CN101044013A - Composite pipes and methods of making same - Google Patents

Abstract

The invention relates to a reinforced multiunit tube and the manufacturing method, often using at least a collective wild phase which is usually provided in an intermediate form (214). The intermediate form usually covers on a core tube (216) and can be consolidated. An optional sheath (212) can be used.

Description

Multiple tube and manufacture method thereof

Claim of priority

The application requires the U.S. Provisional Application Nos.60/621 of submission on October 22nd, 2004,463 (attorney docket 63863; 1062-041P1); 60/717,965 (the attorney docket 63863B that on September 16th, 2005 submitted to; 1062-041P2); 60/718, the 025 (attorney docket 64371 that on September 16th, 2005 submitted to; 1062-051P1); 60/725,399 (the attorney docket 63863C that on October 11st, 2005 submitted to; 1062-041P3), the priority of (express delivery EV789808245US) and submission day rights and interests, all these are all incorporated herein by reference.

The cross reference of related application

The application with submit to simultaneously, own together, the name of common pending trial is called Apparatus andProcess for Manufacturing Shaped Plastic Reinforced Composite Articles (attorney docket 64371A; 1062-051WO); Improved Polyolefinic MaterialsFor Plastic Composites (attorney docket 63863D; 1062-41WO1); PlasticComposite Articles and Methods of Making Same (attorney docket 63863E; 1062-41 WO2); With Improved Microlayer Structures and Methods (attorney docket 63863F; Application 1062-41WO3) is relevant; All these are all incorporated herein by reference.

Technical field

The present invention relates generally to tubing, more specifically, relates to the multiple tube that uses at least a polymerization wild phase.

Background technology

The past many decades, by the development of improved composite, engineering material has obtained marked improvement.Composite makes the designer can be with the favorable characteristics of multi-component material in conjunction with to obtain to have usually the material of one or more character different with single component material.

Progressive field especially rapidly is the reinforced plastics field.For example, be the way of passing through by mixing the character that inorganic wild phase (for example using the fiber of being made by glass, carbon, metal or another inorganic material) improves plastics.In many cases, provide comprise inorganic reinforcement and with thermoplasticity or thermosetting plastics matrix impregnation or with the form (form) of thermoplasticity or the blend of thermosetting plastics matrix.All the more an object lesson of popularizing is glass fiber felt thermoplastic plastics (GMT) composites in recent years, and it uses the glass mat with the thermoplastic dipping of polypropylene and so on usually.Material type difference between glass and the thermoplastic matrix often makes the effort of any recovery of these GMT materials and recirculation complicated.

In recent years, plastics industry is also tested the development of the thermoplasticity " fabric " of using one or more thermoplastic fibres weaving (wherein also using or do not use glass fibre).Usually, these materials provide with weaving and consolidation form, just after with fibrage, their are heated to melt its at least a portion outer surface.After curing, adjacent fiber is consolidated.

Up to now, just making great efforts to obtain being easy to be processed to form the suitable thermoplasticity enhanced form of resulting product.Observe, for example, consolidation step (wherein fiber or other unit with enhanced form heats to fuse together) requires at least the first thermal history, and the step that forms the gained moulded products requires at least the second thermal history.Along with each additional use that adds thermal history, the possibility that form changes increases, and is accompanied by the mechanicalness loss of energy.

A special purposes of plastics reinforced composite materials is the tubing manufacturing.Cabrera incorporated herein by reference, " Recycleable All-Polypropylene Composites:Concept, Properties and Manufacturing ", Technische Universiteit Eindhoven (2004) (ISBN 90-386-2676-2) disclose the example with a kind of method of twining manufactured tubing.Also referring to BP 2279232, it is incorporated herein by reference.The multiple tubing that manufacturing has the wide feature scope is attractive.

Summary of the invention

Roughlly speaking, content disclosed by the invention relates to the method for making multiple tube, and it comprises the following steps: to carry core tube feeding; Cover core pipe (for example being made by polymer) with the intermediate form (intermediate form) that comprises at least one circle (winding) thermoplasticity elongated member, wherein elongated member comprises first thermoplastic and second thermoplastic; Fixed intermediate form; On at least a portion of intermediate form and core pipe, apply sheath has intermediate form with protection core pipe with choosing wantonly.

Described intermediate form generally includes a plurality of elongated member layers, and wherein one deck comprises the elongated member that is stretched at least about 5x (and can up to 15x or higher) at least.Described elongated member can comprise multi-layer co-extruded band (coextruded tape) and consolidation step, when particularly in elongated member, using the acrylic polyolefin, be included in intermediate form and cover after the core pipe, with intermediate form about at least 1 minute of about at least 150 ℃ of maintenances.Can use multi-lay winding.

If the use sheath, it generally includes polymer, and described sheath has the pressure rating (according to ISO 9080) greater than about PE80.Gained tubing has the maximum 250 hours circumferential stress performance of pressure of bearing 7MPa at 80 ℃.At least a of any sheath that applies and/or the thermoplastic of intermediate form can comprise non-migrating processing aid as herein described or surface modifier.In one approach, at least a ethene that comprises in first thermoplastic and second thermoplastic.In particular aspects, elongated member is comprised first thermoplastic of propylene-ethylene copolymers by following making (i), second thermoplastic that (ii) comprises isotactic polypropylene homopolymers (for example having about at least 30% degree of crystallinity, the isotaxy five unit groups greater than about 70%/three unit group ratios); Or combination (i) and (ii).Many microbeddings can be used for elongated member.

In one approach, before at least a portion that sheath is applied to intermediate form and core pipe, carry out the step of fixed intermediate form.In other method, carry out consolidation step by the heat that in applying the step of sheath, obtains.

Description of drawings

Figure 1A and Figure 1B have shown the example of the cross section of possibility elongated member of the present invention.

Fig. 2 A and Fig. 2 B have shown the example according to unconsolidated and fixed intermediate form of the present invention respectively.

Fig. 3 is the perspective view according to exemplary moulding intermediate form of the present invention.

Fig. 4 A-4G has shown according to pipe structure of the present invention.

Fig. 5 A and 5B have shown can be by the exemplary correction data of the present invention's acquisition.

Fig. 6 A and 6B have shown can be by the example data of the present invention's acquisition.

Detailed Description Of The Invention

About the manufacturing according to multiple tube of the present invention, particular aspects relates to be made intermediate form and comprises that step a) provides at least one elongated member of the first thermoplastic, its have can in abutting connection with or interior section (for example internal approach part) fusing before the surface portion of fusing; And b) elongated member is processed into the intermediate form that comprises a plurality of constitutional repeating units, these construction units can move freely usually relative to one another, wherein this form can be processed to form essentially smooth, without wrinkle moulding end article. Generally speaking, in each situation, all do not require (for example for microbedding disclosed herein (microlayer)) although be not, elongated member comprises orientation polyolefine, and the orientation polyolefine that particularly can process according to the present invention keeps its initial configuration substantially.

The procedure of processing of this paper can also comprise fixed and (for example form three-dimensional intermediate form, in single operation, carry out simultaneously or in a plurality of operations, carry out continuously) step, this intermediate form comprises a plurality of constitutional repeating units of at least one elongated member and the first thermoplastic, and it has the surface portion that can melt before at adjacent part (for example in abutting connection with alignment portion); Fixed and intermediate form moulding are placed die cavity; In die cavity, add the second thermoplastic; And from die cavity, release the reinforced composite pipe comprise fixed intermediate form and the second thermoplastic. It is fixed to carry out part in the step that adds the second thermoplastic in die cavity. Certainly, this illustrative aspects can be combined with above-mentioned the first illustrative aspects or be implemented separately. Therefore, can make intermediate form and resulting product by a manufacturer, or make respectively (for example material supplier provides intermediate form to product manufacturer) by different manufacturers. In addition, can before in die cavity, adding the second thermoplastic, in that this form is not fixed situation, carry out above-mentioned steps. Because the high form in the elongated member of the goods part keeps degree, the typical products and its of making according to disclosing of this paper advantageously show excellent impact and correlation properties (particularly because this ability, owing to use unique material to select or combination, and/or processing conditions).

As shown in the present, various aspects of the present invention are with the basis that is found to be to material, procedure of processing or both unique combination---these combinations cause the elongated member material have relatively high form keep degree (with after its incipient extension and be processed into composite article initial configuration before and compare). Thus, content disclosed herein advantageously can make the maintenance of gained composite article such as the performance of impact property and so on.

Can find out that content disclosed herein relates to the new material combination that can be used for field of compound material, particularly with can be by fixed and optional relevant with the elongated member that forms multiple tube by moulding and processing.

As can be seen, the present invention has set forth the polyolefine material various aspects from content disclosed herein, but can not therefore disclosure of the present invention is restricted.Specific progress provided by the invention comprises the special polyolefins combination of materials of having determined to have unique applicability in field of compound material.Especially, one aspect of the present invention be prerequisite used as acrylic (for example propylene-ethylene copolymers, propylene-alpha-olefin copolymers with above-mentioned determined content, their mixture or other) the multilayer elongated member of copolymer, its fusing point is lower than in abutting connection with polypropylene layer, particularly the oriented polypropylene layer.As described herein, in case be processed to form after the goods, gained material (especially oriented polypropylene layer) shows the form of using traditional material to be beyond one's reach before this to compare with its incipient extension state and keeps degree.Therefore, each side of the present invention is that about 3 to 25wt% (for example 5 to 15wt%), melting range are about 50 to 135 ℃ with ethylene contents, and bending modulus is about 8 to about 325Mpa or the propylene-ethylene copolymers of higher (for example at least approximately 375MPa) and comprise that the using of second thermoplastic of polyolefin (for example propenyl polymer) is prerequisite.This propylene-ethylene copolymers can have about Xiao A hardness of 40 to 90, about 1.5 to about 4 molecular weight distribution and at least about 0.3g/10 minute melt flow rate (MFR), or their any combination.

An example of available propenyl polymer is normally isotactic or relative stiffness.For example, it can be the 1% secant bending modulus that has greater than about 1000MPA (more special in about 2000MPa (for example about 2500MPa or higher)), isotaxy five unit groups/three unit group ratios are greater than the polypropylene homopolymer of about 70% (for example greater than about 85%), or the two all has.In addition, this polypropylene has the high melting temperature greater than about 160 ℃ (for example greater than about 165 ℃) usually, the degree of crystallinity of about at least 30% (more special about at least 50% or even 70%), or the both has.

The open of this paper is prerequisite with following understanding also---by using consumption to be lower than the optional non-migrating processing aid or the surface modifier of about 10wt% of the material of elongated member, can obtain favourable outcome with above-mentioned polymer or with other polymer as herein described.As an example, non-migrating processing aid or surface modifier can comprise the reagent that is selected from siloxanes (for example high molecular weight silicone, for example alkylsiloxane, for example dimethyl siloxane), polyolefin, halogen polymer or their any combination.

About the novel combination of material, disclosing of this paper determined by using geophysics textile material (for example polyolefin geophysics fabric) to make the beat all method of composite therein.For example, a kind of such method has been imagined provides the intermediate form that comprises the geophysics fabric, and Overmolded (overmolding) or otherwise process this intermediate form to form the step of pipe structure.Randomly, can use above-mentioned non-migrating processing aid or surface modifier.

The open of this paper also shows, the present invention relates to at least 4 layers of stack layer is the embodiment of feature, each layer includes polymer, each layer all has less than about 50 microns thickness (more generally obviously thinner, for example may even be thinner than about 5 microns), and each layer to be adjacent layer different at least one feature that is selected from composition, degree of crystallinity, molecularly oriented, molecular weight, melt speed, high melting temperature, glass transition peak value, crystallization temperature, sealing initiation temperature, softening point, molecular weight distribution or its any combination.

As can be seen, but be not restrictively, except the characteristic of material itself and their form processing, the goods made from material as herein described that also relate to of the present invention are made the method for further concrete grammar and this based article of use of this based article.

Elongated member and intermediate form

Intermediate form of the present invention at first is discussed, and generally speaking, these forms comprise that at least one has the elongated member of the composition that comprises at least a thermoplastic." elongated member " typically refer to one of dimension (for example length) be longer than at least one other dimension (for example width, highly, thickness or diameter) element, especially, the length of elongated member at this obviously greater than (for example about greatly at least 10 times or higher) width or height.Therefore, elongated member can comprise at this, but not necessarily is limited to, and is selected from the element of fiber, shaft, rope, yarn, band, monofilament, band (straps) or its any combination.From above recognizing, in many aspects in, film also can be considered in the implication of " elongated member ".Miniaturized component also is feasible, for example whiskers or tablet.Although " elongated member " broadly treated at this, should be realized that the special preferred form of elongated member specifically comprises one or more in yarn, band, fiber and the monofilament.Highly preferred elongated member is a ribbon form.

In addition, should be realized that elongated member of the present invention is usually through processing to obtain initial configuration, particularly initial orientation state (for example with its uniaxial tension, biaxial stretch-formed or otherwise stretching for example stretches according to the specified ratio of this paper).One of many distinct advantages of using theme acquisition disclosed herein are when process finishing, especially the basic ability that keeps the initial configuration in the elongated member in end article.Therefore, for example, in case machine, the molecularly oriented of elongated member keeps its original state substantially, (for example keeping the about at least 50% of elongated member, more preferably 75% initial orientation).

The size of elongated member makes that usually this element can be by manual operations.Yet, more particularly, described elongated member be designed to certain size so that its can mechanically actuated to be processed into intermediate form.For example, an object lesson of the present invention has been imagined thickness, width or diameter and has been no more than about 5 centimetres, is no more than about 1 centimetre more especially, is no more than about 0.5 centimetre more especially, more special about 1 millimeter elongated member, for example yarn, band, fiber or the monofilament of being no more than.For example, a kind of method is to use width to be lower than 5 millimeters, thickness to be lower than 1 millimeter and the more special elongated member that is lower than 0.5 millimeter (for example about 0.01 to 0.25 millimeter), for example yarn, band, fiber or monofilament.Certainly, intermediate form can comprise a plurality of elongated members, and they have different thickness and/or width separately.For example, the warp thread of woven form can have different thickness respectively with the weft yarn elongated member, and width or both have.In addition, when using film as elongated member at this, they can be obviously bigger (for example, can be wide to about at least 5 meters, and about at least 10,20 or even 40 meters long).

Typical elongated member is continuous in shape.But the length that this element can be to small part along elongated member is by fully density (densified), part density (for example foaming), perforation, wrinkling, twisting or its any combination.Elongated member can have inconsistent character or further feature along the element dimension.

Can recognize that content disclosed herein is general, not necessarily be defined in the embodiment that particularly points out.For example, the invention discloses the various different materials that can be used as elongated member, regardless of the special-purpose of this elongated member.But, especially in open scope about the polymerization reinforced composite, usually the elongated member with one or more this paper is assembled into intermediate form, such as but not limited to weaving, knitting or other form, wherein there are a plurality of constitutional repeating units (for example warp thread and weft yarn use a plurality of elongated members).But repetitive can be simple as the Dan Gequan (windings) of winding arrangement (this structure can use single elongated member to obtain).

Therefore, after forming elongated member, its processing to make intermediate form, is for example made the form that is selected from woven form, winding form, knitting form, type of weave, random dispersion form or its any combination.This form can also be wrapped or otherwise coating or covering.Intermediate form as herein described generally includes a plurality of constitutional repeating units.The example of these construction units is presented among Fig. 2 A.For example, intermediate form 10 can comprise a plurality of constitutional repeating units 12, they are arranged in pattern 14, the basket weave of Fig. 2 A (basketweave) for example, another plain weave weave, twill weave (for example herringbone, tweed, hound-tooch, tartan or other twill), lace, satin weave, or their any combination.The example of specific weave comprises following weave---make the pattern warp elongated member with 1/1 to 14/2 warp/latitude the ratio of (for example 2/1,2/2,3/1 or other ratio) on the weft yarn elongated member, walk up and down.Another specific examples of weave includes, but not limited to 2/1 twill, 2/2 twill, four pieces of satin, 2/2 basket weave, 5H satin weave, 8-H satin weave or other.Therefore, as can be seen, each construction unit of this form can be relative to each other with an arrangement in the multiple feasible structure.For example, as shown in Figure 2A and 2B, the overlap joint unit is orthogonal usually.Also can use other angle of weave as required.Generally speaking, the weight ratio of warp thread and weft yarn elongated member is about 90: 10 to about 40: 60, more preferably about 70: 30 to about 45: 55 (for example about 50: 50).

Although as above disclose exemplary warp and weft yarn scope, other scope also may provide gratifying result.For example, the average of the warp thread elongated member of every cellar area can be identical with the quantity of weft yarn elongated member in the equal area.Quantity separately also can differ from one another.For example, the average of warp thread and weft yarn elongated member can differ 10% or still less (for example, in 4 square centimeters, 18 warp thread elements and 20 weft yarn elements can be arranged) in the per unit area.They also can differ more vast scale, for example differ at least 20%, or even differ at least 50% (for example, in 4 sq, 10 warp thread elements and 20 weft yarn elements can be arranged).

Between warp thread and weft yarn elongated member, the thickness of elongated member, width or both also can be basic identical, and they differ and are no more than about 10% like this.But between warp thread and weft yarn elongated member, the thickness of elongated member and/or width can differ 20% or more.As next further in detail discussing, according to above it should further be appreciated that, intermediate form can comprise multilayer, and wherein two-layer at least have a weave feature different with other layer.

Monobasic (monolithic) elongated member and geophysics fabric

Shown in following argumentation, elongated member that can be used according to the invention can have the structure of basic homogeneous, promptly forms an identical meta structure from the beginning to the end.They can also be along having different compositions, for example by the attainable this point of multi-ply construction on width, thickness or the diameter.For the former, although the winding of monobasic elongated member structure is feasible, more generally, the monobasic elongated member is a woven form, for example common material as the geophysics fabric.

In fact, many specific characteristics of the present invention are effectively to utilize above-mentioned monobasic material, the ability of for example described geophysics fabric.These materials have many civil engineering purposes (although the present invention does not continue to require application at this point), one or more of for example corrosion control/soil conservation, mud fence, landscaping, enhancing, isolation (for example being used for paving the way), draining and other purposes at present usually.Usually, the geophysics fabric shows higher relatively two-way strength and stiffness, and comprise may be not fixed and therefore show the textile fabric of certain infiltration capacity and/or capacitivity (permitivity).The character of geophysics fabric can change in wide region.As an example, the geophysics fabric can show at least approximately 0.3kN, about more especially clamping of 0.5 to about 3kN (grab) hot strength (according to ASTM D4632), at least 10%, for example about 15% clamping hot strength elongation (according to ASTM D4632), 50% or higher level also be possible.Described geophysics fabric shows at least approximately 1000kPa, about more especially 2000 to 10, the Mullen BURSTING STRENGTH (according to ASTM D3786) of 000kPa (for example about 3000 to 7000kPa), at least 0.20kN, more approximately 0.25kN is to the about breakdown strength (according to ASTM D4833) of 0.80kN.The example of commercially available geophysics fabric comprises polypropylene fabric, for example with Propex  (from Propex Fabrics (Georgia)) those that provide of running after fame, and by Don ﹠amp; Low is with title LOTREK, by Mirafi (TenCate Nicolon) with title GEOLON, and by other businessman (US Fabrics for example, Inc. and LINQ Industrial Fabrics, the geophysics fabric that Inc.) provides.

Recognize that the geophysics fabric that can use according to the present invention can be made by one or more thermoplastics (for example polyester, polyolefin or its composition).Certainly, various thermoplastic disclosed herein can be made the geophysics fabric separately.Geophysics fabric (but not being certain) usually comprises alignment portion, and the goods that use weaving geophysics fabric to make among the present invention comprise elongated member, this element to comprise alignment portion, keeps the part of its initial configuration through processing (for example stretching) especially substantially.Although a kind of method for optimizing considers to use weaving geophysics fabric, the geophysics fabric also can be (for example being made by common acupuncture and hot sticky staple fiber and/or continuous monofilament) of nonwoven.The geophysics fabric is made by lobe film or extrusion molding monofilament or analog usually, and therefore processed to comprise alignment portion usually.Fabric can comprise one or more multifilament.In one side more of the present invention, the geophysics fabric can comprise the fiber of one or more natural generations, for example jute, hemp or analog.

Can recognize that from the argumentation of this paper the geophysics textile material can be used in each embodiment disclosed herein.As an example, but be not restrictively, the geophysics fabric can be Overmolded according to content disclosed herein; In the multilayer intermediate form, combine, be combined in multi-layered textile and/or the winding intermediate form with one or more other geophysics fabrics; Can use one of the homopolymers of this paper or copolymer or their combination; Or any combination of above-mentioned situation.

The multilayer elongated member

Others to elongated member are discussed in greater detail now, realize that a commonsense method of technology described herein is to use the multilayer elongated member as the pipe reinforcing material.Especially, the multilayer elongated member use usually the part of first surface at least and with the second portion of this first's adjacency, wherein first and second parts are in composition, polydispersity, form, melt flow or its any combined aspects difference.For example, a kind of ad hoc approach is at least one elongated member of having imagined first thermoplastic, and it has the surface portion that can melt before at adjacent part (for example being orientated adjacent part).

The present invention has advantageously provided and has used single polymer (for example as before at described polymer A or B aspect the geophysics fabric itself) or multiple in abutting connection with polymer (polymer A and polymer B-be known as in this article A-B component structure for example of planting, A-B for example, A-B-A, A-B-C, A-B-C-D, or the like, or their any combination, A-B-D for example, A-B-C-B-D, A-C-B, or other, wherein C and D are meant but the possible polymer that is not limited to add, for example use microbedding instruction shown in this article may run into those) make the ability of the elongated member of band and so on.When using different polymer in elongated member, they can have same composition or different the composition separately.They can be from identical or different polymer group (for example polyolefin).They can be from the polymer (for example polypropylene) of particular type identical in the gang, but differs from one another on some features (for example weight average molecular weight, polydispersity, form, melt speed or other melt characteristics, or their any combination).Should be realized that one or more in the component (for example, A, B, C, D or some other components) need not to be polymer, and can be additive or other functional material.

The multilayer embodiment at first is discussed, what for example may run in the material that comprises component A and B (for example A-B-A elongated member) is such, A and B component are usually relative to one another to become ATM layer relationsATM to arrange (for example Figure 1A, and put ground (for example bicomponent material) or core/skin relation (for example Figure 1B)).The B component can be only part (for example expose at least one side (referring to, for example Figure 1A has shown two exposed side)) or around its edge fully (shown in Figure 1B) covered by the A component.Recognize that the stratification embodiment of Figure 1A can also comprise circular edge or surface.B component is usually located at the inside of elongated member, and is the material that fusing point is higher than component A.Therefore, the structure and material of elongated member makes component A melt before B component, and can keep the shape of B component at least substantially.Will appreciate that the relative quantity of component A and B component can change.In some purposes, for example, less relatively skin (for example A layer of A-B-A multiple layer combination) can be applied on the relatively large internal layer (B layer).Other purposes can be used bigger skin.For example, for the A-B-A combination, the relative volume of each layer can be about 1: 1: 1 to 1: 35: 1, about more especially 1: 10: 1 to 1: 25: 1, about especially again 1: 15: 1 to 1: 20: 1 (for example 1: 17: 1).A-B skin-cored structure can use similar ratio, but omits in the outer field respective amount one.For example, ratio becomes 1: 1 but not 1: 1: 1.

As above introduce, the elongated member made from these components (for example A-B-A multilayer elongated member) (for example co-extrusion band) preferably comprises about component A of 1 to 20wt% and about B component of 80 to 99wt%.Although this relative scale is the typical proportions according to many different elongated members of the present invention, it should not be regarded as restrictive.For example, for some purposes, also can in elongated member, use the component A ratio bigger, and can obtain good result in light of the disclosure herein than B component.For example, B component (for example comprises polyacrylic polymer, for example polyacrylic homopolymers) amount estimates that about 50wt% that can be lower than gross weight (for example is lower than about 45wt% of gross weight, maybe may for gross weight about 10 to about 45wt%, or be in particular again gross weight about 20 to about 40wt%).

Generally speaking, when elongated member comprises at least component A and B component, the fusing point of component A and B (it can take place within certain temperature range) is different, and wherein the fusing point of component A (the maximum fusion temperature that just, has the material of melting range) is lower than the fusing point of B component.In addition, the higher material of fusing point is usually by partially oriented at least (for example single shaft or biaxial orientation).Relatively fusing point can differ about 5 ℃, but more generally differs about at least 10 ℃, more preferably about at least 20 ℃, and in an object lesson, can differ nearly about at least 25 ℃ (for example about 30 ℃) or higher.Such as but not limited to, component A can have about 130 ℃ fusing point, and B component can have and is higher than about 160 ℃ fusing point.Because the temperature span (spread) of fusing point, the result has realized certain range of work (window)---in this scope, component A can flow and be fixed to realize when cooling off with the adjacent material fusion.Simultaneously, remain below its fusing point by the processing temperature with B component, remarkable deterioration takes place and damages the risk of its character (for example whole high bending modulus of elongated member) in the initial configuration that can reduce B component.Otherwise when process finishing, especially the basic ability of the initial configuration in the elongated member that keeps can realize other benefit again in end article.Except the ability that keeps form, near the temperature range lower limit fixed has the elongated member of making and is not easy additional benefit lax or that shrink usually.

As mentioned above, as can be seen, what be selected for argumentation is fusing point (for example can obtain by differential scanning calorimetry according to ISO 11357-3) with reference to the melt characteristic temperature.Should be realized that for some materials, fusing point can not accurately be specified (for example, because it exists) in certain temperature range.Therefore, for this class material, the technical staff will appreciate that the fusing point of mentioning typically refers to maximum fusion temperature.In addition, in some cases, by replacing to another measurement of correlation standard of this material melt characteristics, glass transition temperature or polymerization softening temperature, maximum crystallization temperature (for example described in the WO 2004/033509 (incorporated herein by reference)) or even sealing initiation temperature (for example at Isothermal Crystallization Kinetics andMorphology of Polypropylenes and Propylene/Ethylene (P/E) Copolymers; C.H.Stephens, B.C.Poon, A.R.Kamdar, S.Chum, P.Ansems, K.Swogger, described in the A.Hiltner and E.Baer. (Presented at the SPE ANTEC Conference inChicago, IL, in May, 2004), incorporated herein by reference), may be more easily and each component is used another similar approach.

Therefore, effectively, select the required span (for example about 5,10,20,25 or 30 ℃ difference in this class melt characteristic temperature of polymer) of the relevant melt characteristic temperature of each component A and B usually so that the fusion of component A can be initial solid-stately carrying out under the situation of high mechanical performance than component A down at it of not reducing that B component has.

The a kind of of sandwich construction may benefit be to prepare elongated member so that the ability of property difference to be provided in the each several part of elongated member, and elongated member can accurately be regulated at special-purpose, particular process condition group or their combination thus.Find out that from the summary of this paper the mode that obtains favourable sandwich construction can become according to the subsidiary result who is pursued, and can use multiple technologies to obtain sandwich construction.For example, one or more parts can be applied, lamination, bonding, surface treatment (for example atmospheric treatment (for example oxidation or similar processing), corona discharge, or other plasma treatment), flame injection, ionization, radiation, powder coated, hot melt apply, or otherwise are connected on another part.In other method, can make different piece stand different heat treatment, differently strained processing or other processing conditions.In a method again, with different piece co-extrusion together.Also can use the combination of said method.

In more detail, usually, elongated member of the present invention is derived from film (this film can be non-oriented, but be more typically uniaxial orientation, biaxial orientation or other).For example, quite be typically, described elongated member (particularly is selected from least a yarn, band, the elongated member of fiber or monofilament) can be by making molten polymer (for example at the melt temperature of polymer, for example for various polyolefin or other thermoplastic at about 200 to 240 ℃) (for example carry out inflation film process, as disclosed air quenched blown films method in WO2005035598, it is incorporated herein by reference), make by cast film or sheet material (for example using chilled roll) or by film or sheet extrusion (for example passing through water-bath) the molten polymer quenching of extruding.Also can use the combination of these methods.For example sound wave cuts, hot knife cuts, their combination or alternate manner are cut into preset width with film or sheet material to use suitable cutting operation then.The lobe film is processed to required dawn number (for example about 1000 to about 20 by heating period (for example using hot platform) or stretched operation (the optional stretching furnace that is used for drawing by high temperature) subsequently, 000, for example can be greater than about 13,500) and weight (for example at least approximately the 7g/ dawn and may be at least up to about 9g/ dawn or higher, be higher than about 10g/ dawn more especially).For some embodiments, the lobe film can have about 60 to 300 tex characteristic (the approximately weight of the band of 10km length).Also can and be wound on the bobbin the lobe film fibrillation to be used in the final products subsequently.Described entire method is continuation method normally, but not necessarily.

As further special example, the method of another feasible formation elongated member (particularly being selected from the elongated member of yarn, band, fiber or monofilament) can be with suitable die head (optional have taper perforate), for example compressing tablet die head (for example Collin Teachline extruding machine) make molten polymer (for example 90 to 230 ℃ melt temperature) through extrusion molding step (for example making it pass through 20 to 40 ℃ water-bath thereafter) to form the at most approximately cast-sheet of 10mm thick (more generally approximately 1mm is thick).This sheet material is cut into about 1 to 20mm, about more especially 2 to 10mm (for example about 5mm) are wide, and are stretched to about 2 to 10 (for example about 5) or higher draw ratios at about 50 to 70 ℃ (for example 60 ℃) between goddets in one or more heating furnaces.Then gained yarn, band, fiber or monofilament (for example are higher than about 120 ℃ at one or more high temperature, for example at about 140 to 200 ℃ (for example about 170 ℃)) further stretch with the draw ratio that appends of one or more about at least 2 to 8 (for example about 3.5), this produces desired thickness (for example about 0.3 to 2mm, about more especially 0.05 to 0.3mm (being that about 1mm is when thick in cast-sheet particularly) or may be greater or lesser).Can also be included in the one or more stretching step under the temperature of the fusing point that is lower than strained polymer.A kind of feasible stretched operation is included in about 170 ℃ of material extendings that will comprise polypropylene homopolymer at least 5, and is more special at least 10, more special at least 15 draw ratio.

In other method, for example be used for the uniaxial orientation method for processing, extrude flat or round section bar, then according to the technology orientation that forms the uniaxial orientation elongated member to obtain required toughness and dawn number.Then, elongated member can be wound on the bobbin.Recognize that said method is suitable for forming the elongated member that comprises two kinds of polymer, the co-extrusion of for example passing through two kinds of polymer is to form band or monofilament.

In the manufacture process of multilayer elongated member, also need to make the rheological characteristic of each layer to be similar to substantially to help avoiding material gathering or other consequence of desirable shear stress not during by any feeding section (feedblock) and die head assembly.

From finding that above because the present invention relates to stretch, the technical staff will appreciate that many substituting drawing process are feasible.Under many such situations, commonly, make film or sheet material, for example be used to form yarn, band, fiber or monofilament through one or more stretchings (for example single shaft, twin shaft or other) step.Stretching can be carried out in single phase operation or multistage operation (for example two terrace work).Stretch and under high-temperature, carry out usually (for example particularly for polyolefin, be higher than about 60 ℃, more generally be higher than about 100 ℃, for example about 100 to about 200 ℃, more special up to about 190 ℃ (for example about 120 to 180 ℃, more special in polypropylene, about 140 to about 190 ℃, for example about 150 ℃ to 170 ℃), recognize, may be with listed different at the temperature conditions of other material of polyester and so on).Alternatively consider,, stretch usually and to carry out in the temperature that is higher than than in the fusion temperature of low-melting component and about 10 ℃ in the maximum fusion temperature of higher melt component for comprising higher and than the system (for example A-B-A type structure) of low-melting component.Can select the film stretching amount (comparing) in per stage as required with its isotropism melt state, for example be about 2 * to about 20 * or higher (for example, about 4 * to 10 *, about 8 * to 15 * or may be about 15 * to 18 *, or even about 25 * to 40 *).In addition, stretching can be finished by single phase (one-off drawing has been realized whole stretchings like this) or multistage operation (for example repeatedly continuously elongated).Higher or lower amount of tension may be feasible.In addition, make openly, also can use a plurality of consecutive steps to realize required amount of tension although stretch at single phase especially.In each stage, film temperature can keep constant or change in certain temperature range.In this article with reference to the relatively openly tension values of gained elongated member with the film that forms by the isotropism melt.In the argumentation of this paper, more refer in detail to the others that elongated member forms.

But, ideally, stretching in case after finishing, elongated member (especially being selected from yarn, band, the elongated member of fiber or monofilament) shows initial configuration, comprise orientation (uniaxial orientation usually, but may also have twin shaft or other is orientated component).Thereupon the elongated member of Chan Shenging normally material do not stretch with it or relaxed state is compared aspect strength and stiffness raising is arranged.For example, after stretching, elongated member (especially comprises higher and than those (for example A-B-A type structures) of low-melting component, usually show at least approximately 13GPa according to the present invention, more special at least approximately 18GPa passes through the elastic modelling quantity that ASTM D-638 records, at least approximately 150MPa, more generally at least approximately 300MPa pass through the hot strength that following ASTM method of testing D-638 records.Can recognize that the basic maintenance of form (with subsidiary attracting character) is one of interests that can be obtained by the present invention.Certainly, can find also that above-mentioned character is not enforceable according to the argumentation of this paper.Many materials as herein described (for example geophysics fabric and other) also have about modulus of 5 to 12GPa usually.

The material that is used for elongated member

In following argumentation, as can be seen, the particular polymers composition by selecting to be used for each layer, the size of each layer, one of the mode or the combination of making the mode of each layer or assembling each layer can realize the specific progress in the present technique.In a particular aspects, this paper shows following understanding---and the recent technological progress in the polymer arts has remarkable purposes in the polymer composites field.For example, according to the argumentation of this paper, as can be seen, the present invention is favourable and unexpectedly utilized various traditional polymers and the heat and the mechanical performance of the polymer found in the recent period.

The example of particular polymers that can be used according to the invention (no matter it is monobasic elongated member or multilayer elongated member), the present invention includes one or more polyolefin, for example thermoplastic olefin, poly-(α) alkene, polyvinyl, propenyl polymer or their any combination (no matter being one or more the form in copolymer, blend or the mixture).Generally speaking, for sandwich construction, use combination of materials---wherein will be than low melting point polymer and higher melt polymer co-extrusion to form layer.Although arbitrary layer can be amorphous or partially crystallizable at least, the polymeric layer of higher melt has higher relatively degree of crystallinity (for example, at least 30%, more generally at least 50%, or even 70%) in the object lesson as herein described.Described in entire chapter, one of advantage of the present invention is, even after processing is used to make the material of composite article, at least the material of higher melt layer keeps its form substantially, even for example after consolidation step, also keep higher relatively degree of crystallinity (for example, at least 30%, more generally at least 50%, or even 70%).

Polyvinyl includes but not limited to Alathon or ethene and at least a C ₃-C ₂₀The EVA of alpha-olefin, and can refer to the ethene polymers (SLEP) of VHD polyethylene (UHDPE), ultra-high molecular weight polyethylene (UHMWPE), high density polyethylene (HDPE) (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE) (LDPE), linear low density polyethylene (LLDPE) (LLDPE), very low density polyethylene (VLDPE), ultra-low density polyethylene (ULDPE) or substantial linear.Can make polyvinyl by one or more distinct methods, include but not limited to high pressure, solution, slurry or gas-phase reaction, adopt one or more different catalyst systems, for example chromium (Cr), Z-N (Z-N), metallocene, constrained geometry (CG) or other advanced non-metallocene complex compound.For as in the A-B structure than low-melting component A, need to use the polypropylene copolymer that contains one of above-mentioned polyvinyl or possible another alpha-olefin (for example butylene, or analog).Other feasible material comprises the blend of polypropylene copolymer and (being total to) polyethylene (for example heterophasic polypropylene).

Propenyl polymer includes but not limited to Noblen or propylene and at least a C ₂Or C ₄-C ₂₀The EVA of alpha-olefin, and can refer to homopolymer polypropylene (hPP), random copolymer polypropylene (RCP), high-crystallinity polypropylene (HCPP), modified rubber polypropylene (being generally the hPP or the RCP matrix of " rubber " phase) with dispersion, be also referred to as anti-impact or block copolymer (ICP), or propylene-ethylene copolymers.Can make propenyl polymer by the whole bag of tricks, include but not limited to solution, slurry or vapor phase method, use various catalyst systems, for example Z-N (Z-N), metallocene or other advanced non-metallocene complex compound.Propenyl polymer can be isotactic, syndiotactic or atactic, but is preferably isotactic.

Be used for comprising propylene-ethylene copolymers (it can be a modified rubber) than the particularly preferred polyolefinic example of low-melting component (for example component A of A-B-A elongated member); More preferably have Narrow Molecular Weight Distribution, for example can run after fame and run after fame available from those of ExxonMobil available from Dow Chemical or with VISTAMAXX with VERSIFY, or its combination.Polymer that can be used according to the invention (especially is used as than low-melting component, the component A of A-B-A combination for example, or as one or more layers of microbedding material as herein described) more more specifically example be included in WO03/040201A1, disclosed U. S. application 2003-0204017 and United States Patent (USP) 6,525, those disclosed in 157, all these are all incorporated herein by reference.For example, described material can be the propylene-ethylene copolymers that does not contain diene substantially.Be used for the component A of A-B-A combination or be that the polypropylene homopolymer made with metalloscene catalyst is so that it shows relatively low fusing point as one or more layers possible material standed for of microbedding material as herein described.The examples of commercial of this type of material comprises ACHIEVE (can available from ExxonMobil) and METOCENE (can available from Basell); Also referring to Kunzer and Wieners, Kunstoffe Plast Europe 86 (in May, 1996) 5, page or leaf 666-670, it is incorporated herein by reference.In this available a kind of commercial polyethylene examples of material is can be with the material of trade name AFFINITY available from The Dow ChemicalCompany.

In one approach, described copolymer can be with the stable state manufacturing in the metallocene catalyst agent method that uses single reactor.In other method, described copolymer can use non-metallocene metal coordination complex (for example heteroaryl ligand catalyst placed in the middle of the metal in the presence of the active co catalyst of aikyiaiurnirsoxan beta and so on) manufacturing.Certainly, can use foregoing other catalyst method.In one embodiment, copolymer comprises about 5wt% to the unit of the about ethylene derivative of 25wt% and the about propylene derived unit of 75wt% to 95wt%, and percentage by weight is in the gross weight of the unit of propylene-and ethene-derive.The unit that is low to moderate the ethylene derivative of about 3wt% (or lower) also is feasible.

No matter separately still and another polymer preferred propylene-ethylene copolymers used herein (, for example polypropylene homopolymer or random polypropylene are used in combination, and no matter be used in skin (for example than the low melting point layer) or the internal layer (for example higher melt layer)) preferably special-purpose propylene-ethylene copolymers and therefore have two, the combination of three or more following properties (for example combination of all these): a) about 1.5 molecular weight distribution (MWD) to about 4 (for example 2 to 3), b) about at least 0.3 (for example, approximately 0.5g/10 minute), about more especially 0.3 to about 50g/10 minute (for example, 2 to 25g/10 minutes) melt flow rate (MFR) (under 230 ℃) (MFR) (according to ASTM D1238), c) about 0.80 to about 0.95g/cc, the density of about more especially 0.85 to 0.91 (for example, 0.858 to 0.888g/cc) (according to ASTM D792); D) co-monomer content of about 3 to 25wt% (for example, 5 to 15wt%); E) about 0 to about-50 glass transition temperature (Tg) of ℃ (for example-15 to-35 ℃); The melting range of f) about 40 to about 160 ℃ (for example, 50 to 135 ℃); G) about 25 to about 100, about more especially 40 Xiao A hardness to about 90 (for example, 50 to 75); And h) about 5 to 1000MPa, or more special 8 to 325MPa (for example, 10 to 280MPa), or the bending modulus (according to ISO 178) of higher (for example, surpassing 2000MPa).Illustrate and without limitation, this class material (for example can have about 8 to about 325MPa, about 10 to 280MPa) bending modulus, about ethylene contents of 3 to 25wt% and optionally be lower than about 135 ℃ maximum fusing peak value, about 25 to about 100, about more especially 40 Xiao A hardness to about 90 (for example, 50 to 75); Or their combination.The commercial examples of this analog copolymer can be run after fame available from Dow Chemical Company with VERSIFY.In a specific examples, in elongated member and the gained composite article after this made, observe above-mentioned characteristic according to disclosing of this paper.

Described material preferably can be one or more in random copolymer, the heterophasic copolymer with random matrix, clarification copolymer (for example using nucleator as herein described/fining agent clarification) or the isotactic copolymer usually.

Generally speaking, especially for elongated member with A-B composition structure (for example A-B-A material), not only B component comprises that fusing point is higher than the polymer of component A, and the B component material keeps form normally substantially after processing, shows the rigidity higher than the material of component A, toughness and may in addition the oriented material of higher hot strength.Therefore, the B component main contributor of elongated member overall mechanical properties normally.

In a specific exemplary, B component comprises the material of relative higher stiffness, and particularly polyolefin polymer is as major part.In one aspect, the special requirement B component comprises or even is made of oriented polypropylene substantially.Usually, the molecular weight distribution of B component can be narrow, in or wide.For various uses, it is feature that used B component can have nuclear material with multimodal.A particularly preferred base polymer that is used for higher melt material (for example B component) has greater than about 1000MPa (for example greater than about 1200MPa, for example approximately 1500MPa) or higher according to ASTM D790, the bending modulus of ISO 178.Object lesson comprises homopolymer polypropylene (hPP), random copolymer polypropylene (RCPP) or its combination.The example of commercially available material comprises can be available from The Dow Chemical Company (for example, run after fame with INSPIRE and to supply with), ExxonMobil (for example, run after fame with PP9122, PP9852E1, PP2252, PP4712E1, PP4772, PP4792E1 etc. and to supply with), Basell (for example, run after fame supply with) or Borealis (BORMOD) with ADSTIF, METOCENE or MOPLEN those.Another material that is fit to be used as in A of the present invention or the B component is can be available from the ADFLEX (for example Z104) of Basell.

An attractive polyacrylic specific examples used in this invention comprises, or more particularly substantially (for example by the isotactic polypropylene homopolymers, as according to the open preparation of WO 2004/033509 and US 20040122196 and analysis, they are incorporated herein by reference; Other that analyze for material characteristics is open, referring to the appendix of this paper) constitute.Correspondingly, a specific polyacrylic example that is used in the B component is a feature with the combination (for example combination of all these) of two, three, four, five, six or more following properties: a) as being lower than about 5.5 molecular weight distribution (M according to disclosed content among WO2004/033509 and the U.S. Patent application 2004-0122196 (referring to appendix) by what gel permeation chromatography recorded _w/ M _n), b) less than approximately 25g/10 minute, be more preferably less than about 10g/10 minute and (for example be more preferably less than about 7g/10 minute, less than approximately 5g/10 minute) melt flow rate (MFR) (at 230 ℃) (according to ASTM D1238), c) (for example greater than about 2000MPa, greater than about 300,1% secant bending modulus (according to ASTM D790-00) 000psi), d) according to disclosed content among WO2004/033509 and the U.S. Patent application 2004-0122196 (equally referring to this paper appendix) record less than about 2% (for example, less than about 1%) xylene soluble part, e) less than about 25% turbidity (according to ASTM D1003), f) according to disclosed content among WO2004/033509 and the U.S. Patent application 2004-0122196 (equally referring to this paper appendix) by differential scanning calorimetry record about at least 30%, more special about at least 50%, more special in about 70% degree of crystallinity, g) according to disclosed content among WO2004/033509 and the U.S. Patent application 2004-0122196 (equally referring to this paper appendix) use that nuclear magnetic resonance (NMR) records greater than about 70%, more preferably greater than about 85% be preferably greater than about 95% again, and again more preferably greater than isotaxy five unit groups/three unit group ratios of about 99%; And h) greater than 133 ℃ crystallization temperature (for example, recording) according to the disclosure of WO2004/033509 and U.S. Patent application 2004-0122196 (equally referring to this paper appendix).In an illustrative example, five unit group isotacticities can be at least 96%, more preferably at least 97%, most preferably at least 98%.Usually, polypropylene homopolymer shows the peak melting point of at least 160 ℃ (for example at least 165 ℃ or even 170 ℃).As an example, polypropylene homopolymer shows the peak melting point and about at least 30% of at least 160 ℃ (for example at least 165 ℃ or even 170 ℃), more special about at least 50%, more special more about 70% the degree of crystallinity that is higher than, greater than about 70%, more preferably greater than about 85%, again more preferably greater than about 95%, even more preferably greater than isotaxy five unit groups/three unit group ratios of about 99%, or the combination of this isotacticity and degree of crystallinity.In specific examples, polypropylene homopolymer further shows 1% secant bending modulus (according to ASTMD790-00) greater than about 2000MPa.In a specific examples, at elongated member with after this in the gained composite article of making according to the instruction of this paper, observe above-mentioned characteristic.For example, the material of B component can in fact in the fixed composite article of gained, show with fixed before peak melting point compare the raising (for example improve nearly 3,5 or even 8 ℃) of peak melting point.

For example, a kind of specific polypropylene is to be lower than about 7 M _w/ M _n, be lower than about 7g/10 minute melt flow rate (MFR), be feature greater than the 1% secant bending modulus of about 2000MPa and the xylene soluble part that is lower than 2wt%.The polyacrylic example of this class is disclosed in the WO2004/033509 of the US2004/0122196 that is called " Highly crystalline polypropylenewith low xylene solubles " and " Highly crystallinepolypropylene with low xylene solubles " by name, both are all incorporated herein by reference, wherein also disclose the method for measuring above-mentioned characteristic.

Also recognize in this article, by at the higher melt layer, for example add in the B component (for example with blend, copolymer or their combination) optional minor amount (with respect to B component) than the low melting point polyolefin copolymer, for example propylene-ethylene copolymers (for example, have the above-mentioned type, for example can be available from the VERSIFY of The Dow Chemical Company ^TMCopolymer), can obtain other favourable outcome (for example, helping to stretch).This analog copolymer preferably has two, three or more combination (for example combination of all these) in the above-mentioned characteristic of special-purpose propylene-ethylene copolymers.Do not wish to be limited by theory, it is generally acknowledged in B component to add to be believed to be helpful in the B component layer is adhered on the component A layer than the low melting point polyolefin material; Existence than the low melting point polyolefin material also is believed to be helpful in each fibrillation in the B component layer bonded to each other.Similarly, can change the characteristic of component A by this paper that in component A, incorporates minor amount into for the disclosed material of B component.

More specifically, as used in the B component of elongated member, a kind of method for optimizing is that the amount of about at least 70 weight portions (for example 80 to 100 parts) with B component is used polypropylene homopolymer (for example, the polypropylene homopolymer of making according to the instruction of WO incorporated herein by reference 2004/033509 and US2004122196).If use the polyolefin copolymer (for example aforesaid propylene-ethylene copolymer) of optional minor amount, it can be with the nearly amount existence of about 30 weight portions (for example about 0 to 10 part) of B component.

Described higher melt polymer (for example comprising the B component in the exemplary of A-B structure) is the main contributor of elongated member overall mechanical properties normally.Although all do not require in each case, require B component to show good tensile properties usually, particularly at high temperature (for example about 170 ℃).Correspondingly, it is about at least 8 that B component can show under the situation that can not destroy or significantly damage its overall performance, more preferably about at least 12, more more preferably about at least 16 or higher draw ratio (that is, main body initially with final thickness than).Recognize also that in this article by mix a certain amount of propylene-ethylene copolymers (for example above-mentioned special-purpose copolymer) in B component, this higher relatively stretching is possible.Thus, can also recognize, even the existence of copolymer can reduce the rigidity of B component at the beginning, but also can realize the abundant increase of final expanded material rigidity, because the stretch capability that material improves can produce the higher possibility that sclerosis takes place in drawing process.

For the example of the special preferred material that is used for higher melt material (material B of for example exemplary A-B textural association), use high rigidity (with in a method for optimizing, high isotaxy) Noblen.Above and in the WO2004/033509 of the US2004/0122196 of by name " Highly crystalline polypropylenewith low xylene solubles " and " Highly crystallinepolypropylene with low xylene solubles " by name, described the example of this type of homopolymers, both are all incorporated herein by reference, they can in the single stage drawing method, realize higher stretch capability (for example about at least 10 *, more preferably about at least 15 *, more preferably about at least again 20 *), reduce thus or even eliminate the additional stretch step that can use in this article and/or the demand of annealing steps.Certainly, can recognize, the use of high-crystallinity polypropylene is desirable, but not enforceable, can use the polypropylene (for example various conventional polypropylene, little-atactic polypropylene copolymer and other polypropylene disclosed herein that generates by Ziegler-Natta catalyst) that is not high crystallization to obtain good result yet.

The selected material of each layer for the elongated member of this paper needn't only contain copolymer (for example, propylene-ethylene copolymers) or homopolymers (for example, polypropylene homopolymer).On the contrary, can use other combination of copolymer, blend, mixture or copolymer and homopolymers.Thus, can further regulate characteristic in each layer.For example, for the situation that adopts two kinds of components (for example component A and B component), component A can comprise polypropylene homopolymer and propylene-ethylene copolymers.For example, polypropylene copolymer can constitute about 0 to 100 weight portion of component A, and propylene-ethylene copolymers can constitute about 5 to 100 weight portions of component A.Similarly, can in B component, add a certain amount of another relative resilient material (for example polypropylene plastics gonosome or elastomer, propylene-ethylene copolymers or its combination) to help improving its draw ratio (for example with maximum approximately amounts of 10wt%).

Little-random (promptly＜2wt%C ₂) use of propylene-ethylene copolymers in A and/or B component also be considered within the scope of the invention.Also expect, the material in A and/or the B component does not contain styrene polymer.

Additive in the elongated member material or that therewith use

In one embodiment, the material that is used for elongated member, no matter be as the monobasic material or as the component of multilayer elongated member (for example component A, B or other), can also comprise non-migrating processing aid or surface modifier, it is through selecting to be used for changing mantle friction characteristic and/or the scratch resistance and the abrasion resistant qualities of (improve or reduce) this material.Preferably, this surface modifier is with less relatively amount, and for example the amount with about 10wt% of being lower than material (for example at most about 4%) exists.Quite commonly, selected surface modifier reduces the mantle friction of this material, the scratch resistance that improves component and abrasion resistance, operation (for example improved textile property) or more preferably their combination of improvement elongated member in the intermediate form forming process.Although the skin that this class surface modifier more may be used to expose (for example component A of A-B structure), it also can be used in other place of elongated member, for example in the higher melt material of B component.

The specific examples that is suitable as the material type of non-migrating processing aid or surface modifier comprises siloxanes, polyolefin, halogen polymer (for example, fluoridizing thermopolymer) or their any combination.A kind of particularly preferred reagent comprises high molecular weight silicone, particularly the super high molecular weight siloxanes (for example, functionalized or non-functionalised alkyl siloxanes, as poly-(di-ethyl siloxane), poly-(dimethyl siloxane) or their combination, for example can be with master batch form available from those of commodity Dow Corning MB 50-3 13, MB 50-001, MB 50-321 or the MB 50-021 by name of DowCorning).Can find other selection with reference to WO 01/12715, WO 02/08332, WO 98/13419 (all incorporated herein by reference).

Optional nucleator/fining agent the additive that can contain relatively small amount 500ppm to 2500ppm (for example, 750ppm to 1500ppm) of polyolefin herein.Although nucleator/fining agent additive can be advantageously utilised in the propylene-ethylene copolymers as herein described (and being used among the component A of A-B-A multilayer elongated member for example), but for polypropylene homopolymer, especially be used as those polypropylene homopolymers of the B component of A-B-A multilayer elongated member, special requirement are used this additive.Further, this additive need be used for relating to the pulling method of single phase stretching (it is chosen wantonly for most purposes of using the multistage to stretch) especially.Generally speaking, use nucleator/fining agent additive improves the rigidity of the film that is formed from a resin and improves the crystalline rate of some polymer (for example high crystalline polypropylene based polyalcohol) in the air quenched blown films manufacture process.Described nucleator/additive has also improved the rigidity/clarity balance of gained film.Can use any additives that to clarify simultaneously with nucleation.Nucleator/fining agent additive, ADK NA-11 (methylene-two (4 for example, sodium ascorbyl phosphate) and ADK NA-21 (aluminium hydroxyl two [2,4,8 6-two-tert-butyl-phenyl), 10-four (1, the 1-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] two oxa-phoshocin 6-oxidato]) can be available from Asahi Denka Kokai, and preferably add in the high crystalline polypropylene based polyalcohol of the present invention.Can be available from Milliken ﹠amp; The Millad 3988 of Company (3,4-dimethyl benzylidine sorbierite) is another example of nucleator/fining agent additive available among the present invention.Also can use Sodium Benzoate or even sorb alcohol radical nucleating systems according to the present invention.

The monobasic material that no matter is used in elongated member still is in the multilayer material, this material can also comprise one of two or more other compositions or combination, for example other polymer (for example, polypropylene, polyethylene, fluoroelastomer, its any combination or the like), filler (for example, glass, talcum, calcium carbonate or analog), antigen fibrillation agent (for example, PE), nucleator, releasing agent, fire retardant, conductive agent, antistatic additive, pigment, carbon black, antioxidant, impact modifier, stabilizing agent (for example, ultra-violet absorber) or any combination.For example, when using these additives, they (for example use with the amount of about 15wt% of mostly being most whole component usually, component A and/or B component about 0 to 10wt%, about more especially 2 to 8wt%, and wherein every kind of additive for example is lower than 0.6wt% usually to be lower than about 1wt% of this material, be lower than 0.5wt%, or even be low to moderate about 0.2wt% or lower amount is used).Described component (for example component A or B) can also comprise recirculation waste material (for example from the manufacturing of component A of the present invention, B component or even from the manufacturing of elongated member).Disclose in EP 0829529A1 but not define the example of possible additive, it is incorporated herein by reference.The example of commercially available additive includes but not limited to ERUCAMIDE, IRGANOX B215, IRGANOX B225, MISTRON talcum, IRGANOX 1010 (or thioester), CHIMASORB 944, CHIMASORB119, HOSTASTAT FE2, IRGASTAT and TINUVIN 770.The present invention not only considers to use above-mentioned commodity, also considers to use the corresponding product from other manufacturer.

Can also in the B component (higher melt component) of elongated member material, incorporate other polymeric component that one or more are used to strengthen its performance into.For example, except the polypropylene homo beyond the region of objective existence, high rigidity material can also comprise other thermoplastic, for example PET (PET), polyamide, Merlon, any other thermoplastic polymer as herein described or its mixture.Similarly, can in B component, add a certain amount of relative resilient material (for example polypropylene plastics gonosome or elastomer, propylene-ethylene copolymers or combination) to help improving its stretch capability.

As an example, a kind of method of making elongated member comprises and forms coextruded film so that it produces the A-B-A combination, and wherein component A is that (density is about 0.9g/cm for the random copolymer of propylene and about 3 to 15wt% ethene (for example about 5 to 15wt%) ³), and has a fusing point of about 50 to about 135 ℃ (for example 100 to 140 ℃), B component is that peak melting point is the polypropylene homopolymer of about 150 to 170 ℃ (can recognize that for some embodiments, fusing point may surpass about 170 ℃ (for example about 150 to 180 ℃ or higher)).Correspondingly, the fusing point difference between component A and the B can be low to moderate about 5 to 9 ℃, or is higher than about 75 ℃.The relative quantity of A and B component is about 1: 2: 1 to 1: 25: 1, about more especially 1: 15: 1 to 1: 20: 1 (for example about 1: 17: 1).Component A or B can have any suitable weight average molecular weight, and for example about 50 to about 400kg/mol, and more generally about 200 to about 300kg/mol.

Foregoing is not to limit the present invention.(relate to the cortex (for example component A) that comprises the random copolymer that contains propylene and ethene or another alpha-olefin at WO 03/008190A1 and WO2004028803 (all incorporated herein by reference); Also relate to the use of metallocenyl statistics and convergence thing) in open but be not other example that defines extruded tape or yarn.EP 0776762B1 incorporated herein by reference discloses another example of the material that can be used as elongated member, and cortex (for example component A) comprises the blend of ethylene copolymer and a certain amount of high density polyethylene (HDPE) (for example about 5 to 45wt%) in view of the above.United States Patent (USP) 5,993,711 and 6,045,923 (transferring Lankhorst Indutech B.V.) (all incorporated herein by reference) have also been enumerated the feasible selection thing.According to the former, the section bar of elongated member can comprise one or more vertical flanges and/or longitudinal fluting on one or more surfaces.According to the latter, elongated member can comprise the central core of being made by high density polyethylene (HDPE) and one or more other polyolefinic blend (for example B component), and the amount of high density polyethylene (HDPE) is main thus, promptly surpasses about 50wt%.More particularly, central core is made by (line style) low density polyethylene (LDPE) (＜925 kilograms per cubic meter), very low density polyethylene (＜910 kilograms per cubic meter) or the blend of these product combination of about high density polyethylene (HDPE) of 50 to 90wt% (＞940kg/ cubic meter) and about 10 to 50wt%.In addition, can exist a certain amount of polypropylene to improve the intensity of this material.According to the present invention, another feasible method is to form conducing composite material, and wherein composite comprises at least one current-carrying part, for example is derived from the existence of conductive elongate element.For example, the conductive elongate element can be through coating or uncoated metal wire (for example copper cash).Can from United States Patent (USP) incorporated herein by reference 6,710,253 (transferring Lankhorst indutech B.V.), find other variant.

As general introduction, expect according to the present invention, can use the sandwich construction that comprises two-layer at least (their fusing point difference).Thus, be used in combination higher melt material (it normally is orientated) than low melting material.Be usually located at than low melting material on the outer surface of elongated member, can melt thus.According to open, material therefor can be selected from multiple alternative material, and wherein a kind of particularly preferred combination comprises that propylene-ethylene copolymers as than the low melting material layer, also comprises higher melt polypropylene homopolymer layer (particularly Qu Xiang those).These layers can comprise other additive (for example dimethyl silicone polymer or another suitable non-migrating processing aid or surface modifier) as disclosed herein.For example can in described propylene-ethylene copolymers, mix the higher melt polypropylene homopolymer material of a certain amount of (for example minor amount).Perhaps, or in addition, can also in described polypropylene homopolymer, mix a certain amount of (for example minor amount) than lower melting propylene-ethylene copolymer.Extremely the example of preferable material combination comprises, with as mentioned and combine at the height isotactic polypropylene homopolymers described in US 2004/0122196 and the WO2004/033509 (all incorporated herein by reference), have and can be available from the VERSIFY of The DowChemical Company ^TMSimilar characteristics than lower melting propylene-ethylene copolymer species.

More particularly,, be used to form sandwich construction, comprise that the combined number of material of A-B structure (comprising microbedding as herein described) is very big from above finding out.Do not want to be subjected to the restriction of following explanation, but as general introduction, the disclosure of this paper is considered, be selected from ethylene propylene copolymer (not containing dimethyl silicone polymer) than low melting point layer (component A), ethylene propylene copolymer (containing dimethyl silicone polymer), heterophasic polypropylene (for example, ADFLEX), the ethylene propylene copolymer (not containing dimethyl silicone polymer) that contains polypropylene homopolymer, the ethylene propylene copolymer (not containing dimethyl silicone polymer) that contains random copolymer polypropylene (for example, can run after fame available from The Dow Chemical Company with R771), or their any combination.For above-mentioned material, the preferred example of ethylene propylene copolymer can be run after fame available from The DowChemical Company with VERSIFY.In addition, do not want to be subjected to the restriction of following explanation, but as general introduction, the disclosure of this paper is considered, the isotactic polypropylene homopolymers that higher melt layer (B component) is selected from the isotactic polypropylene homopolymers, contain the at most about propylene ethylene copolymers of 20wt% (for example, can run after fame available from The Dow Chemical Company with VERSIFY), random copolymer polypropylene (for example, can run after fame available from The Dow ChemicalCompany) or their any combination with R771.The present invention has considered any combination of component A example and B component example of the present invention.Above-mentioned material, especially the material of determining in above-mentioned general introduction is attractive especially in following purposes, comprises that they are used to form the purposes of the elongated member that is used for twining or are used in the purposes of other intermediate form of tubing reinforcing material.

Microbedding

The other method of can be separately or being used in combination with the method that above forms the elongated member that comprises component A and B at least is to form the elongated member that comprises one or more layers microbedding." microbedding " is meant the layer that thickness is less relatively, and for example, thickness is lower than about 50 microns, and more preferably less than about 20 microns, more preferably less than about 10 microns, more preferably thickness is lower than about 7 microns again, and more preferably thickness is lower than about 5 microns again.Usually, when using, as a plurality of stack layers, the assembly of preferred coextruded layer (each layer comprises polymer, copolymer or their mixture) is made microbedding.Before for example each microbedding can comprise in the exemplary A-B combination at one of described material of layer of component A and B or both, or another component.The quantity of the single microbedding in the typical elongated member is generally 1 to 4 layer.Yet more generally, described microbedding comprises at least 4 layers or more, more special at least 5 layers or more multi-layered material, and wherein each layer preferably is adjacent layer difference.

More particularly, as an example, the method of a kind of manufacturing microbedding condensate (for example elongated member) is that at least one second fluid with at least one first fluid of first fusion or softening polymeric material and second fusion or softening polymeric material adds in the suitable device die head of this device (for example by), pass through co-extrusion at this, for example by using microbedding melt current divider or hemisphere microbedding co-extrusion feeding section that they are lumped together, thereby with second polymeric material with the discrete portions packing of first polymeric material in the second polymeric material matrix, to form a plurality of belt courses of first polymeric material, form the stratiform condensate thus.Generally speaking, select and rapidoprint, make them by the charging instrument time, stand to shear, the viscosity of different materials differ less than about 3 times (for example, the viscosity differences of each polymeric layer is less than about 1.5 times under feed conditions, for example about 1.25 times or even about 1 times).Therefore, belt course with first plane of one of the main surface of main body (body) almost parallel on continuously basic and discontinuous on second plane vertical with this first plane.In addition, first polymeric material layer can have the main interface with the polymeric main surperficial parallel array of gained.

Do not wish to be limited by theory, but in a particular aspects, microbedding for this paper, the invention provides the method that obtains the continuous polymer material at draw direction, this material have with the boundary (confinement) of this draw direction approximate vertical (for example, using is the polymer of partially crystalline polymer at least, and it is limited in the layer or zone that has than low-crystallinity).Because this qualification, after solidifying, material shows the entanglement amount of reduction usually, and the stretch capability that this can be used for improving described material conversely again makes the gained material have higher relatively rigidity and/or intensity thus.

A kind of method is to use and comprises and intert the structure of a plurality of microbeddings between the different materials of component A and B.For example, this can be expressed as ((A-B) _n-A), wherein n is 2 or bigger integer.Also imagined n and be 3,4 or bigger, 10 or bigger, 20 or bigger, 50 or bigger, 100 or bigger, 200 or bigger and 300 or bigger elongated member (for example 500 to 1000 layers, even may 1000 to 5000 layers or more).Can use any suitable technique to make the microbedding elongated member, for example layer multiplication (layer-multiplying) extrusion molding.A kind of method is for example to use microbedding melt current divider or hemisphere microbedding co-extrusion feeding section co-extrusion multilayer.Randomly, can be expressed on the cooling stick.Except that the extrusion molding step or with the extrusion molding step in combination, can also use lamination.Generally speaking, select each layer polymer so that melt viscosity near to help preventing layer unstability or inhomogeneities, thereby make used polymer have sufficient interfacial adhesion so that adjoining course can leafing.Other exemplary United States Patent (USP) 5,568 that openly sees, 316 (it also discloses as United States Patent (USP) 3,773, and 882 and 3,884,606; 5,269,995; 5,094,793 and 5,094, the use of the co-extrusion device described in 788, all aforementioned patent are all incorporated herein by reference).Also referring to, United States Patent (USP) 5,540,978; 5,448,404; 5,339,198; 5,316,703; 5,217,794; 5,126,880; 6,837,698 and EP 0647183B1, all these are all incorporated herein by reference.Also referring to, the paper of Dooley, " Viscoelastic Flow Effects in Multilayer PolymerCo-extrusion ", Technische Universiteit Eindhoven (2002) is (ISBN90-386-2983-4), and is incorporated herein by reference; With people such as Rastogi, " Heterogeneity inPolymer Melts from Melting of Polymer Crystals ", Nature Materials Vol.4 (in August, 2005) (online publication on July 24 in 2005), incorporated herein by reference; People such as Jin, " Structure of Polypropylene Crystallized in Confined Nanolayers ", PPS-20:Polymer Nanotechnology Symposium (22-24 day in June, 2000), incorporated herein by reference.Yet, should be realized that these aspects of the present invention consider that this paper is not require in the combination of any layer or layer to have any specific reflection degree to the selection of used material.Therefore, can estimate the gained elongated member be reflected in incident on this object visible light less than 40% (or even less than 20%).Similarly, material can not contain any colouring agent to give this object metal appearance.Their selection also can not consider to form layer optical thickness or total optical thickness separately.

Although the adjoining course of microbedding can have the same material type, but more generally, for non-microbedding multilayer embodiment as herein described, the material of adjoining course differs from one another at least one characteristic, for example forms, orientation, degree of crystallinity, molecularly oriented, molecular weight, melt speed, high melting temperature, glass transition peak value, crystallization temperature, sealing initiation temperature, softening point, molecular weight distribution or their any combination.For example, can be in conjunction with different polypropylene, can be in conjunction with different polyethylene, can be in conjunction with different PETs (PETs), or the like.In addition, polypropylene can be combined with polyethylene, PET combines with polypropylene or polyamide is combined with polyethylene, or the like.Any thermoplastic as herein described can be used in the microbedding elongated member, and microbedding openly is not limited to polyolefin polymer.For example, can select above for component A and the described polyolefine material of B each layer of microbedding structure.

One or more microbeddings can also comprise and are selected from Merlon, polyvinyl chloride, (methyl) acrylonitrile, (methyl) acrylate, polyurethane, thermoplastic and high-elastic, thermoplastic olefin, polyamide (for example, nylon 6, nylon 6,6 or other), polysulfones, polyester, polyalkylene terephthalates (for example, poly-(diethyl terephthalate), poly-(dibutyl terephthalate), poly-(terephthalic acid (TPA) 1, the 4-cyclohexanedimethanoester ester) or other), poly-M-phthalic acid alkylene ester (for example, poly-(M-phthalic acid ethyl)), acronitrile-butadiene-styrene, polyarylene sulfide (for example, polyphenylene sulfide), thermoplastic polyurethane, polyphenylene oxide (PPE), polystyrene or their any combination are (with copolymer, blend or form of mixtures) the polymer copolymer of this polymer (or comprise).

The example that is used for the specific A-B combination of each microbedding includes, but are not limited to polypropylene homopolymer and polypropylene copolymer; Polypropylene and propylene-hexane copolymer HDPE and ethylene copolymer; Polyamide (to small part be aromatics or non-aromatics, and can comprise copolyamide) (for example nylon 6, nylon 6,6, nylon 46, nylon 11, nylon 12, nylon 6.6T) and polypropylene; Poly-(PETP) and another polyester, for example poly-(butylene terephthalate) and/or poly-(trimethylene terephthalate); In poly-(ethylidene-2,6-naphthalene) or poly-(terephthalic acid (TPA) cyclohexanedimethanol ester) and poly-(PETP), poly-(butylene terephthalate) or poly-(trimethylene terephthalate) one or more; Polyolefin homopolymer and copolymer (for example, polybutene and poly-4-methylpentene (for example, from Mitsui TPX methylpentene copolymer).

In addition, randomly (and except only being used for the microbedding, can be used for sandwich construction in the present invention), can be between the adjoining course of multilayer elongated member material, for example between the adjoining course of microbedding material, use to connect layer or intermediate adhesive (for example adhesive, priming paint or other) layer.Under the situation of polyolefin multi-layer material, described connect the layer or intermediary adhesive layer generally include the polyolefin that has functional response's group.When consisting of the full different time of chemistry of layer, the use that connects layer or intermediary adhesive layer is particularly useful.For example, when using polyolefin as one deck and use polyester or polyamide during as another layer, comprise that the polyolefinic layer that has functional response's group (for example comprise coupling agent, for example can Polybond  run after fame available from the maleic anhydride-grafted polypropylene modified dose of Crompton-Uniroyal Chemical, the polyolefin that has epoxy functionalities, the polyolefin that has (methyl) acrylate (for example GMA) or (methyl) acrylic acid degree of functionality or other layer) can be used for improving the bonding strength of interlayer.Can also use comprise copolymer (it comprises polyethylene, polypropylene or their mixture) connect the layer or intermediate adhesive.For example but without limitation, a kind of feasible method is can use two-layer or multilayer is the microbedding of polyolefin homopolymer (for example polypropylene or polyethylene) and with propylene copolymer, ethylene copolymer or their mixture these microbeddings is bonded together.Certainly, can recognize, above-mentioned connect the layer or intermediary adhesive layer also can be used in the elongated member that is not microbedding.

Microbedding is considered to show improved stretch capability, and this causes higher intensity or modulus.By in single or multiple drawing process, using higher draw ratio, can realize higher material orientation, thereby improve intensity and toughness.Microbedding also shows improved impact resistance, and this is considered to cause by dissipating by the bigger obtainable greater impact of the independent number of plies.

Not strict being defined in of the microbedding instruction of this paper uses microbedding to form the elongated member that only is selected from fiber, shaft, rope, yarn, band, monofilament or band.Other forms also are possible, particularly film (for example oriented film, for example biaxially oriented film), for example Biaially oriented polypropylene (BOPP) film.Microbedding elongated member (with other elongated members) also can be used in the purposes that does not require big stretch capability or improved impact resistance, the preservative film that for example stretches (cling films), geophysics fabric, raffia, fabric, gunnysack, artificial glass, carpet, strap or similar applications.Certainly, the microbedding elongated member can be used in the intermediate form, fixed or unconsolidated other elongated member for example as herein described.The microbedding material can also with other structure, for example metal, timber, fabric, their combinations or analog are used in combination.

According to aforementioned argumentation at component A and B, exemplary microbedding elongated member comprises at least approximately higher melt material component B of 50wt% (accounting for whole microlayer structures), remainder is than low melting material component A, the more preferably at least about B component of 60wt%, most preferably about B component of 70 to 96wt%, remainder are component A.Preferably, component A comprises about polypropylene copolymer of 0 to 100wt%, and propylene-ethylene copolymers (for example aforementioned special-purpose propylene-ethylene copolymers, for example VERSIFY ^TMCopolymer) can constitute component A about 5 to 100wt%.Component A can also comprise about 0 to 4wt% foregoing non-migrating processing aid or surface modification (for example friction reduces) agent (for example, dimethyl silicone polymer, fluoropolymer, for example fluoroelastomer or analog) that accounts for this component.Component A can also comprise about 0 to 8wt% other the aforesaid composition that accounts for this component.

B component preferably comprise high rigidity polypropylene (for example, random copolymer, or account for this component about 80 to 100wt%, also comprise the propylene-ethylene copolymers of the about 10wt% that accounts for this component at most simultaneously.The remainder of B component can be made of aforesaid other compositions of the about 10wt% that accounts for this component at most.

Foregoing is described for example, and without limitation, to have about 100 to 525 layers or more multi-layered (between the layer that be staggered in the layer that substantially constitutes, constitutes substantially by B component by component A, and optional comprising between other polymers compositions layers) microbedding elongated member is made into to comprise the about 5 said components A to about 25 weight portions, the said components B of about 95 to 75 weight portions is surpassing under the draft temperature of 150 ℃ (for example 165 ℃) it with about 18 to 28 draw ratio stretching.More specifically example is included in the following table.

Wt% composition B	Wt% composition A	Number of plies #	Draw ratio at＞150 ℃
				92	8	3	20
92	8	129	20
				92	8	129	＞22
80	20	129	24
				80	20	129	24＞26
80	20	513	24

The gained microlayer structures can show at least approximately 10GPa, the stretch modulus of more special 12GPa at least (for example 12 to 15GPa) (according to ASTM D-638 or ISO 527).Can use these materials and to surpass 18 draw ratio (for surpassing the draft temperature of 150 ℃ (for example 165 ℃) stretching down), particularly for have at least 4 layers the stratiform condensate---it comprises at least: comprise first polymeric material that is selected from thermoplastic polymer, thermoplastic copolymer or its combination and have less than the ground floor of about 50 microns thickness and comprise second polymeric material that is selected from thermoplastic polymer, thermoplastic copolymer or its combination and have the second layer less than the adjacency of about 50 microns thickness.When each layer in first and second polymeric materials when composition, crystallization degree, molecularly oriented, molecular weight, melt speed, high melting temperature, glass transition peak value, crystallization temperature, seal initiation temperature, softening point, molecular weight distribution or its any combined aspects differ from one another (for example, the microbedding that comprises propenyl polymer, the adjoining course different with another), this is particularly like this.

For example but without limitation, also can in containing about 3 to 33 layers microbedding elongated member (ratio of its B component and component A is about 3: 1 to about 9: 1 (for example about 4: 1)), use a kind of feasible two-step stretch method.First is stretching in about 65 ℃ finishes (about 6.5 draw ratios), and second stretching step is finished (about 3 draw ratios) at about 165 ℃.Correspondingly, for other stretched operations that are used herein to elongated member that have with the aforementioned operation different characteristic, at the fusing point that is higher than one deck but be lower than under the fusing point of another layer (for example restraint layer) and carry out one-off drawing.Certainly, can recognize that draft temperature can be according to the selected material of microbedding is become.For example but without limitation, elongated member can comprise polyester (for example PET), draft temperature can be about 120 ℃ to about 250 ℃.In addition, for example by improving according to people such as Zuo " InSitu Synchotron SAXS/WAXD Studies on Stretching of IsotacticPolypropylene, Poly.Mat ' ls Sci.﹠amp; Eng., the Hermans Orientation Function that 93 (2005) 761.n addition record, the orientation that improves higher melt material at least in drawing process is also in the open scope of this paper, also make the microbedding elongated member (for example containing about 3 to 150 alternating layers, for example 5 to 129 layers) combine polypropylene and PET (promptly from Equipolymers Lighter C88).Can use the layer that connects that for example comprises maleic anhydride inoculated polypropylene (for example from Crompton POLYBOND 3002).The following arrangement of five layer materials: PP-poly thio rubber adhesive-PET-poly thio rubber adhesive-PP, 7/3/80/3/7 ratio.The following arrangement of 129 layer materials: (PP-poly thio rubber adhesive-PET-poly thio rubber adhesive) n-PP, wherein n is 32, wherein the ratio of material is with identical in five layer materials.As general introduction, and without limitation, this instruction relates to the manufacturing of the microlayer structures that generally includes at least 4 stack layers, and these layers have less than about 50 microns thickness and each layer with respect to its adjoining course separately in difference aspect at least a characteristic that is selected from composition, degree of crystallinity, molecularly oriented, molecular weight, melt speed, high melting temperature, glass transition peak value, crystallization temperature, sealing initiation temperature, softening point, molecular weight distribution or its any combination.In one approach, one deck at least of elongated member and polymer that may every layer are propenyl polymer (for example polypropylene homopolymer, for example isotactic polypropylene homopolymers).For example, one or more layers (with in addition all the layer) can use polypropylene.At least the polymer of one deck can also comprise ethene.The polymer of at least two adjoining courses can comprise ethene (for example being selected from propylene-ethylene copolymers, linear low density polyethylene (LLDPE), high density polyethylene (HDPE) or their any mixture).

Can use multiple other particular combinations of polyolefine material at microbedding.For example but without limitation, can form co-extrusion multiple layer combination body, it comprise melt index (MI) be lower than about 4, molecular weight distribution less than about 5 and maximum fusing point be about at least 128 ℃ polyolefin (for example Natene) and maximum fusing point polyolefin adjoining course (for example copolymerization of ethylene) less than 125 ℃.Can carry out one-off drawing at least to coextruded layer at about 115 to 141 ℃.Another object lesson comprise by Ziegler-Natta catalyst make polyacrylic in abutting connection with microbedding, wherein each adjoining course is respectively the alternating layer of homopolymers, random copolymer or homopolymers and random copolymer.A feasible combination is a polypropylene homopolymer layer of considering use and Natene layer adjacency again, or optional intermediate layer, for example propylene-ethylene copolymers, random polypropylene, ethylene copolymer or their mixture of comprising.Usually, the polymer of at least two adjoining courses has the maximum fusion temperature that differs about at least 5 ℃ separately.

Can between two-layer at least stack layer, use additive or other functional materials, for example connect layer or intermediary adhesive layer.The same with disclosing of other places of this paper, described material can comprise the non-migrating processing aid or the surface modifier that are selected from siloxanes (for example dimethyl siloxane), halogen polymer or its combination on the exposed surface that is positioned at one deck at least.

Fixed and the moulding of intermediate form

At the relative commitment (particularly with the intermediate form moulding before) of processing, needing (but not being enforceable) abutment structure unit in each case is to be movable relative to each other.A kind of method that realizes this point is to form intermediate form, but it is not carried out fixed procedure of processing, and this step can make the abutment structure unit irreversibly link together, for example by splicing, fusion, fastening or otherwise assemble these unit.Void space between can filler cells, and intermediate form density.Correspondingly, not fixed these characteristics of intermediate form are useful especially, for example by at least a material is heated above one or more steps of one or more temperature of fusing point with the form that causes material fusing and fusion, and weld with adjacent unit effectively.This heating can be tied in intermediate form (constrained) or freely carry out simultaneously.In addition, this heating steps can be at the same time applies under the situation of power middle form and carries out.

For example and without limitation, common polyolefin intermediate form (no matter being to comprise that geophysics fabric or sandwich construction (for example A-B-B structure) or both comprise) can be fixed by following one or more steps---with (for example about 100 to about 175 ℃ of one or more temperature of this form more than the fusing point of the exposed surface of elongated member, more special in about 150 ℃) when keeping the enough time (for example about 1 to about 5 minutes), apply at least approximately 50kN (more special power greater than about 150kN (for example 350kN).The long or short period also is feasible (for example at high temperature fixed about 0.25 hour, about 0.5 hour, or even be higher than about 1 hour).

The gained intermediate form can comprise or be made of individual layer (it is chosen wantonly can comprise one or more styles) substantially.Also imagined in the part of each laminar surface or comprised the intermediate form of multilayer (its optional can comprise one or more styles) on all.For example, if the use multilayer, one or more layers can differ from one another aspect one or more following: for example whether the width of the heat treatment of the composition of material type, elongated member, elongated member, elongated member or other dimensions, model type, this layer be fixed, existence, thickness, form or their any combination of rete.Explanation for example, be selected from film, coating (for example solvent coating, extrusion coating or other), woven form, winding form, knitting form, type of weave, random dispersion form or its any combination at least one ground floor can with at least one second layer adjacency that is selected from film, coating (for example solvent coating, extrusion coating or other), woven form, winding form, knitting form, type of weave, form of foam, random dispersion form or its any combination.At least one deck is optional is the geophysics fabric or comprises microbedding.In this example, shown in first or the second layer in one deck can be by fixed at least.

In intermediate form is under the situation of individual layer, and uses under the situation of multilayer as the part of intermediate form at needs, can process one or more layers to prevent each construction unit and/or each layer separation.For example, for the single or multiple lift form, can fix one or more layers (, optional fixed to one another) with suitable method (for example by along one of this form, at least a portion thermally coupled construction unit at two or more edges) for multilayer form.Can use other processing methods, for example mechanical step (for example crimping, fastening, hook nail (stapling), riveted joint, sew up or other), adhesive Connection Step (for example with drops of adhesive or pearl, adhesive tape or other) or their combination.Adopt this mode can easily handle intermediate form, for example be used for carrying, store, place die cavity, or other, to such an extent as to reduce the possibility that each construction unit separates infringement intermediate form integrality simultaneously.

When in intermediate form, using multilayer, can select the number of plies according to the needs of desired use.For example, can use two-layer above, three layers, four layers, five layers or more multi-layered.Correspondingly, intermediate form can have the little thickness that is of uniform thickness with wherein elongated member under concretion state not, but also can be bigger, and for example about 0.25 to about 2.5cm or bigger.Correspondingly, under concretion state, intermediate form can produce about 0.8 millimeter to about 1.5 centimetres or bigger thickness, for example about 0.1 to 0.8 centimetre or bigger, particularly about 0.3 to 0.5 centimetre thickness.

In another aspect of this invention, before forming end article, intermediate form (its can comprise aforesaid one or more layers) randomly is formed into required structure.This moulding can be in consolidation step (for example in thermoforming or other high-temperature moldings or drop stamping process) or even carry out in other operations of following or do not follow fixed cold stamping or being used for causing the local train sclerosis.In consolidation process, intermediate form at first can independently dangle usually (drapableupon itself).After fixed, it is semi-rigid at least that this form becomes, and preferably it can carry deadweight.Typically, once moulding and fixed after, this intermediate form of the present invention can keep shape usually for a long time, for example surpasses for 2 weeks, surpasses 1 month more especially, surpasses 3 months more especially again.Thus, intermediate form manufacturer can make this form of certain stock, and it can store until needs for a long time subsequently and be assembled into composite.

Can recognize that in the process of preparation intermediate form of the present invention, described form can be (promptly is reinforced by plastic deformation or harden) of strain hardening below the recrystallization temperature scope of composition material.Strain hardening can be before fixed, among or carry out afterwards.If after fixed, carry out, then strain elongation preferably keep below about 15%, more preferably less than about 10%.If before fixed or among carry out, the strain elongation can be about at least 10 to 40%.Higher or lower amount also is possible.A kind of specific forming method of intermediate form (no matter individual layer or multilayer) comprises the use resilient structures, and it allows intermediate form displacement in deformation process (for example sliding).In common pending trial of submitting to that is called " Apparatus and Process forManufacturing Shaped Plastic Reinforced Composite Articles " and the U.S. Provisional Application of owning together 60/718,025 (attorney docket 1062-051P1) (incorporated herein by reference) various ad hoc approach were disclosed on September 16th, 2005.As an example, consider to make the intermediate form distortion that comprises a plurality of thermoplasticity elongated members, in deformation process, clamp the intermediate form that has heated simultaneously displaceablely.Intermediate form is clamped, so that when applying the power that makes the intermediate form distortion, intermediate form moves freely under indeformable situation in predetermined limits.With the thermoplasticity elongated member of intermediate form to the fixed three-dimensional article that has the predetermined orientation of elongated member with formation of small part.Randomly, in second forming operation, (for example be lower than the temperature of displaceable clamping step, for example be equal to or less than room temperature substantially) the punching press intermediate form.

Certainly, many geometries are feasible, and are considered to can be used within the scope of the invention.In addition, intermediate form needs not to be multilayer form, and can be individual layer.The moulding intermediate form can be further processed as disclosed herein like that, and for example molded another material that closely contacts with the moulding intermediate form is to form reinforced composite.As can be seen, moulding intermediate form of the present invention generally includes three-dimensional structure.In addition, it is generally acknowledged that the moulding intermediate form does not produce size or shape conversion that any vision can detect as a rule when being processed to form the gained composite.But, according to disclosing of this paper, can be before fixed, among or afterwards with the intermediate form strain hardening (for example being no more than about 10% elongation) that is shaped.

Form or moulding after, intermediate form optional can be as required by further heat treatment, coating (for example priming) or other procedure of processings to change its a kind of or multiple character.In addition, can the optional treatment elongated member and/or by its intermediate form of making to give its degree of functionality.For example, can use by changing elongated member and/or intermediate form the surface can and/or chemical property (for example be used to improve crosslinked) give the step of degree of functionality.Priming paint (for example polyolefin dispersion) can be applied on elongated member and/or the intermediate form surface as required.

Intermediate form of the present invention is suitably processed to form resulting product.Can use many distinct methods.For example, before or after fixed, can be with this form and raw material (bulkmaterial) (for example aforementioned second thermoplastic, it can have any suitable form, for example sheet material, mechanograph, sheet material, tubing, or the like) combination to be forming the moulded products that will strengthen with the material of intermediate form, described raw material be moulding, not moulding or its combination.Can use any suitable package technique, for example intermediate form can bond on the raw material, its can mechanical fasteners to raw material, it can be soldered on the raw material, it can or permeate with the raw material dipping, its can with the raw material heat fused, be laminated on the raw material, or their any combination.

Intermediate form can with raw material at thermoforming, vacuum forming, pressure forming, compression molding, blowing, injection moulding, rotational molding, hot pressing, lamination (for example, extrusion laminate, for example by with intermediate form and raw material charging by roll, wherein intermediate form below raw material and/or above), (this can choose wantonly and comprise constraint raw material and/or intermediate form) assembling in the step of extrusion-blown modling, profile extrusion, hydroforming (hydroforming) or its any combination (with fixed, part is fixed or concretion state not).Intermediate form can also itself comprise insert or other elements or carrier, and this assembly and raw material are fitted together.For example, can twine extruded profile, then with this assembly and raw material assembling with elongated member.

Be used to make multiple tube, or an object lesson that comprises the structure of multiple tube comprises Overmolded, and comprise the following steps: to form and fixed intermediate form, moulding and fixed intermediate form are placed mold cavity, and in having this chamber of intermediate form, add the liquefaction raw material, wherein after solidifying, resulting product comprises the curing raw material that are molded onto on the intermediate form and strengthen with intermediate form.More particularly, the moulding and the fixed intermediate form that will comprise first thermoplastic place the injecting molding die chamber, and pass through raw material, the second thermoplastic injection moulding just comes molded (for example embedded mold pressing or Overmolded) second thermoplastic in this die cavity.

Temperature during second thermoplastic adding die cavity wants enough high with the close adhesion contact form curing again to take place so that it can make to the fusing of small part intermediate form and with second thermoplastic.In this, can control the temperature of the mould that second thermoplastic enters to help the control solidification rate.For example, a kind of method is to use the fluid-cooled mould, the cold mould of liquid (for example water) for example, and the mold wall temperature that will be close to die cavity remains on low more about more than 15 ℃, about more especially more than 30 ℃ than the minimum fusing point of the material in the intermediate form (for example component A material in A-B or the A-B-A section bar material).

As example more specifically, for for (it comprises about 3 to 8 layers A-B-A elongated member (band for example to having intermediate form with thermoplastic (for example polypropylene material) injection moulding, wherein component A comprises that fusing point is about 120 ℃ material)) die cavity in, use water-cooled mould (, for example comprising that tool steel, PX5, H13, S7 or the analog of chromium and molybdenum (for example P20) made) that the wall around the die cavity is remained on about 80 ℃ for example by tool steel.After injection moulding, be that about 2 to 4 millimeters and gross weight are about 0.3 to 1 kilogram typical component for wall thickness, mechanograph was kept about 5 to 60 seconds or more of a specified duration in mould before releasing.For example, for goods manufactured according to the present invention, it should be about 15 to 35 seconds usually the time.The example of suitable moulding press is 300 tonnes of Demag injection (mo(u)lding) machines.

In another aspect of the present invention, molded large-size components (for example the longest dimension greater than about 0.5 meter, more special in about 1 meter) is with the reinforcing material of the intermediate form that comprises under the concretion state (even only be low to moderate about 10 volume % fixed).As an example, can prepare the automobile buffer assembly (it can also comprise one or more miscellaneous parts, for example bumper bar) of enhancing, or require to use the miscellaneous part of large plate (platen) instrument.Thus, can make many parts by injection moulding, they require compression molding to form formed body before this.

As implied above, molded with intermediate form with the raw material that make to strengthen composite article thermoplastic normally.This class material can be (for example use one or more fibers, microsphere, nano particle or other, for example glass, clay, talcum or analog are filled) of not filling or filling.But in some embodiments, this material can be thermosetting plastics (for example urethanes, rubber, epoxy resin, or other).Although the optimal seeking of raw and processed materials be with intermediate form in the thermoplastic of thermoplastic with identical type, needn't be like this.Can be used for the material of second thermoplastic in the raw material and/or can be made into the material that elongated member uses including, but not limited to any material used in first thermoplastic of intermediate form, vice versa.Object lesson comprises the thermoplastic olefin polyolefin, the VHD polyethylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), very low density polyethylene, the VHD polypropylene, high density poly propylene, middle density polypropylene, low density polypropylene, the extra-low density polypropylene, Merlon, polyvinyl chloride, (methyl) acrylonitrile, (methyl) acrylate, polyurethane, thermoplastic and high-elastic, thermoplastic olefin, (for example nylon 6 for polyamide, nylon 6,6 or other), polysulfones, polyester, poly terephthalic acid alkylene (for example poly-(PETP), poly-(butylene terephthalate), poly-(to dibenzoic acid 1,4-cyclohexanedimethanol ester) or other), poly-naphthalenedicarboxylic acid alkylene (for example poly-(naphthalenedicarboxylic acid second diester)), acronitrile-butadiene-styrene, poly arylidene thio-ester (for example polyphenylene sulfide), thermoplastic polyurethane, PPE, polystyrene, or no matter their any combination (is copolymer, blend or form of mixtures).Also can use other polymeric materials as herein described.

For example but without limitation, a kind of ad hoc approach is that raw material and/or elongated member material are selected from polyolefin, Merlon, polystyrene, vinyl-based, polyamide, poly terephthalic acid alkylene, polyester, polyphenylene sulfide, (methyl) acrylate or their any combination.

As can be seen, raw material can be selected so that it can be coloured molded.Perhaps, can be with its coating to obtain required outward appearance.

Although the raw-material fusing point that combines with intermediate form can be lower than the minimum fusing point of any material in the intermediate form, wish that generally raw-material fusing point more generally is higher than the peak melting point of any material in the intermediate form.For example, the difference of the peak melting point of any material surpasses 10 ℃ in raw-material fusing point and the intermediate form, and more special 30 ℃, more special again 50 ℃.

In another aspect of the present invention, reinforced composite manufactured according to the present invention shows excellent size stability in wide temperature range.For example, the linear coefficient of thermal expansion (40 ℃ to+80 ℃) can be about 17 to 24 μ m/m-℃, is more particularly about 19 μ m/m-℃.

After forming the moulding composite article, can carry out one or more aftershapings or secondary operation to resulting product as required, for example (but being not limited to) machining, coating, ultra-sonic welded, solvent bonding, hectographic printing, silk screening, drop stamping, engraving, surface treatment, bending, compacting, corona discharge, plasma treatment, flame spray, their any combination, or other.

It should further be appreciated that, combine, can use one or more heating stepses middle form with any moulding or consolidation step.This class step or can be undertaken by conduction, convection current, radiation or its any combination according to any other heating steps of the present invention.Can use baking oven as thermal source.Also can use radiofrequency heat source and/or microwave heat.Heating can be carried out at inert atmosphere or in air.In addition, heating steps can comprise the step of carrying out under the different pressures that a plurality of each comfortable different temperatures, each leisure apply.

With reference to Fig. 3, shown the illustrative example of moulding three-dimensional article 100.Goods have upper surface 102.Although may 104 produce loose fibers or wearing and tearing edge at the edge according to procedure of processing, but they (for example can be eliminated, by suitable punching, finishing or other cutting step they are removed, or avoid by the step that is applicable to the edge that connects intermediate form.As shown in the multilayer of using the band fabric (drapable) form of can dangling made, not fixed with respect to part 108, the inside of goods 106 can be fixed.Shown in loose fiber be exemplary, and think and can they be removed by suitable punching, finishing or other cutting step.

With regard to undocumented degree still, also considered other version of the present invention.For example, elongated member can be made of single material (for example thermoplastic of polyolefin and so on) of planting substantially, or it can comprise dissimilar materials, for example is selected from glass fibre (for example E-glass, S-glass or other), carbon fiber, metallic fiber, different plastic optical fibre (for example aramid fibre), ceramic fibre (for example silicon carbide fibre), natural fiber, their combination or other material.Elongated member can be applied or uncoated.Intermediate form can be flooded with suitable chemical agent, polymerizable compound, filler or other impregnating agent.Can on intermediate form or gained moulded products, apply surface finish agent and/or extra play, comprise that for example one or more are used to reduce the component of static, photostability, hydrophily, hydrophobicity, anti-flammability, coloring, electrical conductivity or its any combination.

For aforementioned content, can recognize that the ability that forms goods attractive in appearance is another potential benefit of the present invention.For example, a kind of embodiment is to use to have different in width, thickness, color, its any combination or other a plurality of elongated members in intermediate form.Thus, can obtain desired texture, profile, pattern or further feature.In addition, complicated formed body and constructed in accordance be can form, rib, filler rod, ripple or other projection for example formed.

Can also in the goods that are used in combination weaving or non-woven fibre (for example continuously or chopping glass or other) felt, use intermediate form of the present invention.

All right described intermediate form used according to the invention is as the substitute of plastic foil in multilayer (for example lamination) goods.

Except foregoing, a plurality of elongated members of the present invention can shred and random or controlled being dispersed in the intermediate form of the present invention.Can be with reference to United States Patent (USP) incorporated herein by reference 5,872,067 understands others.

Use

Goods manufactured according to the present invention show excellent impact resistance and other mechanical performance.For example, automobile component is considered to impact in side impact, knee bar and glove box door, top cover (header) and rail head impacts and/or bumper property aspect meeting or above the energy management standard for example United States Federal Motor Vehicle Safety Standard (" FMVSS ") 214, FMVSS 208, FMVSS 201 and/or the standard of in 49 C.F.R.581, otherwise specifically including.

Can find other feasible variant with reference to existing document, such as but not limited to, WO2004/028803, WO 03/008190, WO 98/46422, WO 94/12334, WO91/11324; United States Patent (USP) 6,710,253,6,045,923,5,993,711 and EP 1403038A1, they are all incorporated herein by reference.

Material of the present invention is applicable to many different purposes, from the automobile component to the construction material to apparatus and other purposes.Example comprises, but be not limited to, spare tyre liner (spare tire wellliner), cargo liner, railway carriage or compartment lining (bed-liner), backrest, fender, fascia, knee bar, glove box, automotive trim, buffer, spoiler, air diffuser, hood, the gas dam, fuel tank, sunshade top deflecting plates, automobile screen stone (stone guard), car body panel, wheel liner (vehicle well liner), tumbler switch, shift knob, hand braking handle, luggage top cover case, door handle, flak jackets, the helmet, shell, floatation device, shipping container, luggage, attache, shin guard, elbow support, knee-pad, chest protector, face shield, tubing, desktop, pressure vessel, protecting screen, the down-hole equipment shell, shell, safety box, lock, fluid container, the floor, wall or other sheet material, roof Material, outcase of refrigerator, the washing/drying machine shell, bench, seat, cross bar, handheld tool, prosthese, orthotic, wheelchair or its assembly, housing of TV set, the audiofrequency apparatus shell, the portable instrument shell, camera case, the consumer electronic products shell, air-conditioner compressor outer housing, crossbeam, crossbeam, instrument board, shutter just, sole, or other.

In one aspect, material of the present invention is particularly useful for constructing pipeline or container, in particular as pipeline or container protective cover and/or that carry fluid.For example, the present invention relates to be used for the heavy duty industrial purposes, for example be used to carry chemical reactant or product or channel, water, sewage or even the manufacture method of the pipeline of gas, this class pipeline is hard or semi-rigid normally, and chooses wantonly on part or all of its length to flexible.

The tubing that uses material of the present invention to make shows good physical characteristic, and for example improved circumferential stress performance, ring stress performance, durability and low-temperature impact property are particularly compared with the not enhancing tubing of similar material.

With reference to Fig. 4 A-4D as can be seen, the structure of tubing 200 of the present invention can be made of single wall 202 substantially, or as shown in Fig. 4 B, it can comprise two or more walls 204 and 206 (wherein at least one comprises intermediate form).When using many walls, they can be concentric as among Fig. 4 B, or they can comprise one or more outer walls 208 and one or more built-in wall 210 (otherwise it can be the single or multiple lift structure) as among Fig. 4 C, for example is used to delimit the tributary and manages.They can be straight, or are wrapped at least a portion of its length.Wall construction can comprise one or more circles, flat or curved cross section.Other structure also is feasible.Fig. 4 D has shown a kind of example of preferable configuration, and wherein sheath 212 covers on the structure of Fig. 4 B.The embodiment of all right coverage diagram 4A of sheath and 4C.The following square structure adjacency that described sheath is shown as and is in contact with it, but also open with its below spacing structure at least a portion of portion within it.Recognize that the container of making can comprise the tubing with at least one blind end herein.

The wall 202 of delimiting the pipe of Fig. 4 A is made of intermediate form of the present invention as herein described (particularly fixed intermediate form) usually substantially.For the tubing of type shown in Fig. 4 B and the 4C, at least one wall construction comprises according to intermediate form disclosed herein (for example being made by aforementioned component A and B).Intermediate form is in concretion state usually, but also can be not fixed substantially.The tubing part that does not comprise intermediate form can comprise and is applicable to any material of making pipeline, flexible pipe or conduit, and can be metal, plastics, composite, the individual layer made by suitable material, multilayer or other.Preferably, the core pipe comprises polymer (for example polyolefin), more preferably polyethylene, polypropylene or PET.In one aspect, tube wall can be made by any material as herein described.For example, the core pipe can be the extrusion molding element with one or more components (for example said components A and B).In a specific embodiments, tubing comprises the polyethylene with suitable stable bag (stabilization package) pressure classification with convenient pressure grade (for example being equal to or greater than the PE 80 that records by ISO 9080).

As among Fig. 4 E-G as can be seen, the elongated member 214 of intermediate form (having width (w)) can be being applicable to the mode of making flexible pipe, container or other pipe structure around core pipe 216 parcels or twine (for example spiral winding), and optional by fixed.On the one hand, a plurality of elongated members can be woven together to cover the core pipe, durability and low-temperature impact resistance that this can cause tubing to improve again.Elongated member can use any suitable angle (α) around the winding of core pipe, and wherein the vertical axis of angle tubing is about 30 ° to 90 °.More preferably, winding angle more preferably greater than 50 °, but is lower than 55 ° (for example about 45 ° to 54 °) greater than about 45 °.On the one hand, in order to realize the attractive combination of axial and circumferential stress performance, angle is about 54.7 °.But, should be realized that if desired, bigger winding angle also may be desirable, for example greater than about 60 ° (for example 60 to 75 °), or even greater than about 75 °.Any suitable intermediate form be can use, twister, fabric or combination comprised.Twister can be adjacent to each other or overlap continuously, or they can be with spacing (p) each interval, it is about 5 to 500 millimeters for example for diameter (d), 1000 millimeters or even 2000 millimeters, about more especially 10 millimeters to 100 millimeters or bigger tubing, this spacing can be at most about 10,25 or even about 50 millimeters or bigger.Twine the number of plies and do not wait, to realize the desired properties of gained tubing.For example, twining the number of plies can be for about 1 to 100, or even about 2 to 50.Some embodiments can be used up to about 25 winding layers, and some can comprise about 10 or winding layer still less.

On the one hand, the core pipe is by multilayer, and for example two layers, three layers, four layers, five layers or more multi-layered elongated member cover.Every layer is used identical or different material.In preferred embodiments, use two-layer at least layer to cover the core pipe with same material.Every layer with respect to the reverse in the opposite direction winding of vertical axis angle same (counterwound), like this can equilibratory layer structure.Certainly, should be realized that, can between each winding layer, change winding angle, change composition or other characteristic of elongated member, change the width or the thickness of elongated member, apply rete, apply coating, change spacing, or their any combination.Winding step can be carried out in room temperature.It also can carry out at high temperature (for example about at least 40 ℃).

In addition, can on the part or all of outer surface of tubing, comprise optional but preferred sheath.For example, it covers at least a portion outermost layer of core pipe/intermediate form sub-assembly.Sheath can be to improve any material of tubing to the resistivity of wearing and tearing, scuffing, lobe, Chemical exposure, ultraviolet ray or the injury of other type, and can contain the reagent of the long-time stability that otherwise improve this material.Preferably, sheath comprises the polyethylene with suitable pressure rating (for example being equal to or greater than the PE 80 that records by ISO 9080) pressure classification.

Tubing can be any by fixed, and usually subsequently in any elongated member part, it shows with original state and compares, and form keeps substantially.For example, the core pipe before being covered by sheath by fixed (for example by conduction heat, advection heat, radiant heat or its combination).In a method for optimizing, after one or more layers covers tube core or after having added the sheath covering that tubing is fixed.In addition, can use a plurality of consolidation step, although preferred consolidation step only.A kind of favorable method is to apply intermediate form then with intermediate form fixed (for example by conduction heat, advection heat, radiant heat or its combination) on tubing.Fixed can be at about 100 to about 175 ℃, more special in carrying out the enough time (for example about 1 to about 5 minutes) under about 150 ℃ high temperature (for example, for the polyolefin elongated member).The long or short period also is possible, for example about 0.25 hour or (as previously mentioned) more of a specified duration at most.In consolidation process, suppose that material to the small part of the elongated member of intermediate form is melted and is fused on the tubing.Under this method, the laser weld that need not choose wantonly or other local heat treatmet step just can be fixed to the enhancement layer from intermediate form on the tubing of below.

Preferably, the tubing of constructing according to the present invention meets or exceeds following physical parameter, for example at 20 ℃ greater than the about circumferential stress performance in 50 years of 10MPa; Cling to and 80 ℃ 9.2, greater than at least 500 hours, more special slow crackle greater than 1000 hours was expanded (SCG) performance (according to test method ISO 13479); 0 ℃ of rapid crackle expansion (RCP) performance (according to test method ISO 13477) greater than 10 crust; Or the combination of this two specific character.

In an exemplary, construct and have interior pipe the tubing of (for example pipe in the thermoplasticity, for example polyethylene, polypropylene or its combination), two-layer fixed co-extrusion band skin (they be applied to not fixed winding or weaving intermediate form at first in pipe on).Band has other local described A-B component structure as this paper at least.In a specific examples, in band is applied on the pipe before, the draw ratio that band is stretched at least 4, and is more special at least 8, more special more at least 12 (for example 16).With every layer of following applying of co-extrusion band: the winding angle with about 50 to about 60 ° (for example 54 °) twines at least one elongated member.Band in being placed on the pipe in by in heating at least 1 minute (for example 160 ℃ 4 minutes) more than 150 ℃, but preferably be shorter than greater than 0.25 hour band is fixed.Compare with independent use core pipe, this exemplary tubing shows at least 20%, more preferably at least 30% good inflation intensity (according to test method ISO 1167, use 1 crust/minute the pressure speedup until breaking).(use 80 ℃ of 7MPa) when comparing circumferential stress performance (according to test method ISO 1167), independent core pipe broke at 10 hours, and this exemplary tubing only just broke after about 250 hours.Ground similar to the above was being tested 500 hours with the exemplary tubing that four layers of co-extrusion band are made at least, did not show any breaking in more preferably about at least 1000 hours.

From above finding out, the invention still further relates to a kind of trade method, in view of the above, with sending in combination of raw material (for example polypropylene), first mechanism supplies unconsolidated intermediate form to second mechanism.Second mechanism is fixed with its moulding with this intermediate form, the molded then composite article that wherein has this consolidation form.Perhaps, send in combination with raw-material, first structure is to the fixed intermediate form of second mechanism supply.The molded subsequently composite article that wherein has this consolidation form of second mechanism.First or second mechanism can outside molded or replace molded ground, will have goods vacuum forming, punching press, compacting, the thermoforming of this consolidation form.As can be seen, first mechanism can supply the intermediate form of shaped form or plain film form.Can also make intermediate form and the gained composite article that comprises it by single mechanism.

The following example is not in order to limit the present invention.Recognize the relevant open manufacturing of extending and be used for multiple tube easily by the technical staff of this paper.

Embodiment

Embodiment 1: use drop-dart impact test (according to ISO 7765-1) in room temperature with (-) 40 ℃, to comprise the performance with the bond pad (1.85 millimeters thick) of the co-extrusion band (being designated as sample X) (about 0.04 millimeters thick * 3 mm wides) of the propylene-ethylene copolymers of polypropylene homopolymer co-extrusion disclosed herein, with shown in 1.5 and 2.2 millimeters thick with CURV ^TMThe performance of the material buied (be denoted as " sample A " and " sample B) of running after fame compares.Fig. 5 A and 5B have shown according to the obtainable data of the preferred embodiments of the invention.

Embodiment 2: use the polypropylene raw material, with three layers of (3L) fixed twills co-extrusion polypropylene ribbon (the about 0.04 millimeters thick * 3 mm wides) intermediate form on this polypropylene raw material one side, injection moulding spare tyre case.Resulting product does not have wrinkle, and at 8MPH when-30 ℃ are impacted, compare with the 40% long glass fibres composite that has 20% glass filled polypropylene matrix and to show 400% improvement.Observe and do not have broken complete ductile rupture; Promptly in impact process, do not observe the chip that flies upward.

Embodiment 3: repeat embodiment 2, but intermediate form is placed on the raw-material both sides of polypropylene, it shows rigidity and the impact resistance of comparing raising with embodiment 2 composites.

Embodiment 4: repeat embodiment 3, but use the single-layer polypropylene band in the twills of intermediate form.Resulting product does not have wrinkle, and compares with the 40% long glass fibres composite that has 20% glass filled polypropylene matrix when-30 ℃ are impacted at 8MPH and to show improvement.Observe and do not have broken complete ductile rupture.

Embodiment 5: the sample of being made spare tyre case (2.2 centimetres of dark, 15 centimetres wide, 25 centimeter length and 2.25 millimeters wall thickness) composite by fixed 6 layers of (6L) intermediate form (fixed each layer about 0.18 millimeters thick) made from weaving co-extrusion polypropylene ribbon.Intermediate form is placed this chest bottom.It is carried out impact test and compares with baseline construct blow-molded 30% short glass fiber reinforced polypropylene.The transmission device speed of 8mph is used in this test, has the fixture of 5.1 centimetres of circular impact devices.This test is carried out in room temperature with at-30 ℃, and comprises that eccentric bump has the chest bottom of intermediate form, thereby makes its tension with bearing load.The result is presented among Fig. 6 A and the 6B.

Embodiment 6: as the example of the fixed operation of a kind of being tied (constrained) that is used for the multi-layered textile intermediate form, the compression molding press of manually controlling can be heated to preselected temperature (for example, 110 to 150 ℃).To be cut into the size identical (for example 30 * 30 centimetres) according to the weaving intermediate form of above-mentioned instruction wherein with machine direction cutting fabric abreast with the press plate.Pile up several layers of fabric and place between the protective layer (for example Mylar film), and this is piled up part place between metallic plate top and the bottom, be transported in the press.Immediately press cuts out, and apply power (for example applying 150kN 1 minute).Subsequently, increase dynamics (for example to 350kN 3 minutes).The cut-out press heats, and carries out the spacious water cooling of press when workpiece still is under the pressure.Open press, and take out plate and Mylar film.The gained workpiece shows fixed (for example density is greater than 95% solid density).

Embodiment 7: as the example of thermoforming operation, and compression molding press (for example manual, as to be furnished with the mould of the box part that is used to be of a size of 20 * 20 * 4 centimetres).The extrusion molding crystalline p p sheet is all pressed (for example, passing through sheet extrusion) with the weaving intermediate form layer by layer on both sides.Laminate is heated in press (5 minutes contact heat), then thermoforming and under pressure, cooling off press before the demoulding.The temperature of different samples does not wait for from 180 to 165 to 150 ℃.Observe, under the temperature that reduces, height is subjected near the leafing step-down stress angle and the acute angle.

Embodiment 8: be furnished with the fixed intermediate form of thermoforming (30 * 30 centimetres of plate surfaces) on the manual Fonteyne compression molding press of box part mould.Original shaping temperature (T _{Formpiston side and cavity side}) be 150 ℃.By contacting heat, it was heated in press 5 minutes.Then press cuts out, and apply the power 1 minute of 5kN.Resulting product shows attractive surface smoothness.

Embodiment 9: use extruding machine (at 165 (drop in) to 190 ℃ of operations, and die head temperature is 200 ℃).Top roll, central roll and following roll temperature are respectively 90,80 and 40 ℃.Use 0.8-0.10 rice/minute linear speed.Raw material has 35 centimetres sheet width, 1.0 to 1.2 millimeters polypropylene thickness, and respectively do for oneself 0.2 millimeters thick and 50cc of intermediate form is wide.With intermediate form first roller from above charging, and in independent operation, with intermediate form first roller from below feeding.In an operation again, at the opposite layer of first roller from top and bottom feeding intermediate form.Obtain good bondingly, and do not detect amount of warpage or only detect unconspicuous amount of warpage.

According to above recognizing, goods manufactured according to the present invention show many beneficial characteristics, include but not limited to, recyclability, compare the ability that reduces wall thickness (and be accompanied by weight and material cost is saved), good low-temperature impact resistance with reinforcing material not, when impacting, do not have fragmentation, good long term creep resistance, good long term fatigue resistance, good abrasion resistance, long term dimensional stability or their any combination.

For example but without limitation, compare with glass filled polypropylene material, can reach the twice, three times or even four times of baseline room temperature toughness and low-temperature toughness according to self-reinforcing composite of the present invention (for example PP composite material) (density) with about 0.8 gram/cubic centimetre.

Should be realized that, in a particular aspects of the present invention, many aforementioned properties are that material is selected the result with the combination of processing conditions---this combination causes during all procedure of processings before finishing until end article, high form in the elongate member component of intermediate form keeps degree, for example keeps its orientation substantially.Especially, a method of the present invention is to avoid using before thermoforming, punching press or other intermediate form forming step any step of fixed intermediate form.Current material used consolidation step before any such intermediate form forming step.But for many novel embodiments disclosed herein, this orientation retentivity is not enforceable.Therefore, the technical staff will appreciate that, uses the various prior art materials of consolidation step still to can be used for making in these embodiments composite before the intermediate form forming step.In addition, can use the multilayer intermediate form, wherein be not that all layers all pass through and are used to keep the processing that is orientated.

" first " and " second " is not to be limited in the combination that only is made of first and second parts herein.When so describing, theme of the present invention can suitably comprise the 3rd, the 4th or more parts." elongated member " is not the coverage that will get rid of a plurality of elongated members.In addition, " (methyl) acrylate " is meant acrylate and/or methacrylate.Unless indicate separately, the use of " fixed " or " moulding " and so on procedure of processing does not require fixed or moulding fully; Also comprise the fixed or moulding of part.The saying of " A-B " component structure is not got rid of the existence of other layer or other material different with B with component A.In addition, the saying of " a kind of " or " one " element or step is not got rid of other element or step.Before certain limit, use term " approximately " or " being similar to " both to refer to that the upper limit also referred to lower limit and is not subjected to quantitative limitation listed in this scope (for example, " about 1 to 3 " is to comprise " about 1 to about 3 ").Unless indicate separately, or as indicating by alternate manner in the literary composition, " mixture " of polymer or " combination " comprise mixture, blend or even the copolymer of this base polymer.

Unless indicate separately, the size of various embodiments as herein described and geometry are not restrictive to the present invention, and other size or geometry also are possible.Can provide a plurality of structure members by single integrated morphology or step.Perhaps, single integrated morphology step can be divided into independent a plurality of parts or step.But, these functions can be gathered in single parts or the step." comprise ", " having " and " comprising " also comprise more restrictive term " by .... constitute " and " substantially by ... formation ".

In addition, although a certain feature of the present invention may only be made description in an exemplary, this feature can combine with one or more further features of other embodiment according to any given purposes.For example, the microbedding elongated member can be incorporated in the tubing, tubing can be used in combination with raw material and intermediate form, can in elongated member, comprise thermosets, can in the elongated member of non-co-extrusion band, comprise microbedding, or can be used in the others of the present invention about the material that a part of the present invention or aspect are mentioned.According to above recognizing, the manufacturing of the unique texture of this paper and operation thereof also constitute method of the present invention.

It being understood that foregoing description only to be used to illustrate and nonrestrictive.On the basis of reading above-mentioned explanation, the many embodiments except that the example that is provided and many purposes are conspicuous for those skilled in the art.Therefore should not determine invention scope, and should determine with reference to the full breadth of the counterpart of claims and these claims with reference to above-mentioned explanation.The disclosure of all articles and list of references (comprising application and open) is all incorporated herein by reference.Do not represent the abstention of this theme aspect the theme of in following claim, ignoring disclosed herein any, and should not be considered as the part that the inventor is not considered as this theme disclosed theme of the present invention.

Appendix

Without limitation, unless indicate separately, following content is the example that is used for understanding the method for testing of described herein and the character that claims are cited.

Use Q1000 TA equipment to measure degree of crystallinity by differential scanning calorimetry (DSC).In this is measured, 10 milligrams of little propylene polymerization matter samples are enclosed in the aluminium DSC dish.Sample is put into the DSC chamber that purges with 25 cc/min nitrogen, and be cooled to approximately-100 ℃.By being heated to 225 ℃ with 10 ℃/minute, set up the standard thermal history of sample.Sample is kept melting fully guaranteeing in 3 minutes at 225 ℃.Then sample is cooled to approximately-100 ℃ with 10 ℃/minute.Keep isothermals 3 minutes with stabilisation at-100 ℃ in sample again.Then it is reheated to 225 ℃ with 10 ℃/minute.Record is for the observed melting heat of rescan (the Δ H in 80-180 ℃ of scope _{Observed value}).Set up the relation of observed melting heat and degree of crystallinity (accounting for sample, for example the percentage by weight of polypropylene specimen weight) by following formula: degree of crystallinity %=(Δ H _{Observed value})/(Δ H _{Isotaxy pp}) * 100, wherein at B.Wunderlich, Macromolecular Physics, volume 3, Crystal Melting, Academic Press, New York, 1960, write down melting heat (the Δ H of isotactic polypropylene among the p48 _{Isotaxy pp}), it is 165 joule/gram polymer (J/g).As above measure the high crystallization temperature of melt with 10 ℃/minute cooldown rate by DSC.Peak value measurement fusion temperature by melting transition.Similar analysis is applicable to the material beyond the polypropylene, changes described Δ H value into other material.

By the following determining molecular weight distribution of gel permeation chromatography (GPC) (MWD) (for example for polypropylene homopolymer).Are being furnished with 4 line style mixed bed columns by gel permeation chromatography (GPC), analyzing polymers on the Polymer Laboratories PL-GPC-220 high temperature chromatogram arrangement of 300 * 7.5 millimeters (Polymer Laboratories Plgel Mixed A (20-micron granularity)).Furnace temperature is 160 ℃, and the Autosampler hot-zone is 160 ℃, and warm area is 145 ℃.Solvent is to contain 200ppm 2,1,2 of 6-di-t-butyl-4-cresols, 4-trichloro-benzenes.Flow velocity is 1.0 ml/min, and injection volume is 100 microlitres.By under gentle agitation, sample being contained 200ppm 2 what nitrogen purged at 160 ℃, 1,2 of 6-di-t-butyl-4-cresols, dissolving is 2.5 hours in the 4-trichloro-benzenes, the 0.2wt% sample solution that preparation is used to inject.

Use the elution volume of 10 Narrow Molecular Weight Distribution polystyrene standards (from PolymerLaboratories, EasiCaI PS1,580-7,500,000 gram/moles) in conjunction with them, deduced molecular weight is measured.Use suitable Mark-Houwink coefficient (as Th.G.Scholte, N.L.J.Meijerink, H.M.Schoffeleers, and A.M.G.Brands, J.Appl.Polym.Sci., 29,3763-3782 (1984) is described, incorporated herein by reference) and polystyrene (as E.P.Otocka, R.J.Roe, N.Y.Hellman, P.M.Muglia, Macromolecules, 4,507 (1971) is described, incorporated herein by reference) in the Mark-Houwink formula: { η }=KM ^a(wherein for the analysis of polypropylene specimen, K _Pp=1.90E-04, a _Pp=0.725 and K _Ps=1.26E-04, a _Ps=0.702), the equivalent weight of working sample polymer (for example polypropylene).

Unless indicate separately,, measure 1% secant bending modulus by ASTM D790-00 for the listed material of this paper; According to ASTM D792 density measurement; Infer fusion temperature by differential scanning calorimetry according to ISO 11357-3; And according to ISO 178 mensuration bending moduluses.

According to ASTM D1238-01 test method 230 ℃ of melt flow rate (MFR)s with 2.16 kilograms of weight measurement propenyl polymers.According to ASTM D 1238-01 test method at 190 ℃ of melt index (MI)s with 2.16 kilograms of weight measurement polyvinyls.

By with adding the dimethylbenzene (inhibited xylene) of 200 milliliters of inhibition in 4+/-0.1000 gram sample dissolution to the 250 milliliter Erlenmeyer flask and by pipette, measure xylene soluble part.In order to suppress dimethylbenzene, in beaker, in 200 milliliters of dimethylbenzene, add 18.35 gram Irganox 1010, and stir until dissolving.After Irganox 1010 dissolvings, pour solution into 4.9 gallons of diformazan benzos solution is fully mixed.Put into stirring rod, water-cooled condenser is placed on the flask and with the flask assembly place on magnetic stirrer/hot plate.Vigorous stirring is also regulated heating to obtain gentle boiling, dissolves fully until sample.In this program, should on condenser, keep blanket of nitrogen.After sample dissolution, the flask assembly is taken off from magnetic stirrer/hot plate, take out stirring rod, add a cover then.Allow flask be cooled near room temperature (30 ℃, about 1 hour of cooling cost).On flask, add and put lead ring and be immersed in the water bath with thermostatic control.Temperature in flask reaches after 25+/-0.5 ℃, leaves standstill more than 30 minutes in water again.In cooling procedure, insoluble partly precipitated.Filtering solution; Then 100 ml aliquots samples of filtrate are placed in the aluminium dish and nitrogen flow down be evaporated to dried.By residual polymer is weighed, measure the DDGS that exists.

Isotaxy five unit group percentages, isotaxy three unit group percentages and isotaxy five unit groups/three unit group ratios are by the following mensuration of those of ordinary skills: ¹³Nuclear magnetic resonance (NMR) provides the direct measurement of the steric regularity of poly-(propylene) homopolymers.The end of the chain is ignored in analysis used herein and counter-rotating (inverse) is inserted.Claim (mm, mr and rr) for three unit group names, " m " represents meso, and " r " represents racemic.Isotaxy three unit group percentages are measured values of mm three unit groups.V.Busico, R.Cipullo, G.Monaco, M.Vacatello, A.L.Segre, Macromolecules 1997,30, and 6251-6263 has described the method for using NMR assay determination isotaxy five unit groups and three unit groups.

Isotaxy five unit groups/three unit group ratios are ratios of isotaxy five unit group percentages and isotaxy three unit group percentages.When measuring isotaxy five unit groups and isotaxy three unit class values,, in the mixture of 2-o-dichlorohenzene, prepare sample by 0.5 gram polypropylene homopolymer is dissolved in 1.75 gram tetrachloroethanes-d2 (TCE-d2) and 1.75 grams 1.Sample is mixed with promotion 150 ℃ of homogenizing and with hot rifle heating in heater (block).On VarianUnity+400MHz, at 120 ℃, use 1.32 seconds acquisition times, 0.7 second duplicate delays, 4000 collections and proton decoupling (fm-fm modulation) continuously under sample rotation and non-rotary situation, are carried out the NMR experiment.Used total scanning time is 2.25 hours.

Claims (23)

1. method of making multiple tube, described comprising the following steps:

A) carry core tube feeding;

B) cover the core pipe with the intermediate form that comprises at least one circle thermoplasticity elongated member, wherein said elongated member comprises first thermoplastic and second thermoplastic;

C) fixed described intermediate form; With

D) choose wantonly and at least a portion of intermediate form and core pipe, apply sheath has intermediate form with protection core pipe.

2. method according to claim 1, wherein said core pipe comprises polymer.

3. method according to claim 1 and 2, wherein said intermediate form comprise a plurality of elongated member layers, and wherein one deck comprises the elongated member that is stretched to about at least 5x at least.

4. according to each described method of claim 1 to 3, wherein said elongated member comprises multi-layer co-extruded band, and described consolidation step comprises, after covering the core pipe with intermediate form, with intermediate form about at least 1 minute of about at least 150 ℃ of maintenances.

5. according to each described method of claim 1 to 4, the thermoplasticity elongated member of wherein said intermediate form comprises two-layer at least winding.

6. according to each described method of claim 1 to 5, wherein said sheath comprises polymer.

7. according to each described method of claim 1 to 6, wherein gained tubing has the maximum 250 hours circumferential stress performance of pressure of bearing 7MPa at 80 ℃.

8. according to each described method of claim 1 to 7, any sheath that wherein applies and/or at least a thermoplastic of intermediate form comprise non-migrating processing aid or surface modifier.

9. according to each described method of claim 1 to 8, wherein said non-migrating processing aid or surface modifier comprise high molecular weight silicone.

10. according to the method for claim 9, wherein said non-migrating processing aid or surface modifier comprise dimethyl siloxane.

11. according to each method of claim 1 to 10, the wherein at least a ethene that comprises in first thermoplastic and second thermoplastic.

12. according to each described method of claim 1 to 10, wherein (i) first thermoplastic comprises propylene-ethylene copolymers, (ii) second thermoplastic comprises the isotactic polypropylene homopolymers, it has about at least 70% degree of crystallinity, the isotaxy five unit groups greater than about 85%/three unit group ratios; Or combination (i) and (ii).

13. method according to claim 12, wherein (i) described first thermoplastic has following feature: show about 0.3 to about 50 the gram/10 minutes according to the melt flow rate (MFR) of ASTM D1238 at 230 ℃; According to about 0.858 to about 0.888g/cc the density of ASTM D792; D) about ethylene contents of 5 to about 15wt%; About 50 to about 135 ℃ melting range; About 50 to about 75 Xiao A hardness; With according to ISO 178 about bending moduluses of 10 to about 280MPa; Wherein (ii) second thermoplastic comprises polypropylene homopolymer, this polypropylene homopolymer show be lower than about 7 the gram/10 minutes according to the melt flow rate (MFR) of ASTM D1238 at 230 ℃; 1% secant bending modulus greater than about 2000MPa; At least about 70% degree of crystallinity; Isotaxy five unit groups greater than about 85%/three unit group ratios; With greater than about 133 ℃ crystallization temperature; Or combination (i) and (ii).

14. according to each described method of claim 1 to 13, wherein said elongated member comprises a plurality of microbeddings.

15. according to each described method of claim 1 to 14, wherein said sheath is made by thermoplastic.

16., wherein before applying sheath at least a portion of intermediate form and core pipe, carry out the step of fixed intermediate form according to each described method of claim 1 to 15.

17., wherein cover step and be included at least four layers of winding layer of winding on the core pipe according to each described method of claim 1 to 16.

18. according to each described method of claim 1 to 17, wherein consolidation step was carried out about 1 to about 5 minutes at about 100 to 175 ℃.

19., wherein carry out consolidation step by the heat that in applying the step of sheath, obtains according to each described method of claim 1 to 18.

20. according to each described method of claim 1 to 19, wherein said tubing has at least one blind end.

21. according to each tubing of making according to claim 1 to 20.

22. the purposes of each tubing of making according to claim 1 to 20.

23. tubing that comprises fixed intermediate form, this intermediate form comprise at least one stretching, the co-extrusion elongated member, this element comprises the propylene ethylene copolymers layer that contains about 3 to 15wt% ethene and the polypropylene homopolymer intermediate layer between the propylene ethylene copolymers layer.

Images