CN103124626A - Multilayer plastics items with barrier properties and process for producing the same - Google Patents

Multilayer plastics items with barrier properties and process for producing the same Download PDF

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Publication number
CN103124626A
CN103124626A CN2011800455919A CN201180045591A CN103124626A CN 103124626 A CN103124626 A CN 103124626A CN 2011800455919 A CN2011800455919 A CN 2011800455919A CN 201180045591 A CN201180045591 A CN 201180045591A CN 103124626 A CN103124626 A CN 103124626A
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CN
China
Prior art keywords
layer
barrier properties
polymer
extruding
hydro carbons
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011800455919A
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Chinese (zh)
Inventor
D·尤利茨
R·赫尔米格
H·莱曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kautex Textron GmbH and Co KG
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Kautex Textron GmbH and Co KG
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Application filed by Kautex Textron GmbH and Co KG filed Critical Kautex Textron GmbH and Co KG
Publication of CN103124626A publication Critical patent/CN103124626A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/03—Fuel tanks
    • B60K15/03177—Fuel tanks made of non-metallic material, e.g. plastics, or of a combination of non-metallic and metallic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/10—Forming by pressure difference, e.g. vacuum
    • B29C51/105—Twin sheet thermoforming, i.e. deforming two parallel opposing sheets or foils at the same time by using one common mould cavity and without welding them together during thermoforming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0625—LLDPE, i.e. linear low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/086—EVOH, i.e. ethylene vinyl alcohol copolymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/16—EPM, i.e. ethylene-propylene copolymers; EPDM, i.e. ethylene-propylene-diene copolymers; EPT, i.e. ethylene-propylene terpolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/04—PVOH, i.e. polyvinyl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0032—Pigments, colouring agents or opacifiyng agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0044—Stabilisers, e.g. against oxydation, light or heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0065—Permeability to gases
    • B29K2995/0067—Permeability to gases non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7172—Fuel tanks, jerry cans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/70—Scrap or recycled material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Abstract

The present invention relates to multilayer plastics items, encompassing at least two layers based on non-polar polyolefins and, located between the said two layers and in direct contact with the same, a layer with barrier properties with respect to hydrocarbons, and also to a process for producing the same.

Description

Laminated plastics article and production method thereof with barrier properties
The present invention relates to the laminated plastics article, it comprise based on the two-layer at least of non-polar polyolefinic and comprise described two-layer between and with it the contact to hydro carbons have barrier properties the layer, the invention still further relates to its production method.
The container that is made of plastics now is widely used in transporting and storing dangerous liquids and gases product, because they have chemical resistance, and mechanical strength, good machinability is included in the processability in complicated moulding process particularly, and low weight.In the structure of vehicle, as exemplifying, the fuel container that is made of plastics has almost completely substituted the metal fuel container of previous routine.Now, portable or non--fixing container, for example for the gasoline cistern (petrol canister) of flammable liquid and analog, bottle, cylinder and fuel tank are also almost only by plastics-production.Than low weight/volume ratio, avoid finding in etching problem and low-cost production the special advantage of plastic containers especially.
Particularly, in described applying portion, to the liquid that is positioned at container/fuel tank internal and/or gas impermeable be important.Therefore, as exemplifying, current plastic containers must meet the strict Abgasgesetz with regard to the infiltration of hydrocarbon.
Vistanex, polyethylene for example, polypropylene and copolymer thereof have very good mouldability and machinability and high mechanical strength.Yet they are to volatile nonpolar organic matter matter, and especially the permeability of hydro carbons is relatively high.Therefore, transportation importantly is provided and/or stores to comprise hydro carbons, for example gasoline or diesel oil are in the suitable processing of container of interior dangerous substance.Especially by fluoridizing, coating or plasma polymerization can be significantly improved by the barrier properties of the plastic containers of these polyolefin manufacturings.
The common shortcoming of surface modification and coating process is that the barrier layer must be applied on the inside and/or outer surface of container, therefore is exposed under ambient influnence not protectedly.Therefore, along with time lapse, separation and/or the chemical modification on above-mentioned barrier layer can occur, and this can cause the remarkable infringement of barrier properties naturally.
Therefore, present research and development mainly concentrate on for example passes through coextrusion processes, produce and construct multilayer system, the polymer that wherein has barrier properties, be mainly that ethylene-vinyl alcohol copolymer (EVOH) and polyamide (PA) are integrated with polyolefin and other compositions, obtain multilayer materials.The common location of barrier polymers is roughly the centre of chamber wall; This first result that causes is to be minimized in the bending stress that produces in barrier polymers, and wherein when applying mechanical load, described barrier polymers great majority are relatively crisp, and the second result is that matrix material protection barrier polymers is avoided ambient influnence.Same possible situation is to use coextrusion technology, will be still further layer be integrated in multilayer materials, and therefore this method obtains the material with wide in range various advantageous properties that only uses single polymers not realize.
Yet shortcoming is usually as the polymer that has barrier properties and use, and for example ethylene-vinyl base co-polymer and polyamide have polarity usually, and with respect to nonpolar basic material, for example polyethylene and polypropylene, the bond properties that does not have any kind.Even two-layer also " bonding " of the described material of coextrusion is to going up each other under molten condition, after process for cooling or more early, they also are separated into the layer that separate in two spaces.
Therefore, use coextrusion, introduce adhesion-promoting layer between the layer of being made by the basic material of polyolefin manufacturing cheaply and the barrier layer of being made by obvious more expensive barrier polymers (it use bed thickness therefore also minimize), described adhesion-promoting layer is guaranteed inconsistent polarity and the durable bonding of nonpolar layer in other cases.As exemplifying, now, container in the motor vehicles part has six layers of structure that obtain by coextrusion usually, described six layers of structure comprise the basal layer that (from the inboard of container to the outside) made by the HDPF of " original (virgin) ", comprise recycled material, for example again comminution of material (being HDPE in fact equally) or consisting of the comminution of material layer, adhesion-promoting layer, barrier layer, another adhesion-promoting layer and another layer of being made by " original " HDPE.
Yet, for example for two extra extruders, introduce the installation cost of two-layer at least extra adhesion-promoting layer in the coextrusion thing, and other costlinesses of the system used of expressing technique reconstruct the impact that also has the huge increase of capital expenditure cost of this class system.
Other method provides uses polyarylamide as barrier material, moreover needs adhesion promotor herein, in order to guarantee stable being bonded to based on polyolefinic basic material.Yet, in this case, do not apply adhesion promotor in two independent stratums between basic material and barrier layer, but in first being processed, it joined in basic material.Yet this method requires very a large amount of adhesion promotors, and this is expensive equally.
Therefore, an object of the present invention is in the situation that do not damage the plastic article barrier properties, the technique of simplification is provided, this technique is favourable with regard to material cost and/or capital expenditure, and described cost and/or expense are along with production has the increase of each extruding layer that the laminated plastics article of barrier properties use and raises.But also should be preferably to the chemical resistance of plastic article, heat resistance or mechanical strength be infringement not.
Astoundingly, have now found that, allow to produce the method for the laminated plastics article with barrier layer, described barrier layer has concurrently to the barrier properties of hydro carbons with to the adhesion promotion performance of non-polar polyolefinic, and it can other extruding layers be combined by coextrusion processes with (from other extruders), but itself can be extruded by extruder.
The container of producing by the inventive method has good barrier properties to hydro carbons, and, also having extraordinary mechanical stability, described mechanical stability also is applicable to the adhesion strength between (applies to) independent extruding layer.
therefore, the invention provides the method for producing the laminated plastics article, it comprise based on the two-layer at least extruding layer of non-polar polyolefinic and described two-layer between and with it directly contact hydro carbons is had the extruding layer of barrier properties, wherein the method is included in the step of producing tubulose laminated plastics parison in the blowing system of coextrusion, wherein by proper what a extruder, by blend have barrier properties the layer extrude, described blend comprises that hydro carbons is had the polymer of barrier properties and comprises the polymer with adhesion promotion performance, and carry out described extruding under the melt temperature when the inner generation of blend has at least some layerings (demixing) of the polymer of barrier properties and the polymer with adhesion promotion performance to hydro carbons in extruder.
In the blend with barrier properties that causes because of two kinds of polymer viscosity difference at the temperature of using, the layering of two kinds of polymer occurs in the following manner, and the polymer that described mode makes great majority have barrier properties is disposed generally on the centre of extruding layer.
For the present invention, wording " based on the extruding layer of non-polar polyolefinic " refers to by weight, the extruding layer that is mainly formed by polyolefin, wherein these polyolefin can involve respectively " original " polyolefin, wherein polyolefinic ratio accounts for the comminution of material (" comminution of material again ") of main amount, or these mixture.Wording on this meaning " nonpolar " refers to without any polar group, acidic group for example, anhydride group, amide groups, the polyolefin of ester group or hydroxyl.
For purpose of the present invention, the layer that wording " directly contact " refers to hydro carbons is had barrier properties side and its downside thereon is bonded to respectively on layer based on nonpolar alkene.
For purpose of the present invention, wording " extruding layer " refers in coextrusion processes, any layer that can extrude by proper what a extruder, and with whether it has the structure-irrelevant of homogeneous on each size.On the contrary, for purpose of the present invention, different pattern or unevennesses is not extruding layer in described layer, even they itself have the structure of stratiform.
Due to the layering that realizes by the present invention in blend between two kinds of polymer, the polymer that therefore has a barrier properties exists with particle and the distribution heterogeneous of overlapping layer structure form mutually the extruding layer with barrier properties is inner.This method only use an extruder and only a kind of blend produce the goods that can be described as coating/sandwich construction of having realized blocking effect, in described structure, can be described as the structure that the structural correspondence of three layers of wall provides in the known plastic container with six layers of wall construction.
For purpose of the present invention, wording " layer structure that multilayer is overlapping " refers to mainly be parallel to the structure on plane, extruding layer place, and described structure space is limited and preferably form maximum successional interior poly-material layer by being in contact with one another.
In the method for the invention, melt temperature scope in the extrusion of the layer with barrier properties is preferably 160 ℃-260 ℃, and preferable range is 180 ℃-240 ℃, and preferable range is 200 ℃-225 ℃, especially preferred scope is 205 ℃-215 ℃, and especially scope is 208 ℃-212 ℃.Yet, if temperature higher than 260 ℃, two kinds of polymeric blends and gained layer have obviously relatively poor barrier properties in having the extruding layer of barrier properties.
In order to extrude in the method for the invention the layer with barrier properties, preferred use does not have the screw extruder of cutting out section and/or mixing portion, and especially preferred use does not have cutting out section and do not have the screw extruder of mixing portion.
In the method for the invention, preferably select respectively independently of one another the freely group of following composition based on the polyolefin in polyolefinic two-layer at least extruding layer: nonpolar high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), polypropylene (PP), ethylene-propylene copolymer and these mixture, can use or " original " material herein, perhaps comminution of material (" comminution of material again "), perhaps or these mixture.Preferably this is two-layer respectively based on nonpolar high density polyethylene (HDPE) (HDPE).
As hydro carbons being had the polymer of barrier properties, preferably to use at the temperature of 210 ℃ and under the load at 2160g, melt flow speed is 2-10g/10min, the polymer of preferred 3-5g/10min (measuring according to ISO1133).The density of polymer is preferably approximately 1.0-1.3g/cm 3(measuring according to ISO1183).The melting range of the barrier polymers of using is preferably 160 ℃-200 ℃, and preferable range is 180 ℃-190 ℃ (measuring according to ISO11357).
As hydro carbons being had the polymer of barrier properties, the polymer that uses in the inventive method preferably selects the polymer in the group of free following composition: ethylene-vinyl alcohol copolymer (EVOH), polyarylamide, polyamide (PA), polyvinyl alcohol (PVOH), PET (PET), and their mixture.The polymer that hydro carbons is had a barrier properties is ethylene-vinyl alcohol copolymer (EVOH) especially preferably, and especially is preferably based on the molecular composition of copolymer, and the ethene ratio is the ethylene-vinyl alcohol copolymer of 28-36mol%.In an especially preferred embodiment, the layer with barrier properties does not comprise polyamide together with ethylene-vinyl alcohol copolymer.
Polymer with adhesion promotion performance is preferably selected from the functionalized polyolefin of polar group, preferably with unsaturated carboxylic acid or with the functionalized polyethylene of carboxylic acid anhydrides.The example of this base polymer is ethene and unsaturated carboxylic acid or carboxylic acid anhydrides, acrylic acid for example, methacrylic acid, the copolymer of maleic acid or maleic anhydride.Especially the copolymer of optimal ethylene and maleic anhydride, wherein copolymer preferably includes the gross weight based on polymer, 0.05-5wt% maleic anhydride, more preferably 0.1-1wt%, and especially preferred 0.2-0.3wt% maleic anhydride.
The scope of weight portion and the ratio of the weight portion of the polymer with adhesion promotion performance that has the polymer of barrier properties in blend is preferably 15:85-40:60, especially preferable range is 20:80-35:75, especially scope is 25:75-30:70, in each situation based on the gross weight of this blend.
The thickness 2-10% of the bed thickness sum of described layer and two-layer polyolefin layer preferably with extruding layer of barrier properties, preferred 3-8%, and especially preferred 5.5-7.5%.
The laminated plastics article of producing by the inventive method can with based on polyolefinic two-layer and have and comprise further extruding layer together with the layer of barrier properties, described extruding layer independently of one another by coextrusion be applied to polyolefin-basic unit one deck or two-layer on, and directly contact with the extruding layer that hydro carbons is had barrier properties.As exemplifying, in the fuel container situation, (from the inboard, namely from towards a side of fuel) can be preferred following layer structure: HPDE, for purpose of the present invention, extruding layer with barrier properties comprises HDPE as main component, the comminution of material of being made by comminution of material again of the HPDE of black.
Same possible be, the one deck in plastic article or more multi-layered extruding layer especially comprise additive based on polyolefinic extruding layer, fiber for example, and filler, pigment, antioxidant etc., but be not limited to these.Yet the extruding layer that preferably has barrier properties does not comprise filler, for example is called the material of clay.
Preferably, be used for transporting or be used for storing liquid and/or gaseous hydrocarbons, especially fuel, the multilayer hollow plastic body of gasoline or diesel oil for example, the spare and accessory parts that perhaps are used for described hollow plastic body consist of the plastic products of producing in the method for the invention, filler neck (filler neck) for example, pump, loading pipe, fill-flatten indicator (fill-level indicators), and ventilation unit, for example valve, or permanent plant, but be not limited to these.The laminated plastics article especially preferably include fuel container.
The present invention further provides the laminated plastics article, it comprises two-layer at least based on non-polar polyolefinic, and described two-layer between and with it directly contact hydro carbons is had the layer of barrier properties, the layer that wherein has barrier properties comprises that hydro carbons is had the polymer of barrier properties and comprises the polymer with adhesion promotion performance, and the polymer that wherein has a barrier properties exists with particle and the distribution heterogeneous of overlapping layer version mutually the layer with barrier properties is inner.
The layer that the present invention has a barrier properties forms the so-called three-decker of a barrier material in the middle of concentrating on, and this be expressing technique and in the expressing technique process result of the particular hierarchical of blend.Use only three extruders, this method obtains so-called five layers of wall construction.
These laminated plastics article of the present invention are preferably by above-described the inventive method production so that two-layer based on non-polar polyolefinic, with betwixt and the layer with barrier properties that directly contacts with it involve respectively extruding layer.
Further step, perhaps to obtain the possibility of actual plastic article be respectively well known by persons skilled in the art to the parison produced in the methods of the invention of processing.
Can be for this purpose, according to known way, to have axially or the extruder head that used in the methods of the invention of the capitiform formula design of raw material radially, wherein from extruder out molten material flows the axle peripheral shaft to or Radial Flow.Also can by the flow channel that designs suitably, molten material flows be departed from extruder head.In another possible layout, can provide separator herein, side cutting or subdividing multilayer tubular parison, by a plurality of elongations, straight linear die gap, with sheet material-or the parison form of net shape occur.
As exemplifying, therefore can according to known way, by extrusion-blown modling, obtain fuel container by described tubular parison.As an alternative, also can cut parison open, obtain the semi-finished product product of at least two sheet, then hot forming obtains half-shell (half-shells), then welding, obtain ducted body, but the present invention is not restricted on these above-mentioned possibilities.
The present invention also can comprise and extrude the semi-finished product product, and described semi-finished product product is sheet material or net form, and intends being used for hot forming.

Claims (13)

1. produce the method for laminated plastics article, it comprise based on the two-layer at least extruding layer of non-polar polyolefinic and described two-layer between and with it directly contact hydro carbons is had the extruding layer of barrier properties, wherein the method is included in the step of producing tubulose laminated plastics parison in the blowing system of coextrusion, it is characterized in that only with an extruder, by blend have barrier properties the layer extrude, described blend comprises that hydro carbons is had the polymer of barrier properties and comprises the polymer with adhesion promotion performance, and carry out described extruding under the melt temperature when carrying out at least some layerings of the polymer that hydro carbons had the polymer of barrier properties and have the adhesion promotion performance in blend inside in extruder.
2. the method for claim 1, the polymer that it is characterized in that having barrier properties exist the extruding layer with barrier properties is inner, with particle and mutually the form of overlapping layer structure anisotropically distribute.
3. claim 1 or 2 method, is characterized in that melt temperature range is 160 ℃-260 ℃, and preferable range is 200 ℃-225 ℃, and preferable range is 205 ℃-215 ℃, and especially preferable range is 208 ℃-212 ℃.
4. any one method of claim 1-3 is characterized in that the layer that has barrier properties in order to extrude using the screw extruder that does not have cutting out section and/or mixing portion, does not preferably have cutting out section and does not have the screw extruder of mixing portion.
5. any one method of claim 1-4, it is characterized in that selecting respectively independently of one another the freely group of following composition based on the polyolefin in polyolefinic two-layer at least extruding layer: nonpolar high density polyethylene (HDPE) (HPDE), low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), polypropylene (PP), the mixture of ethylene-propylene copolymer and these, preferably this two-layer be respectively non-polarity high density polyethylene (HDPE) (HDPE).
6. any one method of claim 1-5, it is characterized in that to the polymer that hydro carbons has a barrier properties be the freely polymer in the group of following composition of choosing: ethylene-vinyl alcohol copolymer (EVOH), polyarylamide, polyamide (PA), polyvinyl alcohol (PVOH), and their mixture, preferably ethylene-vinyl alcohol copolymer (EVOH), especially be preferably based on the molecular composition of copolymer, the ethene ratio is the ethylene-vinyl alcohol copolymer of 28-36mol%.
7. any one method of claim 1-6, it is characterized in that the polymer with adhesion promotion performance is selected from the functionalized polyolefin of polar group, the copolymer of optimal ethylene and unsaturated carboxylic acid or carboxylic acid anhydrides, the especially copolymer of optimal ethylene and maleic anhydride.
8. any one method of claim 1-7, the scope of weight portion and the ratio of the weight portion of the polymer with adhesion promotion performance that it is characterized in that having the polymer of barrier properties in blend is preferably 15:85-40:60, preferred 20:80-35:75, especially preferred 25:75-30:70, in each situation based on the gross weight of this blend.
9. any one method of claim 1-8, the thickness that it is characterized in that having the extruding layer of barrier properties is the 2-10% of the bed thickness sum of described layer and two-layer polyolefin layer, preferred 3-8%, especially preferably 5.5-7.5%.
10. any one method of claim 1-9, it is characterized in that the laminated plastics article comprise further extruding layer, described further extruding layer independently of one another by coextrusion be applied to polyolefin basic layer one deck or two-layer on, and directly contact with the extruding layer that hydro carbons is had barrier properties.
11. any one method of claim 1-10 is characterized in that for transportation or is used for storing the multilayer hollow plastic body of liquid and/or gaseous hydrocarbons, perhaps is used for the spare and accessory parts of described hollow plastic body, the preferred fuel container.
12. laminated plastics article, it comprises two-layer at least based on non-polar polyolefinic, and described two-layer between and with it directly contact hydro carbons is had the layer of barrier properties, the layer that wherein has barrier properties comprises that hydro carbons is had the polymer of barrier properties and comprises the polymer with adhesion promotion performance, it is characterized in that, polymer with barrier properties exists the layer with barrier properties is inner, with particle and mutually the form of overlapping layer structure anisotropically distribute.
13. the laminated plastics article of claim 12 is characterized in that comprising respectively based on the two-layer and therebetween of non-polar polyolefinic and the layer with barrier properties that directly contacts with it the extruding layer of producing by claim 1-12 any one or multinomial method.
CN2011800455919A 2010-09-24 2011-08-26 Multilayer plastics items with barrier properties and process for producing the same Pending CN103124626A (en)

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