be used as the filler of PE Processing.
Embodiment 6
A. be that 200 purpose rice husk powders and mixture of fly ash are put into high mixer and stirred with granularity, rice husk powder and flyash weight ratio are 60: 40, adding granularity simultaneously is 200 purpose sodium acid carbonate powders, stirred 2 minutes, and added the frivolous oil of monoalkoxy pyrophosphate class titanate esters, aluminium titanium compound coupling agent DL-1618, Tissuemat E, polypropylene wax and HK again and stirred 15 minutes;
B. after polyethylene and two kinds of useless refuse bags cleaning fragmentations of polypropylene, adding antioxidant 1010, auxiliary antioxidant 618, optothermal stabilizer 770, crosslink agent DCP, fire retardant TPP, matal deactivator DNP, granularity are that 400 purpose neodymia, granularity are 100 purpose nano-calcium carbonates (through the limited Passivation Treatment in stearic acid surface), then itself and step a gained material are mixed, mixing time is 5 minutes, and the addition part by weight of two kinds of waste plastic mixtures of polyethylene and polypropylene and rice husk powder and flyash is 50: 50;
C. with the resulting modified mixture of step b, put into and mould wooden special-purpose extruder, extruded material heats, pressurizes under 180 ℃, this extruded material is elastico-viscous body behind fusion plastification, wherein the draw ratio of extruder is 1: 32, and screw speed is 32 rev/mins, and the compression section temperature is 140 ℃;
D. with the prefabricated hardware that is fixed to of metallic aluminium, al member weight is 6% of goods gross weight, then this aluminum metal member is carried out surface treatment, adopt mechanical force to suppress spiral groove in component surface, then al member is inserted in the core rod of injection molding, as the reinforcement of product, wherein in this core rod, be provided with fixture and flush mounting;
E. the resulting elastico-viscous body of step c is put into core rod, then start syringe pump, matched moulds, pressurization, cooling and shaping take out product then, and wherein pressure is 25MPa, and chilling temperature is 40 ℃;
F. the product with step e gained moves back mould, ejects, deburring and arrangement obtain finished product.
Made by above step and to mould wooden metal composite structure material F, it is 1100 * 200 * 30 panels, and stacking test (300kg, 24 hours): bending strength deflection degree value is 2.8mm, and the deflection degree residual value is 1mm.
In addition, mould wooden metal composite structure material F through waste and old after long-term the use, available alligator fragmentation after al member separates, is recycled, and residue can be used as the filler of polyethylene, polypropylene processing.
Mould the physico-chemical property of wooden metal composite structure material product by the foregoing description 1 to embodiment 6 gained, further embody advance of the present invention as described below:
1. realized the thermoplasticity waste or used plastics and strengthened the polynary compound of powder, metal material, produced have high resistance to compression, the environment protective plastic-wood metal composite structure material of high bending intensity.
2. adopt enhancing powder and the metallic material components handled through modification to form the enhancing system jointly, improved the resistance to compression of moulding wooden metal composite structure material, the flexural strength produced.
3. adopt the mould pressing process once-through method to produce and mould wooden metal composite structure material, under the effect of modifier, with waste polyolefine plastics and the blend of enhancing powder, directly fusion is a resilient materials, after this technical process does not need granulation, heating and melting again, thus the degraded of high polymer reduced, saved production cost.
4. from moulding the aspect of performance of wooden metal composite structure material, it can substitute wood materials fully, and easy realization of industrialization can be protected China's Forest Resources in large area.
5. improve the degree of utilizing of thermoplasticity waste or used plastics, solved the white pollution that waste or used plastics causes, had the remarkable environmental benefit.
6. the waste product of moulding wooden metal composite structure material can 100% recycling after fragmentation, can not produce new environomental pollution source.
Although the present invention is illustrated in conjunction with the preferred embodiments, above embodiment only is exemplary, and for the person of ordinary skill of the art, the present invention can have various changes and variation.Various change of the present invention, variation and equivalent are contained by the content of appending claims.
Claims (17)
1. mould wooden metal composite structure material for one kind, comprising:
Matrix material, described matrix material are thermoplastic plastics, waste plastics or its mixture;
Strengthen powder, described enhancing powder is wood fibre and/or trade waste flyash;
Hardware; And
Modifier, described modifier is selected from the group of being made up of modifier A, modifier B, modifier C, modifier D and modifier E, described modifier A is selected from the group of being made up of faintly acid salt and alkalescent salt, described modifier B is selected from the group by titante coupling agent, aluminium titanium compound coupling agent, dispersant and coupling material solvent composition, described modifier C is selected from the group of being made up of rare earth material and nano material, described modifier D is selected from the group of being made up of antioxidant, optothermal stabilizer, nucleator, crosslinking agent and fire retardant, and described modifier E is a matal deactivator.
2. according to claim 1ly mould wooden metal composite structure material, wherein said thermoplastic waste plastic is a polyolefin.
3. according to claim 2ly mould wooden metal composite structure material, wherein said polyolefin is polyethylene and/or polypropylene.
4. according to claim 1ly mould wooden metal composite structure material, wherein said wood fibre is wood chip, plant stalk or the rice husk powder of granularity between 60～200 orders.
5. according to claim 1ly mould wooden metal composite structure material, wherein said hardware material is iron, copper or aluminium, and described hardware weight accounts for 5～15% of described sandwich gross weight.
6. according to claim 1ly mould wooden metal composite structure material, wherein said hardware material is an iron.
7. according to claim 1ly mould wooden metal composite structure material, wherein said hardware be shaped as wire, stratiform, netted or helical form.
8. according to claim 1ly mould wooden metal composite structure material, wherein said hardware places described limit, angle and the stress of moulding wooden metal composite structure material product to concentrate the position.
9. according to claim 1ly mould wooden metal composite structure material, wherein said limit, angle and stress concentrate the geometric center at position to place axisymmetricly.
10. according to claim 1ly mould wooden metal composite structure material, wherein said faintly acid salt is an ammonium chloride, and described alkalescent salt is sodium acid carbonate or sodium acetate.
11. according to claim 1ly mould wooden metal composite structure material, wherein said titante coupling agent is monoalkoxy pyrophosphate class titanate coupling agent or chelating titanate coupling agent.
12. according to claim 1ly mould wooden metal composite structure material, wherein said dispersant is a polyolefin-wax, described coupling material solvent is a mineral oil, and described rare earth material is the oxide of neodymium or praseodymium, and described nano material is the nano-calcium carbonate of average grain diameter between 40nm～100nm.
13. according to claim 1ly mould wooden metal composite structure material, the part by weight of wherein said matrix material and described enhancing powder is between 90: 10～40: 60.
14. a production method of moulding wooden metal composite structure material may further comprise the steps:
A. matrix material is mixed with the enhancing powder, add modifier A, wherein said matrix material is thermoplastic plastics, waste plastics or its mixture, described enhancing powder is wood fibre and/or trade waste flyash, the part by weight of described matrix material and described enhancing powder addition is 90: 10～40: 60, and described modifier A is selected from the group of being made up of faintly acid salt and alkalescent salt;
B. step a gained mixed material is put into high mixer and stir, when temperature rises to 80～140 ℃, add modifier B, wherein said modifier B is selected from the group by titante coupling agent, aluminium titanium compound coupling agent, dispersant and coupling material solvent composition;
C. when temperature rises to 120～160 ℃, step b gained material is put into the low machine that mixes, between 30～60 ℃ of temperature, cool off, stir, and adding modifier C, modifier D and modifier E, wherein said modifier C is selected from the group of being made up of rare earth material and nano material, described modifier D is selected from the group of being made up of antioxidant, optothermal stabilizer, crosslinking agent, nucleator and fire retardant, and described modifier E is a matal deactivator;
D. with the resulting modified mixture of step c, put into extruder, the extruded material that between 100～200 ℃, heats, pressurizes, described extruded material is elastico-viscous body behind fusion plastification;
E. with the prefabricated hardware that is fixed to of metal material, described hardware weight accounts for 5～15% of described sandwich gross weight, then described hardware is carried out surface treatment, at described metal component surface compacting groove, then described hardware is inserted in the core rod of molding die or injection molding, as the reinforcement of product;
F. the resulting elastico-viscous body of steps d is put into described core rod, then primer fluid press or syringe pump, matched moulds, pressurization, cooling and shaping taking-up product then.
15. according to claim 14ly mould wooden metal composite structure manufacture of materials method, wherein be provided with fixture and flush mounting described in the step e in the core rod.
16. an another kind of production method of moulding wooden metal composite structure material may further comprise the steps:
A. will strengthen powder puts into high mixer and stirs, add modifier A and modifier B simultaneously, wherein said enhancing powder is wood fibre and/or trade waste flyash, described modifier A is selected from the group of being made up of weak acid salt and alkalescent salt, and described modifier B is selected from the group by titante coupling agent, aluminium titanium compound coupling agent, dispersant and coupling material solvent composition;
B. in matrix material, add modifier C, modifier D and modifier E, mix with step a gained material then, wherein said matrix material is thermoplastic plastics, waste plastics or its mixture, the part by weight of described matrix material and described enhancing powder addition is 90: 10～40: 60, described modifier C is selected from the group of being made up of rare earth material and nano material, described modifier D is selected from the group of being made up of antioxidant, optothermal stabilizer, crosslinking agent, nucleator and fire retardant, and described modifier E is a matal deactivator;
C. with the resulting modified mixture of step b, put into extruder, the extruded material that between 100～200 ℃, heats, pressurizes, described extruded material is elastico-viscous body behind fusion plastification;
D. with the prefabricated hardware that is fixed to of metal material, described hardware weight accounts for 5～15% of described sandwich gross weight, then described hardware is carried out surface treatment, at described metal component surface compacting groove, then described hardware is inserted in the core rod of molding die or injection molding, as the reinforcement of product;
E. the resulting elastico-viscous body of step c is put into described core rod, then primer fluid press or syringe pump, matched moulds, pressurization, cooling and shaping taking-up product then.
17. production method of moulding wooden metal composite structure material according to claim 16 wherein is provided with fixture and flush mounting in the core rod described in the steps d.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101186755B (en) * | 2007-11-20 | 2010-10-13 | 广州华工百川科技股份有限公司 | Method for preparing coconut shell and thermoplastic plastic composite material |
| CN100999610B (en) * | 2006-01-12 | 2011-06-22 | 中国林业科学研究院木材工业研究所 | Wood plastic composite material composection and formed board thereof and their preparation process |
| CN102787714A (en) * | 2011-05-20 | 2012-11-21 | 严铁松 | Foamed plastic building template with five composite core layers |
| WO2014198081A1 (en) * | 2013-06-09 | 2014-12-18 | 东莞劲胜精密组件股份有限公司 | Plastic and metal composite material and manufacturing method thereof |
| CN104724350A (en) * | 2015-02-09 | 2015-06-24 | 喜悦(宁波)塑料包装品有限公司 | Thick wall plastic uptake tray based on composite material and forming method thereof |
| CN104787427A (en) * | 2015-02-09 | 2015-07-22 | 喜悦(宁波)塑料包装品有限公司 | Logistics container |
| CN110315621A (en) * | 2019-06-25 | 2019-10-11 | 广东技术师范大学天河学院 | A kind of composite material and preparation method |
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2003
- 2003-05-23 CN CN 03136938 patent/CN1255263C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999610B (en) * | 2006-01-12 | 2011-06-22 | 中国林业科学研究院木材工业研究所 | Wood plastic composite material composection and formed board thereof and their preparation process |
| CN101186755B (en) * | 2007-11-20 | 2010-10-13 | 广州华工百川科技股份有限公司 | Method for preparing coconut shell and thermoplastic plastic composite material |
| CN102787714A (en) * | 2011-05-20 | 2012-11-21 | 严铁松 | Foamed plastic building template with five composite core layers |
| WO2014198081A1 (en) * | 2013-06-09 | 2014-12-18 | 东莞劲胜精密组件股份有限公司 | Plastic and metal composite material and manufacturing method thereof |
| US9987780B2 (en) | 2013-06-09 | 2018-06-05 | Guangdong Janus Intelligent Group Corporation Limited | Plastic-metal composite material and manufacturing method thereof |
| CN104724350A (en) * | 2015-02-09 | 2015-06-24 | 喜悦(宁波)塑料包装品有限公司 | Thick wall plastic uptake tray based on composite material and forming method thereof |
| CN104787427A (en) * | 2015-02-09 | 2015-07-22 | 喜悦(宁波)塑料包装品有限公司 | Logistics container |
| CN110315621A (en) * | 2019-06-25 | 2019-10-11 | 广东技术师范大学天河学院 | A kind of composite material and preparation method |
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| CN1255263C (en) | 2006-05-10 |
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Assignee: Danyang Xinmeilong Autocar Soft Decoration Piece Plant Assignor: Zhang Shuzheng|Jin Shaopei Contract fulfillment period: 2006.6.18 to 2023.5.10 contract change Contract record no.: 2008320001096 Denomination of invention: Plastic-wood-metal composite structure material and method for producing the same Granted publication date: 20060510 License type: Exclusive license Record date: 20081110 |
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