CN101043996A - Plastic composite articles and methods of making same - Google Patents

Abstract

The invention provides a reinforcing composite product and a preparation method, which normally adopts a polymer wild phase of an intermediate form (10), and the form comprises a monadic structure (for example, physical geography textile materials), a multilayer slender component, or a combination. The intermediate form can be prepared and processed, so as to form the composite product, comprising the intermediate form process in any consolidation steps (for example, a cladding form or other forms), generally, the trend to the polymer reinforcing materials, and the morphology keep degree of relevant height caused in the products with relatively smooth surfaces.

Description

Plastic composite articles and preparation method thereof

Claim of priority

(the attorney docket 63863 of U.S. Provisional Application 60/621,463 submitted this application claims on October 22nd, 2004；1062-041P1)；60/717,965 (the attorney docket 63863B that September in 2005 is submitted on the 16th；1062-041P2)；60/718,025 (the attorney docket 64371 that September in 2005 is submitted on the 16th；1062-051P1)；60/725,399 (the attorney docket 63863C that on October 11st, 2005 submits；1062-041P3), the priority of (express delivery EV789808245US) and submitting day equity, it is all these incorporated herein by reference.

Cross reference to related applications

The application with submit simultaneously, co-own, co-pending entitled Apparatus andProcess for Manufacturing Shaped Plastic Reinforced Composite Articles (attorney docket 64371A；1062-051WO)；Improved Polyolefinic MaterialsFor Plastic Composite (attorney docket 63863E；1062-41WO 1)；ImprovedMicrolayer Structures and Methods (attorney docket 63863F；1062-41WO3)；With Improved Composite Pipes and Method of Making Same (attorney docket 63863G；Application 1062-41WO4) is related；It is all these incorporated herein by reference.

Technical field

The present invention relates generally to the composite materials with enhancing by polymer phase, with relate more particularly to include polymer reinforcing material composite material, its processing (by overmolded or other means) normally tends to cause in polymer reinforcing material relatively high form to keep degree.

Background of invention

Over the past several decades, by the development of improved composite material, engineering material has obtained marked improvement.Composite material is enabled a designer in conjunction with the favorable characteristics of various ingredients material to obtain material usually with one or more properties different from independent component material.

The especially rapid field of progress is reinforced plastics field.For example, being current way incorporation inorganic reinforcement phase (such as using the fiber made of glass, carbon, metal or another inorganic material) Lai Gaijin plastic nature.In many cases, the form (form) for providing comprising inorganic reinforcement and being blended with thermoplasticity or thermosetting plastics matrix impregnation or in other ways.A more universal specific example is Glass Mat Thermoplastic (GMT) composite material in recent years, usually using the glass mat with such as polyacrylic thermoplastic dipping.Material type difference between glass and thermoplastic matrix often complicates the effort of any recycling and the recycling of these GMT materials.

In recent years, plastics industry also tests the development of the thermoplasticity " fabric " for the one or more thermoplastic fibres (wherein also with or without the use of glass fibre) for using certain weave.In general, these materials are provided with weaving with consolidation form, that is, after braided fiber, they are heated to melt its at least part outer surface.After hardening, adjacent fiber is consolidated.

So far, the effort for providing suitable thermoplasticity enhanced form (its formation resulting product easy to process, especially by the product for moulding or being fabricated type at high temperature) is restricted.It has been observed that for example, consolidation step (wherein heating other units of fiber or enhanced form to fuse together) requires at least the first thermal history, and the step of forming gained moulded products requires at least the second thermal history.With the use of each additional thermal history, a possibility that morphologic change, increases, and along with the loss of mechanical performance, such as impact strength.

In paper " the RecycleableAll-Polypropylene Composites:Concept; provide the summary of various PP composite material technologies in Properties and Manufacturing ", Technische Universiteit Eindhoven (2004) (ISBN 90-386-2676-2) of Cabrera incorporated herein by reference.The document is hereby incorporated by reference.

Therefore, it is still necessary to improved composite system, with the one or more obstacles for overcoming current material to be faced.

Summary of the invention

The present invention relates to the discoveries of new material, and preparation and the combination and method of processing the new material.On the one hand, to various embodiments of the present invention, it is generally contemplated that the form includes one or more constitutional repeating units using the intermediate form at least one elongated member for including the first thermoplastic material.Intermediate form is suitable for before consolidation, during or after be processed (heat lamination or molding such as under high-temperature and pressure, such as by thermoforming or pass through moulding technology such as blow molding, compression molding, rotational molding or injection molding or other) and optionally strain hardening (reinforced or harden by the plastic deformation of the recrystallization temperature range lower than composition material) to form shaped composite article, such as may include at least with the second thermoplastic material of the identical or different type of the first thermoplastic material (being such as used as raw material).In specific example, in its end-state, it is smooth and wrinkle-free that consolidation, which limits one or more elongated members of constitutional repeating unit and the surface of moulded products (in spite of the second thermoplastic material is included), therefore does not show visual folding line or wrinkle in the exposed portion of form substantially substantially in the composite article of acquisition.Furthermore, compared with being subjected to other thermal history with the material of consolidated intermediate form before shaping, usually there is product of the invention the relatively high form in unit to keep degree (such as compared with the initial configuration for forming elongated object), for saving the performance such as impact property.

In another aspect of this invention, intermediate form (regardless of whether consolidation) can be used in composite article, but the essence for not having the surface or product exposed to the open air does not require high-quality surface to cover with paint, lacquer, colour wash, etc..It therefore, is not wrinkle-free embodiment there may be wherein intermediate form.

In another aspect of this invention, it is contemplated by the invention that intermediate form experience heat treatment, the heat treatment makes it significantly relax from its original state until its state in the product obtained, cause the basic variation of form, or additionally results in any basic variation of its bending modulus or correlated performance.For example, embodiment imagine that intermediate form only undergoes minimum number number the impact of thermoplasticity form or the heat treatment of correlation properties can be changed substantially (as only once, twice or thrice).Another embodiment imagines intermediate form and (such as forming shaped form and during molding step) twice is only undergone can to change the impact of thermoplasticity form or the heat treatment of correlation properties substantially.Therefore, a scheme according to the present invention is any consolidation step for preparing shaped form without heating intermediate form before requiring the shaped form the step of.

In a specific aspect of the invention, the first thermoplastic material and the second thermoplastic material are identical plastic type, and more specifically they are polyolefin, and even more specifically they are acrylic.Using this mode, it is contemplated by the invention that simple scheme can be with the plastic products of Efficient Cycle to manufacture.

In another aspect of this invention, it is contemplated that provide the improved method for manufacturing the material of reinforced plastics product, which includes at least the first thermoplastic material and the second thermoplastic material.For example, it is envisioned that material supplier is supplied to the first thermoplastic material of user processed by user and the intermediate form of the second thermoplastic material.

Brief description

Figure 1A and Figure 1B shows the example of the cross section of feasible elongated member of the invention.

Fig. 2A and Fig. 2 B respectively illustrates the example according to the present invention not consolidated with consolidated intermediate form (intermediate form).

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

Fig. 4 A-4G shows pipe structure according to the present invention.

Fig. 5 A and 5B show the exemplary comparative data that can be obtained through the invention.

Fig. 6 A and 6B show the example data that can be obtained through the invention.

Detailed description of the invention

In the first particular aspects, method of the invention is related to manufacturing intermediate form and comprising steps of at least one elongated member of the first thermoplastic material a) is provided, with the surface portion that can be melted before the fusing of adjacent or interior section (such as internal approach part)；And elongated member b) is processed into the intermediate form including multiple constitutional repeating units, these structural units can usually move freely relative to one another, and wherein the form can be processed to form essentially smooth, wrinkle-free molding final product.In general, though not in being required to (such as illustrating for the microbedding (microlayer) of this paper) in each situation, elongated member includes orientation polyolefine, the orientation polyolefine that can especially process according to the present invention in the case where keeping its initial configuration substantially.

In another particular aspects, method of the invention is related to intermediate form article of manufacture.Therefore, under this aspect, procedure of processing include consolidate and formed three-dimensional intermediate form (such as, carry out in single operation or be carried out continuously in multiple operations simultaneously) the step of, the intermediate form includes multiple constitutional repeating units of at least one elongated member and the first thermoplastic material, has the surface portion that can be melted before adjacent part (such as adjacent alignment portion)；Consolidation and molding intermediate form are placed in die cavity；The second thermoplastic material is added in die cavity；And the enhancing composite article including consolidated intermediate form and the second thermoplastic material is released from die cavity.Partial consolidation can also be carried out in the step of the second thermoplastic material is added into die cavity.This illustrative aspect can of course be implemented in conjunction with above-mentioned first illustrative aspect or individually.Therefore, can be by manufacturer's manufacture intermediate form and resulting product, or manufacture (such as material supplier provides intermediate form to product manufacturer) respectively from different manufacturers.In the case where furthermore, it is possible to the form not consolidated before the second thermoplastic material is added into die cavity carry out above-mentioned steps.Since the high form in the elongated member portion of product keeps degree, the typical products according to made of disclosure herein advantageously show excellent impact and correlation properties (especially because ability, due to use unique material select or combine and/or processing conditions).

Various aspects of the invention are based on the discovery to material and/or the unique combination of procedure of processing --- and these combinations cause Elongated Member Materials that there is relatively high form to keep degree (compared with the initial configuration after its initial tensile and before being processed into composite article).As a result, disclosure herein be advantageously able to valuably to keep gained composite article as impact property performance.

As can be seen that disclosure herein is related to can be used for the new material combination of field of compound material, especially with can consolidate and optionally molding and processing (such as, but not limited to overmolded) is related to form the elongated member of composite article.

As can be seen that various aspects are illustrated with polyolefine material, although the explanation is not limited to this from disclosure herein.Specific progress provided by the invention includes the special polyolefins combination of materials determined in field of compound material with unique applicability.Particularly, the premise of one aspect of the present invention is to identify acrylic (such as propylene-ethylene copolymers, propylene-alpha-olefin copolymers as multilayer elongated member, their mixture is other) copolymer, fusing point is lower than adjacent polypropylene layer, especially oriented polypropylene layer.After processing as described herein is to form product, resulting materials (especially oriented polypropylene layer) show to keep degree using the form compared with its initial drawn state that traditional material is unable to reach before this.Therefore, each aspect of the present invention with ethylene contents is about 3 to 25wt% (such as 5 to 15wt%), melting range is about 50 to 135 DEG C, and bending modulus be about 8 to about 325Mpa or higher (for example, at least about 375MPa) the use of propylene-ethylene copolymers and the second thermoplastic material including polyolefin (such as propenyl polymer) premised on.This propylene-ethylene copolymers can have the molecular weight distribution of the Xiao A hardness of about 40 to 90 (or higher), about 1.5 to about 4, and at least about 0.3 gram/10 minutes melt flow rate (MFR)s or any combination of them.

One example of available propenyl polymer is usually isotactic or relative stiffness.For example, it can be with 1% Secant flexural modulus for being greater than about 1000MPA (being particularly greater than about 2000MPa (such as about 2500MPa or higher)) and/or greater than five unit group of isotaxy/tri- unit group ratios polypropylene homopolymer of about 70% (being greater than about 85%).In addition, this polypropylene usually has the crystallinity of highest fusion temperature and/or at least about 30% (particularly at least about 50% or even 70%) greater than about 160 DEG C (being greater than about 165 DEG C).

Disclosure herein is also premised on following understanding --- by being used together optional non-migrating processing aid or surface modifier of the dosage lower than the about 10wt% of the material of elongated member with above-mentioned polymer or with other polymer as described herein, favourable outcome can be obtained.As an example, non-migrating processing aid or surface modifier may include the reagent selected from siloxanes (such as high molecular weight silicone, such as alkylsiloxane, such as dimethyl siloxane), polyolefin, halogen polymer or any combination of them.

About the novel compositions of material, disclosure herein has determined the unexpected method by manufacturing composite material using geophysical textile material (such as polyolefin geophysical textile) wherein.For example, a kind of such method, which contemplates, provides the intermediate form for including the steps that Geophysical textiles and with thermoplastic material that intermediate form is overmolded (overmolding).It is optionally possible to use above-mentioned non-migrating processing aid or surface modifier.

Disclosure herein also shows, the present invention relates to the embodiments of the elongated member characterized by least 4 layer heap laminations, each layer includes polymer, each layer all has (more generally significantly thinner less than about 50 microns of thickness, such as may even be thinner than about 5 microns), and each layer is adjacent layer difference at least one feature selected from composition, crystallinity, molecularly oriented, molecular weight, meltflow ability, highest fusion temperature, glass transition peak, crystallization temperature, sealing initiation temperature, softening point, molecular weight distribution or any combination thereof.

In an arrangement, elongated member at least one or may the polymer of each microbedding be acrylic polymer (such as polypropylene homopolymer, such as isotactic polypropylene homopolymer).For example, polypropylene can be used in one or more (or even all) microbeddings.It can also include ethylene with the polymer of at least one microbedding.The polymer of at least two adjacent microbeddings may include ethylene (as selected from propylene-ethylene copolymers, linear low density polyethylene, high density polyethylene (HDPE) or its any mixture).The polymer of each adjacent microbedding may include polyethylene.Typically, the peak melting temperature of every kind of the polymer of at least two adjacent microbeddings differs at least about 5 DEG C.

Additive or other functional materials can be used between at least two layers of stack layer, such as (tie-in) layer or intermediary adhesive layer is coupled (its use is not limited only to microbedding as described herein, may be also used in disclosed any multilayered structure).These materials can also include the above-mentioned non-migrating processing aid or surface modifier at least one layer of exposed surface.

Although the use of the material referring to disclosed in entire description (such as disclosed propylene-ethylene copolymers, isotactic polypropylene homopolymer or combinations thereof) is illustrated herein, the microbedding improvement of this paper is not limited only to this kind of material.A variety of materials combination, the first polymeric material for example including polyolefin and the second polymeric material including polyamide can be used；The first polymeric material including polyolefin and the second polymeric material including polyester；The first polymeric material including polyamide and the second polymeric material including polyester；It or even include a kind of the first polymeric material of polyester and the second polymeric material including another polyester.

As can be seen that the present invention can be used for many different purposes.A kind of preferable use is estimated to manufacture multiple tube using disclosure herein.The method for contemplating manufacture multiple tube as general introduction, these explanations comprising the following steps: core pipe is provided；Core pipe (such as being made of polymer) is covered with the intermediate form for including at least one circle (winding) thermoplastic elongated member, wherein elongated member includes the first thermoplastic material and the second thermoplastic material；Consolidated intermediate form；Apply sheath optionally at least part of intermediate form and core pipe to protect the core pipe for having intermediate form.

As can be seen that but be not limited to, other than the characteristic of material itself and their form processing, aspect of the invention further relates to the product made of material described herein, manufactures the further specific method of this based article, uses the method for this based article.

Elongated member and intermediate form

It is turning initially to intermediate form of the invention, it is however generally that, these forms include the elongated member that at least one has the composition including at least one thermoplastic material." elongated member " typically refers to the element that one of dimension (such as length) is longer than at least one other dimension (such as width, height, thickness or diameter), particularly, the length of elongated member is significantly greater than width or height (for example, at least about 10 times or higher) herein.Therefore, elongated member may include herein, but be not necessarily limited to, and be selected from the element of fiber, shaft, rope, yarn, band, monofilament, band (straps) or any combination thereof.From the foregoing it will be appreciated that film also may be considered that in the meaning of " elongated member " in many aspects.Miniaturized component is also feasible, such as whiskers or tablet.Although " elongated member " is broadly treated herein, however, it should be understood that the particularly preferred form of elongated member specifically includes one of yarn, band, fiber and monofilament or a variety of.Highly preferred elongated member is ribbon form.

Moreover, it should be appreciated that elongated member of the invention generally goes through processing to obtain initial configuration, especially initial orientation state (such as being uniaxially stretched, biaxial stretch-formed or stretch in other ways, such as stretched according to ratio specified herein).When many particular advantages that subject matter disclosed herein can be used to obtain are included in process finishing, the ability of the initial configuration in elongated member is especially kept substantially in the final article.Thus, for example, after processing, the molecularly oriented of elongated member keeps its original state substantially, (such as keeping at least about the 50% of elongated member, more preferable 75% initial orientation).

The size of elongated member usually enables the element hand-manipulated.More particularly, determine that the size of elongated member allows it to mechanically actuated to be processed into intermediate form.Such as, a specific example of the invention contemplates thickness, width or diameter and is particularly no more than about 1 centimetre no more than about 5 centimetres, then particularly not more than about 0.5 centimetre, particularly it is no more than about 1 millimeter of elongated member, such as yarn, band, fiber or monofilament.For example, a kind of method is lower than 5 millimeters, thickness using width lower than 1 millimeter and particularly lower than the elongated member of 0.5 millimeter (such as about 0.01 to 0.25 millimeter), such as yarn, band, fiber or monofilament.Certainly, intermediate form may include multiple elongated members, and each has different thickness and/or width.For example, the warp thread and weft elongated member of woven form can be respectively provided with different thickness and/or width.In addition, when using film as elongated member herein, they can be significantly larger (for example, can be wide at least about 5 meters, and at least about 10,20 or even 40 meters long).

Typical elongated member is continuous in shape.But the element can at least partially along the abundant density of length (densified) of elongated member, part density (such as foaming), perforation, corrugation, twisting, or any combination thereof.Elongated member can have inconsistent property or other feature along element dimensions.

Will recognize, disclosure herein be it is universal, be not necessarily limited to the embodiment particularly pointed out.For example, the present invention indicates the various different materials that can be used as elongated member, the special-purpose regardless of this elongated member.But, especially in the declared range about polymeric reinforced composites, the elongated member of one or more this paper is usually assembled into intermediate form, such as, but not limited to weaving, knitting or other forms, wherein there are multiple constitutional repeating units (such as warp thread and weft yarn use multiple elongated members).But repetitive unit can be simple as each circle (windings) of winding arrangement (this structure can be used single elongated member and obtain).

Therefore, it after forming elongated member, is processed to manufacture intermediate form, such as the form selected from woven form, winding form, knitting form, type of weave, random dispersion form or any combination thereof.The form can also be wrapped up or be coated with or cover in other ways.Intermediate form as described herein generally includes multiple constitutional repeating units.The example of these structural units is shown in fig. 2.Such as, intermediate form 10 may include multiple constitutional repeating units 12, they are arranged in pattern 14, such as the basket weave of Fig. 2A, another plain weave, twill-weave (such as herringbone, tweed, hound-tooch, tartan or other twills), lace, satin weave or any combination of them.The example of specific weave includes following weaves --- and pattern warp elongated member is walked on weft elongated member up and down with the warp/latitude ratio of 1/1 to 14/2 (such as 2/1,2/2,3/1 or other).Another specific examples of weave include, but are not limited to 2/1 twill, 2/2 twill, crowfoot satin, 2/2 basket weave, 5H satin weave, 8-H satin weave or other.Thus, it will be seen that each structural unit of the form can be arranged relative to each other with a variety of feasible constructions.For example, as shown in Figure 2A and 2B, overlap joint unit is usually orthogonal.Also it can according to need and use other weaving angles.In general, the weight ratio of warp thread and weft elongated member is about 90: 10 to about 40: 60, more preferably from about 70: 30 to about 45: 55 (such as about 50: 50).

Although as above disclosing exemplary warp and weft yarn range, other ranges may also provide satisfactory result.For example, the average of the warp elongated member of every cellar area can be identical as the quantity of weft elongated member in same area.Respective quantity can also be different from each other.For example, the average of warp thread and weft elongated member can differ 10% or less (for example, in 4 square centimeters, can there is 18 warp elements and 20 weft elements) in per unit area.They can also differ greater proportion, such as differ at least 20%, or even differ at least 50% (for example, can have 10 warp elements and 20 weft elements in 4 square centimeter areas).

Between warp thread and weft elongated member, the thickness and/or width of elongated member can also be essentially identical, they, which are differed, in this way is no more than about 10%.But between warp thread and weft elongated member, the thickness and/or width of elongated member can differ 20% or more.As being discussed in further detail at once, according to it is also acknowledged that intermediate form may include multilayer, wherein at least two layers with weave characteristic different from each other above.

Unitary (monolithic) elongated member and Geophysical textiles

As shown in following discussion, can elongated member used according to the invention can have substantially uniform construction, i.e., form an identical meta structure from the beginning to the end.They can also width, thickness or diametrically have different compositions, such as by multi-ply construction it is achievable like that.For the former, although the winding of unitary elongated member structure be it is feasible, more generally, unitary elongated member is woven form, such as the material of commonly referred to as Geophysical textiles.

In fact, many specific characteristics of the invention include efficiently using above-mentioned unitary material, such as the ability of the Geophysical textiles.These materials usually have many civil engineering applications (although the present invention does not continue so) at present, such as one of corrosion control/soil conservation, silt fence, landscaping, enhancing, isolation (such as paving the way), draining and other purposes or a variety of.Geophysical textiles quite often show relatively high bi-directional strength and rigidity, and include the textile fabric that may do not consolidate and therefore show certain infiltration capacity and/or capacitivity (permitivity).The property of Geophysical textiles can change in a wide range.As an example, Geophysical textiles can show at least about 0.3kN, particularly about 0.5 to about 3kN clamping (grab) tensile strength (according to ASTM D4632), at least 10%, such as about 15% grab tensile strength extends (according to ASTM D4632), 50% or higher is horizontal and possible.Geophysical textiles show at least about 1000kPa, particularly about 2000 to 10,000kPa (such as about 3000 to 7000kPa) Mullen BURSTING STRENGTH (according to ASTM D3786), at least 0.20kN, the particularly breakdown strength of about 0.25kN to about 0.80kN (according to ASTM D4833).The example of commercially available Geophysical textiles includes polypropylene fabric, such as it is run after fame those of offer with Propex (come from Propex Fabrics (Georgia)), and by Don & Low with title LOTREK, by Mirafi (Ten Cate Nicolon) with title GEOLON, and by other sellers (such as US Fabrics, Inc. the Geophysical textiles provided with LINQIndustrial Fabrics, Inc.).

It would be recognized that available Geophysical textiles can be made of one or more thermoplastics (such as polyester, polyolefin or combinations thereof object) according to the present invention.Certainly, Geophysical textiles can be made in various individual thermoplastic materials disclosed herein.Geophysical textiles usually (but not being certain) include alignment portion, and herein using weaving Geophysical textiles made of product include elongated member, the element to include alignment portion, especially keeps the part of its initial configuration by processing (such as stretching) substantially.Although a kind of preferred method considers using weaving Geophysical textiles, Geophysical textiles are also possible to (such as being made of usual needle thorn and hot sticky staple fiber and/or continuous monofilament) of nonwoven.Geophysical textiles are usually made of Slit films or extrusion molding monofilament or the like, and are therefore generally increased by work comprising alignment portion.Fabric may include one or more multifilament.In another aspect of the invention, Geophysical textiles may include the one or more fibers naturally occurred, such as jute, hemp or the like.

It will recognize from the discussion of this paper, geophysical textile material can be used in each embodiment disclosed herein.As an example, it but is not limited to, Geophysical textiles can be overmolded according to disclosure herein；Between in multiple layers in form in conjunction with one or more other Geophysical textiles, be incorporated in multi-layered textile and/or winding intermediate form in；One of homopolymer or copolymer of this paper or combination can be used；Or any combination of them.

Multilayer elongated member

It is discussed in greater detail turning now to the other aspects of elongated member, realizes that a commonsense method of technology described herein is using multilayer elongated member.Particularly, multilayer elongated member is usually using at least first surface part and the second part adjacent with the first part, wherein the first and second parts are different in terms of composition, polydispersity, form, melt flow or any combination thereof.For example, a kind of ad hoc approach contemplates at least one elongated member of the first thermoplastic material, there is the surface portion that can be melted before adjacent part (such as orientation adjacent part).

Invention advantageously provides use single polymer (such as polymer A or B itself in terms of Geophysical textiles as described in front of) or a variety of adjacent polymer (such as polymer A and polymer B-herein referred to as A-B component structure, such as A-B, A-B-A, A-B-C, A-B-C-D, etc., or any combination of them, such as A-B-D, A-B-C-B-D, A-C-B, or it is other, wherein C and D refers to but is not limited to additional possible polymer, such as illustrate those of to be likely encountered using microbedding shown in this article) ability of the manufacture such as elongated member of band.When using different polymer in elongated member, they can respectively have same composition or different compositions.They can come from identical or different polymer group (such as polyolefin).They can come from identical certain types of polymer (such as polypropylene) in family, but it is different from each other in some features (such as weight average molecular weight, polydispersity, form, meltflow ability or other melt characteristics or any combination of them).It should be appreciated that one or more components (for example, the other components of A, B, C, D or some) need not be polymer, and it can be additive or other functional materials.

It is turning initially to multilayer embodiment, such as being likely encountered in the material for including component A and B (such as A-B-A elongated member), A and B component are usually relative to one another with layered relation arrangement (such as Figure 1A, juxtaposition (such as bicomponent material) or core-skin relationship (such as Figure 1B)).B component can only part (such as exposure at least side (showing two exposed sides see, e.g. Figure 1A)) or be covered around its edge (as shown in Figure 1B) completely by component A.It would be recognized that the layered embodiment of Figure 1A can also include circular edge or surface.Component B is usually located at the inside of elongated member, and can be the material that fusing point is higher than component A.Therefore, the structure and material of elongated member melts component A before component B, and can keep the shape at least component B substantially., it will be recognized that the relative quantity of component A and component B can change.It uses some on the way, for example, relatively small outer layer (such as A layer of A-B-A multiple layer combination) can be applied on relatively large internal layer (B layers).Biggish outer layer can be used in other purposes.For example, combining for A-B-A, the relative volume of each layer can be about 1: 1: 1 to 1: 35: 1, particularly about 1: 10: 1 to 1: 25: 1, then especially about 1: 15: 1 to 1: 20: 1 (such as 1: 17: 1).Similar ratio can be used in A-B skin-core structure, but omits the corresponding amount of an outer layer.For example, ratio become 1: 1 rather than 1: 1: 1.

As described above, the elongated member (such as co-extrusion band) made of these components (such as A-B-A multilayer elongated member) preferably comprises about 1 to 20wt% component A and about 80 to 99wt% component B.Although this relative scale is the typical proportions of many different elongated members according to the present invention, should not be regarded as limiting.For example, for some purposes the component A ratio bigger than component B can also be used in elongated member, and can obtain good result according to disclosure herein.Such as, component B is (for example including polyacrylic polymer, such as polyacrylic homopolymer) estimated about 50wt% (the such as less than about 45wt% of total weight that can be lower than total weight of amount, or may be about the 10 to about 45wt% of total weight, or again specifically for about the 20 to about 40wt% of total weight).

In general, when elongated member includes at least component A and component B, the fusing point (it can be within certain temperature range) of component A and B are different, and wherein the fusing point (it is, maximum fusion temperature of the material with melting range) of component A is lower than the fusing point of component B.In addition, higher melting-point material is typically at least partially oriented (such as being oriented either uniaxially or biaxially).Relative melting points can differ about 5 DEG C, but more generally differ at least about 10 DEG C, more preferably at least about 20 DEG C, and in a specific example, can differ up at least about 25 DEG C (such as about 30 DEG C) or higher.Such as, but not limited to, component A can have about 130 DEG C of fusing point, and component B can have the fusing point higher than about 160 DEG C.Due to the temperature span (spread) of fusing point, the result is that realizing certain range of work (window) --- within this range, component A can be flowed and be fused with adjacent material to realize consolidation while cooling.Meanwhile the significant risk for deteriorating and damaging its property (such as high bending modulus of entirety of elongated member) of initial configuration generation of component B can be reduced lower than its fusing point by being maintained at the processing temperature of component B.In process finishing, especially keep the ability of the initial configuration in elongated member that other benefits may be implemented again substantially in the final article.Other than keeping the ability of form, the consolidation near temperature range lower limit has the additional benefit for making elongated member usually less easily relax or shrink.

As set forth above, it is possible to find out, selection is fusing point (such as can be obtained according to ISO 11357-3 by differential scanning calorimetry) referring to melt characteristic temperature for discussion.It should be appreciated that fusing point cannot accurately specify (for example, because it exists in certain temperature range) for some materials.Therefore, for this kind of material, technical staff is, it will be recognized that the fusing point mentioned typically refers to maximum fusion temperature.Furthermore, in some cases, by another measurement of correlation standard for being substituted for the material melt feature, glass transition temperature or polymerization softening temperature, maximum crystallization temperature (such as described in WO 2004/033509 (incorporated herein by reference)) or even sealing initiation temperature (such as Isothermal Crystallization Kinetics and Morphology of Polypropylenes and Propylene/Ethylene(P/E)Copolymers；By C.H.Stephens, B.C.Poon, A.R.Kamdar, S.Chum, P.Ansems, K.Swogger, described in A.Hiltner and E.Baer. (Chicago, IL, 2004 years Mays of Presented at the SPE ANTEC Conference in), it is incorporated herein by reference), it the use of another like method may be more easily to each component.

Therefore, effectively, the required span (such as about 5 in this kind of melt characteristic temperature of polymer, difference of 10,20,25 or 30 DEG C or 30 DEG C or more) of the relevant melt characteristic temperature of each component A and B is generally selected so that the melting of component A can be carried out in the case where not reducing mechanical performance higher than component A under its Initial solid possessed by component B.

A kind of possible benefit of multilayered structure is to prepare elongated member to provide the ability of property difference in each section of elongated member, thus elongated member can for special-purpose, particular process condition group, or combinations thereof accurate adjust.Find out from the summary of this paper, the mode for obtaining advantageous multilayered structure can become according to the subsidiary result pursued, and multiple technologies can be used to obtain multilayered structure.Such as, one or more parts can be coated with, be laminated, bonding, being surface-treated (such as atmospheric treatment (such as aoxidize or be processed similarly), corona discharge, or other corona treatments), flame injection, ionization, radiation, powder coated, hot melt apply, or be otherwise connected on another part.In another method, different piece can be made to be subjected to different heat treatment, differently strained processing or other processing conditions.In another method, by different piece together co-extrusion.Also the combination of the above method can be used.

In more detail, in general, elongated member of the invention is originated from film (film can be non-oriented, but more generally uniaxial orientation, biaxial orientation or other).Such as, fairly typical is, elongated member (is especially selected from least one yarn, band, the elongated member of fiber or monofilament) it can be by molten polymer (such as the melt temperature in polymer, such as various polyolefin or other thermoplastics at about 200 to 240 DEG C) progress inflation film process (such as, air quenched blown films method as disclosed in WO2005035598, its is incorporated herein by reference), it is manufactured by cast film or sheet material (such as being quenched the molten polymer of extrusion using chilled roll) or by film or sheet extrusion (such as by water-bath).Also the combination of these methods can be used.Then film or sheet material are cut into preset width, such as sound wave cutting, hot knife cutting, their combination or other means using suitable cutting operation.Slit films then pass through the heating period (such as using thermal station) or stretched operation (optionally employing the stretching furnace for drawing by high temperature) is processed to required denier (such as about 1000 to about 20,000, such as about 13 can be greater than, and weight (for example, at least about 7 g deniers and may at least up to about 9 g deniers or higher, be particularly higher than about 10 g deniers of weight) 500).For some embodiments, Slit films can have about 60 to 300 tex characteristic (weight of the long band of about 10 kms).It by Slit films fibrillation and can also be wound on spool to be subsequently used in final products.The entire method generally but not must be continuation method.

As further special example, another feasible method for forming elongated member (elongated member for being especially selected from yarn, band, fiber and monofilament) can be makes molten polymer (such as in 90 to 230 DEG C melt temperature) by extrusion step (such as the water-bath for making it through 20 to 40 DEG C thereafter) with the cast-sheet of formation at most about 10 millimeters thicks (more typically about 1 millimeters thick) with suitable die head (optionally having taper aperture), such as sheet die (such as Collin Teachline extruding machine).The sheet material is cut into about 1 to 20 millimeter, it is particularly about 2 to 10 millimeters (such as about 5 millimeters) wide, and about 2 to 10 (such as about 5) or higher draw ratio are stretched between godet at about 50 to 70 DEG C (such as 60 DEG C) in one or more heating furnaces.Then by gained yarn, band, fiber or monofilament in one or more high temperature (such as higher than about 120 DEG C, such as at about 140 to 200 DEG C (such as about 170 DEG C)) further stretched with the addition draw ratio of one or more at least about 2 to 8 (such as about 3.5), this generates required thickness (such as about 0.3 to 2 millimeter, particularly about 0.05 to 0.3 millimeter (especially when cast-sheet is about 1 millimeters thick) or may be greater or lesser).Can also include lower than strained polymer fusing point at a temperature of one or more stretching steps.It will include that the material of polypropylene homopolymer is stretched at least 5 that a kind of feasible stretched operation, which includes at about 170 DEG C, and particularly at least 10, then especially at least 15 draw ratio.

In method in another method, such as uniaxial orientation processing, flat or round section bar is squeezed out, then according to the technology orientation of formation uniaxial orientation elongated member to obtain required toughness and denier.It is then possible to which elongated member is wound on spool.It would be recognized that the above method is suitable for forming the elongated member including two kinds of polymer, such as by the co-extrusion of two kinds of polymer to form band or monofilament.

In the manufacturing process of multilayer elongated member, it is also necessary to keep the rheological characteristic of each layer basic approximate to help in material by avoiding the accumulation or other consequences of undesirable shear stress when any feeding section and die head assembly.

From above it can be found that because technical staff is, it will be recognized that many alternative drawing process are feasible the present invention relates to stretching.It is current in many of these cases, so that film or sheet material is stretched (such as uniaxial, twin shaft or other) step by one or more, such as be used to form yarn, band, fiber or monofilament.Stretching can carry out in single-stage operation or multistage operation (such as dual-stage method).The usual progress at elevated temperature of stretching (such as especially for polyolefin, higher than about 60 DEG C, more generally it is higher than about 100 DEG C, such as about 100 to about 200 DEG C, be particularly up to about 190 DEG C (such as about 120 to 180 DEG C, particularly for polypropylene, about 140 to about 190 DEG C, such as about 150 DEG C to 170 DEG C), it is recognized that as the temperature condition of the other materials of polyester can be with listed difference).Alternatively consider, for including higher and system (such as A-B-A type structure) compared with low-melting component, stretches and usually carry out being higher than the temperature compared with the fusion temperature of low-melting component and in about 10 DEG C of the maximum fusion temperature of higher melt component.It can according to need the film amount of tension for selecting per stage (compared with its isotropism melt state), for example, about 2 × to about 20 × or higher (such as 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 completed by single phase (such one-off drawing realizes whole stretchings) or multistage operation (such as repeatedly continuously elongated).Higher or lower amount of tension may be feasible.In addition, multiple consecutive steps can be used also to realize required amount of tension although making disclosure particular for single stage draw.In the various stages, film temperature can keep constant or change in certain temperature range.Tension values are disclosed compared with by the film of isotropism melt composition herein with reference to gained elongated member.It is related to the other aspects of elongated member formation in more detail in the discussion of this paper.

But desirably, after the completion of stretching, elongated member (is especially selected from yarn, band, the elongated member of fiber or monofilament) show initial configuration, including orientation (usual uniaxial orientation, but may also have twin shaft or other orientation components).What is generated therewith is usually the raising of material strength and stiffness compared with its non-stretched or relaxed state.Such as, after the stretch, elongated member (especially including higher and compared with those of low-melting component (such as A-B-A type structure)), at least about 13GPa is typically exhibited according to the present invention, the particularly elasticity modulus of at least about 18GPa measured by ASTM D-638, the tensile strength of at least about 150MPa, more generally at least about 300MPa measured by following ASTM method of testing D-638.It will recognize, holding form (and subsidiary attracting property) is one of the interests that can be obtained by the present invention substantially.Certainly, according to the discussion of this paper it has also been discovered that, above-mentioned property is not enforceable.Many materials as described herein (such as Geophysical textiles and other) also usually with about 5 to 12GPa modulus.

The material of elongated member

In following discussion, it can be seen that by way of for the size of the selection of the particular polymers ingredient of each layer, each layer, each layer of manufacture or one of the mode of each layer of assembling or combination, the specific progress in this technology may be implemented.In a particular aspects, following understanding are shown herein --- the recent technological advances in polymer arts have significant purposes in polymer composites field.For example, according to the discussion of this paper, it can be seen that the present invention is advantageous and the heat and mechanical performance of the polymer that find unexpectedly using various traditional polymers and in the recent period.

The example of particular polymers that can be used according to the invention (no matter it is unitary 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 any combination thereof (either one of copolymer, admixture or mixture or a variety of forms).Generally, for multilayered structure, combination of materials is used --- it wherein will be compared with low melting point polymer and higher melt polymer co-extrusion with forming layer.Although any layer can be amorphous or at least partly crystallize, in specific example as described herein the polymeric layer of higher melt have relatively high crystallinity (for example, at least 30%, more generally at least 50%, or even 70%).As described in entire chapter, possible one of the advantage of disclosure herein is followed to be, even if after processing the material for manufacturing composite article, at least the material of higher melt layer keeps its form substantially, such as kept after consolidation step relatively high crystallinity (such as, at least 30%, more generally at least 50%, or even 70%).

Polyvinyl includes but is not limited to Alathon or ethylene and at least one C₃-C₂₀The copolymer of alpha-olefin, and can refer to the ethene polymers (SLEP) of ultra high density 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.Polyvinyl can be manufactured by one or more distinct methods, including but not limited to high pressure, solution, slurry or gas phase reaction, using one or more different catalyst systems, such as chromium (Cr), ziegler-nata (Z-N), metallocene, constrained geometry (CG) or other advanced non-metallocene complexes.It the use of the polypropylene copolymer containing one of above-mentioned polyvinyl or possible another alpha-olefin (such as butylene, or the like) is desirable for the relatively low-melting component A being used as in A-B structure.Other feasible materials include the admixture of polypropylene copolymer Yu (total) polyethylene (such as heterophasic polypropylene).

Propenyl polymer includes but is not limited to Noblen or propylene and at least one C₂Or C₄-C₂₀The copolymer of alpha-olefin, and it can refer to homopolymer polypropylene (hPP), random copolymer polypropylene (RCP), high-crystallinity polypropylene (HCPP), rubber modified polypropylene (hPP the or RCP matrix usually with " rubber " phase of dispersion), also referred to as anti-impact or block copolymer (ICP) or propylene-ethylene copolymers.Propenyl polymer, including but not limited to solution, slurry or vapor phase method can be manufactured by various methods, use various catalyst systems, such as ziegler-nata (Z-N), metallocene or other advanced non-metallocene complexes.Propenyl polymer can be isotactic, syndiotactic or atactic but preferably isotactic.

Example for the particularly preferred polyolefin compared with low-melting component (such as component A in A-B-A elongated member) includes propylene-ethylene copolymers (it can be modified rubber)；More preferably there is Narrow Molecular Weight Distribution, such as can be run after fame with VERSIFY obtained from Dow Chemical or be run after fame with VISTAMAXX obtained from those of ExxonMobil, or combinations thereof.Polymer that can be used according to the invention (is especially used as compared with low-melting component, such as the component A of A-B-A combination, or one or more layers as microlayer materials as described herein) example more specific again be included in WO03/040201A1, disclosed U. S. application 2003-0204017 and United States Patent (USP) 6,525, those, all these incorporated herein by reference disclosed in 157.For example, the material can be the propylene-ethylene copolymers for being substantially free of diene.It is the polypropylene homopolymer made of metalloscene catalyst so that it shows relatively low fusing point for the component A of A-B-A combination or one or more layers the possibility candidate as microlayer materials as described herein.The examples of commercial of such material includes ACHIEVE (available from ExxonMobil) and METOCENE (available from Basell)；Referring also to Kunzer and Wieners, Kunstoffe Plast Europe 86 (in May, 1996) 5, page 666-670 are incorporated herein by reference.A kind of example of available commercial polyethylene material is the material that The Dow ChemicalCompany can be obtained from trade name AFFINITY herein.

In one approach, copolymer can be manufactured in the metallocene catalyst process using single reactor with stable state.In another method, which can be used nonmetallocene metal-ligand complex compound (such as metal in the presence of the active co catalyst of such as aikyiaiurnirsoxan beta placed in the middle heteroaryl ligand catalyst) manufacture.Of course, it is possible to use foregoing other catalyst methods.In one embodiment, copolymer includes ethylene-derived units of the about 5wt% to about 25wt%, and the propylene derived unit of about 75wt% to 95wt%, and weight percent is with propylene-and ethylene-derived units total weight.Ethylene-derived units down to about 3wt% (or lower) are also feasible.

Preferred propylene-ethylene copolymers used herein (no matter individually or with another polymer, such as polypropylene homopolymer or random polypropylene are used in combination, and be either used in outer layer (such as compared with low melting point layer) or internal layer (such as higher melt layer)) be preferably there are two dedicated propylene-ethylene copolymers and therefore tool, the combination (such as all these combinations) of three or three or more following properties: a) molecular weight distribution (MWD) of about 1.5 to about 4 (such as 2 to 3), b) at least about 0.3 (such as, about 0.5 gram/10 minutes), particularly about 0.3 to about 50 gram/10 minutes (such as, 2 to 25 grams/10 minutes) melt flow rate (MFR) (at 230 DEG C) (MFR) (according to ASTM D1238), c) about 0.80 to about 0.95 gram/cc, the particularly density (according to ASTM D792) of about 0.85 to 0.91 (for example, 0.858 to 0.888 gram/cc)；D) co-monomer content of about 3 to 25wt% (for example, 5 to 15wt%)；E) glass transition temperature (Tg) of about 0 to about -50 DEG C (such as -15 to -35 DEG C)；F) about 40 to about 160 DEG C (for example, 50 to 135 DEG C) of melting range；G) about 25 to about 100, the particularly Xiao A hardness of about 40 to about 90 (for example, 50 to 75)；And h) about 5 to 1000MPa, or particularly 8 to 325MPa (for example, 10 to 280MPa), or the bending modulus (according to ISO 178) of higher (for example, more than 2000MPa).Such as and not restrictive, this kind of material can have about 8 to about 325MPa (such as, about 10 to 280MPa) bending modulus, about 3 to 25wt% ethylene contents and optionally at below about 135 DEG C of maximum fusing peak value, about 25 to about 100, the particularly Xiao A hardness of about 40 to about 90 (for example, 50 to 75)；Or their combination.The commercial examples of this analog copolymer can be run after fame with VERSIFY obtained from Dow ChemicalCompany.In a specific examples, elongated member and thereafter according to made of disclosure herein gained composite article in observe above-mentioned characteristic.

The material preferably usually can be random copolymer, with one of the heterophasic copolymer of random matrix, clarification copolymer (such as being clarified using nucleating agent as described herein/clarifying agent) or isotactic copolymer or a variety of.

In general, especially for the elongated member with A-B composed structure (such as A-B-A material), not only component B includes the polymer that fusing point is higher than component A, and component B material is usually the oriented material for keeping form substantially after processing, showing rigidity more higher than the material of component A, toughness and possible even higher tensile strength.Therefore, component B is usually the significant contributor of elongated member overall mechanical properties.

In a specific exemplary implementation scheme, component B includes the material of the relatively high rigidity as major part, especially polyolefin polymer.In one aspect, special requirement component B includes or is even made of substantially oriented polypropylene.In general, the molecular weight distribution of component B can be it is narrow, in or it is wide.For various uses, component B used can be also characterized by multimodal has nuclear material.A particularly preferred quasi polymer for higher melt material (such as component B), which has, (is greater than about 1200MPa greater than about 1000MPa, such as about 1500MPa) or it is higher according to ASTM D790, the bending modulus of ISO 178.Specific example includes homopolymer polypropylene (hPP), random copolymer polypropylene (RCPP) or combinations thereof.The example of commercially available material include available from The Dow Chemical Company (such as, run after fame supply with INSPIRE), ExxonMobil (such as, run after fame supply with PP9122, PP9852E1, PP2252, PP4712E1, PP4772, PP4792E1 etc.), those of Basell (for example, with ADSTIF, METOCENE or MOPLEN run after fame supply) or Borealis (BORMOD).Another material being suitable for use in A or B component of the invention is the ADFLEX (such as Z104) available from Basell.

An attractive polyacrylic specific examples used in this invention include, or particularly substantially by isotactic polypropylene homopolymer (such as, such as the open preparation and analysis according to WO 2004/033509 and US 20040122196, they are incorporated herein by reference；For other disclosures of material characteristics analysis, referring to the annex of this paper) it constitutes.Correspondingly, the specific polyacrylic example in component B is characterized by the combination (such as all these combinations) of two, three, four, five, six or six or more following properties: a) as the invention according to disclosed in 20040122196 (see appendix) of WO2004/033509 and U.S. Patent application by gel permeation chromatography measure be lower than about 5.5 molecular weight distribution (M_w/M_n), b) it is less than about 25 grams/10 minutes, more preferably less than about 10 grams/10 minutes and more preferably less than about 7 grams/10 minutes (such as, less than about 5 grams/10 minutes) melt flow rate (MFR) (at 230 DEG C) (MFR) (according to ASTM D1238), c) be greater than about 2000MPa (such as, greater than about 300, 1% Secant flexural modulus 000psi) (according to ASTM D790-00), d) according to disclosed in WO2004/033509 and U.S. Patent application 20040122196 (see also this paper annex) invention measure be less than about 2% (such as, less than xylene soluble part about 1%), e) turbidity less than about 25% is (according to ASTM D1 003), f) invention according to disclosed in WO2004/033509 and U.S. Patent application 2004-0122196 (see also this paper annex) measured by differential scanning calorimetry at least about 30%, particularly at least about 50%, particularly it is greater than about 70% crystallinity, g) invention according to disclosed in WO2004/033509 and U.S. Patent application 2004-0122196 (see also this paper annex) is greater than about 70% using what nuclear magnetic resonance (NMR) was measured, more preferably greater than about 85% and still more preferably greater than about 95%, and even more preferably be greater than about 99% five unit group of isotaxy/tri- unit group ratios；And h) the crystallization temperature greater than 133 DEG C (for example, being measured according to the invention of WO2004/033509 and U.S. Patent application 2004-0122196 (see also this paper annex)).In an illustrative example, five unit group isotacticities can be at least 96%, more preferably at least 97%, most preferably at least 98%.In general, polypropylene homopolymer shows the peak melting point of at least 160 DEG C (for example, at least 165 DEG C or even 170 DEG C).As an example, polypropylene homopolymer shows the peak melting point and at least about 30% of at least 160 DEG C (for example, at least 165 DEG C or even 170 DEG C), particularly at least about 50%, still more specifically it is higher than about 70% crystallinity, greater than about 70%, more preferably greater than about 85%, even more preferably it is greater than about 95%, even more preferably greater than about 99% five unit group of isotaxy/tri- unit group ratios or the combination of this isotacticity and crystallinity.In specific examples, polypropylene homopolymer further shows 1% Secant flexural modulus greater than about 2000MPa (according to ASTMD790-00).In a specific examples, above-mentioned characteristic is observed in elongated member and hereafter in the gained composite article according to made of disclosure herein.For example, the material of component B can actually show the raising (such as improve up to 3,5 or even 8 DEG C) of the peak melting point compared with the peak melting point before consolidation in gained consolidated composite article.

For example, a kind of specific polypropylene is with the M lower than about 7_w/M_n, the melt flow rate (MFR) lower than about 7 grams/10 minutes, 1% Secant flexural modulus greater than about 2000MPa and the xylene soluble part lower than 2wt% be characterized.This kind of polyacrylic example is disclosed in the US2004/0122196 of entitled " Highly crystalline polypropylenewith low xylene solubles " and the WO2004/033509 of entitled " Highly crystallinepolypropylene with low xylene solubles ", it is both incorporated herein by reference, wherein also disclosing the method for measuring above-mentioned characteristic.

It is also recognized that herein, by in higher melt layer, such as the relatively low melting point polyolefin copolymer of optional minor amount (relative to component B) is incorporated in component B (such as with admixture, copolymer or combining form), such as propylene-ethylene copolymers (such as, with the above-mentioned type, such as available from the VERSIFY of The Dow Chemical Company^TMCopolymer), other favorable outcomes (for example, helping to stretch) can be obtained.This analog copolymer preferably has the combination (such as all these combinations) of two, three or three or more in the above-mentioned characteristic of dedicated propylene-ethylene copolymers.It is not intended to be subject to theory, lower melting point polyolefinic material is incorporated in component B is believed to be helpful in component B layer is adhered on component A layer；The presence of lower melting point polyolefinic material, which is also believed to help, is bonded to each other each fibrinogen in component B layer.Likewise it is possible to change the characteristic of component A for material disclosed in component B by this paper for being incorporated to minor amount in component A.

More specifically, as used in the component B in elongated member, a kind of preferred method is to use polypropylene homopolymer (for example, polypropylene homopolymer according to made of the invention of WO 2004/033509 and US2004122196 incorporated herein by reference) with the amount of at least about 70 parts by weight (such as 80 to 100 parts) of component B.If can be existed using the polyolefin copolymer (such as above-mentioned propylene-ethylene copolymers) of optional minor amount with the amount of about 30 parts by weight (such as about 0 to 10 part) of up to component B.

The higher melt polymer (the component B in the exemplary implementation scheme for example including A-B structure) is usually the significant contributor of elongated member overall mechanical properties.Though not in what is be required in each case, but usually require that component B shows good tensile properties, especially at high temperature (such as about 170 DEG C).Correspondingly, component B can show at least about 8, more preferably at least about 12 in the case where that will not destroy or significantly damage its overall performance, and even more preferably at least about 16 or higher draw ratio (that is, former initial and final thickness ratio).Herein it is also to be recognized that by mixing a certain amount of propylene-ethylene copolymers (such as above-mentioned dedicated copolymer) in component B, this relatively high stretching is possible.Thus, it will also be recognized that even if the presence of copolymer can reduce the rigidity of component B at the beginning, the abundant increase of final expanded material rigidity also may be implemented, because the stretch capability that material improves can generate higher a possibility that hardening during stretching.

For the example of the particularly preferred material for higher melt material (such as material B in illustrative A-B structure combination), high rigidity (and in a preferred method, high isotaxy) Noblen is used.The example of such homopolymer is described above and in the US2004/0122196 of entitled " Highly crystalline polypropylenewith low xylene solubles " and the WO2004/033509 of entitled " Highly crystallinepolypropylene with low xylene solubles ", it is both incorporated herein by reference, they can be realized in single step stretching process higher stretch capability (for example, at least about 10 ×, more preferably at least about 15 ×, even more preferably at least about 20 ×), thus reduce or even be eliminated to can be used herein it is additional The demand of stretching step and/or annealing steps.Certainly, it will recognize, the use of high-crystallinity polypropylene is desirable, but be not it is enforceable, also can be used not be highly crystalline polypropylene (such as by Ziegler-Natta catalyst generate various conventional polypropylenes, small atactic polypropylene copolymer and other polypropylene disclosed herein) obtain good result.

Material selected by each layer for the elongated member of this paper need not contain only copolymer (for example, propylene-ethylene copolymers) or homopolymer (for example, polypropylene homopolymer).On the contrary, other combinations of copolymer, admixture, mixture or copolymer and homopolymer can be used.Thus, it is possible to further adjust the characteristic in each layer.For example, the case where for using two kinds of component (such as component A and component B), component A may include polypropylene homopolymer and propylene-ethylene copolymers.For example, polypropylene copolymer may be constructed about 0 to 100 parts by weight of component A, and propylene-ethylene copolymers may be constructed about 5 to 100 parts by weight of component A.Likewise it is possible to added in component B a certain amount of another relative resilient material (such as polypropylene plastomer or elastomer, propylene-ethylene copolymers, or combinations thereof) to help improving its draw ratio (such as at most amount of about 10wt%).

Small random (i.e. < 2wt%C₂) use of the propylene-ethylene copolymers in A and/or B component be recognized as within the scope of the invention.It is also anticipated that arrive, the material in A and/or B component is free of styrene polymer.

The additive used or with it in Elongated Member Materials

In one embodiment, material for elongated member, the component (such as component A, B or other) of multilayer elongated member is either still used as unitary material, it can also include non-migrating processing aid or surface modifier, the surface friction characteristics and/or scratch resistance and abrasion resistant qualities of chosen change (increasing or decreasing) material.Preferably, this surface modifier exists with relatively small amount, such as with the amount of the about 10wt% (such as at most about 4%) lower than material.Quite normally, selected surface modifier reduces mantle friction, the scratch resistance for improving component and the abrasion resistance of the material, improves operation (such as improved weaving characteristic) or more preferable their combination of the elongated member in intermediate form forming process.Although this kind of surface modifier is more likely to be used for exposed outer layer (such as component A of A-B structure), other places of elongated member can also be used in, such as in the higher melt material of component B.

The specific examples for being suitable as the material type of non-migrating processing aid or surface modifier include siloxanes, polyolefin, halogen polymer (for example, fluorinated thermopolymers) or any combination of them.A kind of particularly preferred reagent includes high molecular weight silicone, especially super high molecular weight siloxanes (such as, functionalization or nonfunctionalized alkylsiloxane, such as poly- (di-ethyl siloxane), poly- (dimethyl siloxane) or their combination, such as can those of trade name Dow Corning MB 50-313 by master batch form purchased from DowCorning, MB 50-001, MB 50-321 or MB 50-021).It is (incorporated herein by reference) it can be found that other selections referring to WO 01/12715, WO 02/08332, WO 98/13419.

Polyolefin herein optionally can be containing relatively small amount 500ppm to 2500ppm (for example, the nucleating agent of 750ppm to 1500ppm)/clarification agent addition agent.Although nucleating agent/clarification agent addition agent can be advantageously utilised in propylene-ethylene copolymers as described herein (and being used for example in the component A of A-B-A multilayer elongated member), but for polypropylene homopolymer, those of component B especially as A-B-A multilayer elongated member polypropylene homopolymer, special requirement use this additive.For the application in the pulling method for being related to single stage draw, this is further requirement (it is optional for the most purposes for using the multistage to stretch).In general, improving the rigidity of film made of resin using nucleating agent/clarification agent addition agent and improving crystalline rate of certain polymer (such as highly crystalline propenyl polymer) in air quenched blown films manufacturing process.This nucleating agent/additive also improves rigidity/clarity balance of gained film.Any additive for can be used while clarifying and being nucleated.Nucleating agent/clarification agent addition agent, such as ADK NA-11 (methylene-bis- (4,6- di-t-butyl phenyl) sodium ascorbyl phosphate) and ADK NA-21 (aluminium hydroxyl bis- [2,4,8,10- tetra- (1,1- dimethyl ethyl) -6- hydroxyl -12H- dibenzo [d, g] [1,3,2] dioxa phoshocin 6-oxidato]) it is purchased from Asahi Denka Kokai, and be preferably added in highly crystalline propenyl polymer of the invention.The Millad 3988 (3,4- dimethyl benzylidine sorbierite) for being purchased from Milliken Company is another example of available nucleating agent/clarification agent addition agent in the present invention.Sodium benzoate or even sorb alcohol radical nucleating systems also can be used according to the present invention.

No matter it is used in the unitary material or multilayer material of elongated member, the material can also include one of two or more other ingredient or combination, such as other polymer (such as, polypropylene, polyethylene, fluoroelastomer, any combination thereof etc.), filler (such as, glass, talcum, calcium carbonate or the like), antigen fibrillation agent (such as, PE), nucleating agent, release agent, fire retardant, conductive agent, antistatic agent, pigment, carbon black, antioxidant, impact modifier, stabilizer (such as, ultraviolet absorbing agent), or any combination.Such as, when using these additives, they usually be up to entire component about 15wt% amount use (such as, about the 0 to 10wt% of component A and/or component B, particularly about 2 to 8wt%, wherein about 1wt%, such as less than 0.6wt% of the every kind of additive usually to be lower than the material, lower than 0.5wt%, or even as low as about 0.2wt% or lower amount use).Component (such as component A or B) can also include recycling waste material (such as from component A, manufacture of component B or even from the manufacture of elongated member of the invention).It is disclosed in EP 0829529A1 rather than defines the example of possible additive, it is incorporated herein by reference.The example of commercially available additive includes but is not limited to ERUCAMIDE, IRGANOX B215, IRGANOX B225, MISTRON talcum, IRGANOX 1010 (or thioester), CHIMASORB 944, CHIMASORB 119, HOSTASTAT FE2, IRGASTAT and TINUVIN 770.The present invention not only contemplates above-mentioned commodity, it is also contemplated that corresponding product from other manufacturers.

It can also be incorporated in the component B (higher melt component) of Elongated Member Materials one or more for enhancing other polymeric components of its performance.For example, in addition to polypropylene homo beyond the region of objective existence, high rigidity material can also include other thermoplastics, for example, polyethylene terephthalate (PET), polyamide, polycarbonate, any other thermoplastic polymer as described herein, or mixtures thereof.Likewise it is possible to a certain amount of relative resilient material (such as polypropylene plastomer or elastomer, propylene-ethylene copolymers or combination) be added in component B to help its stretch capability is improved.

As an example, a kind of method of manufacture elongated member includes forming coextruded film so that it generates A-B-A combination, wherein component A (such as about 5 to the 15wt%) random copolymer that is propylene with about 3 to 15wt% ethylene (density is about 0.9 gram/cc), and with about 50 to about 135 DEG C (such as 100 to 140 DEG C) of fusing point, component B is that peak melting point is about 150 to 170 DEG C and (will recognize, for some embodiments, fusing point can exceed that about 170 DEG C (such as about 150 to 180 DEG C or higher)) polypropylene homopolymer.Correspondingly, the fusing point difference between component A and B can be down to about 5 to 9 DEG C, or are higher than about 75 DEG C.The relative quantity of A and B component is about 1: 2: 1 to 1: 25: 1, particularly about 1: 15: 1 to 1: 20: 1 (such as about 1: 17: 1).Component A or B can have any suitable weight average molecular weight, such as about 50 to about 400 kg/mol, and more typically about 200 to about 300 kg/mol.

Above content is not meant to limit the present invention.WO 03/008190A1 and WO2004028803 (incorporated herein by reference) (be related to include random copolymer cortex (such as component A), which includes the copolymer of propylene and ethylene or another alpha-olefin；Further relate to the use of metallocenyl statistics and convergence object) in disclose but be not to define other examples of extruded tape or yarn.EP 0776762B1 incorporated herein by reference discloses another example for the material that can be used as elongated member, and cortex (such as component A) includes ethylene copolymer and a certain amount of high density polyethylene (HDPE) (such as about 5 to 45wt%) admixture accordingly.United States Patent (USP) 5,993,711 and 6,045,923 (transferring Lankhorst Indutech B.V.) (incorporated herein by reference) has also enumerated feasible candidate.According to the former, the profile of elongated member can include one or more longitudinal flanges and/or longitudinal groove on one or more surfaces.According to the latter, elongated member may include the central core (such as component B) made of the admixture of high density polyethylene (HDPE) and one or more other polyolefin, and thus the amount of high density polyethylene (HDPE) is main, that is, is more than about 50wt%.More particularly, central core is made of about 50 to 90wt% high density polyethylene (HDPE) (940 kilograms per cubic meter of >) and about 10 to 50wt% (line style) low density polyethylene (LDPE) (925 kilograms per cubic meter of <), very low density polyethylene (910 kilograms per cubic meter of <) or the combined admixture of these products.Furthermore, it is possible to improve the intensity of the material there are a certain amount of polypropylene.Another feasible method is to form conducing composite material according to the present invention, and wherein composite material includes at least one current-carrying part, for example originating from the presence of conductive elongated member.For example, conductive elongated member can be coating or uncoated metal wire (such as copper wire).Other variants can be found from United States Patent (USP) 6,710,253 (transferring Lankhorst indutechB.V.) incorporated herein by reference.

As general introduction, according to the present invention it is contemplated that the multilayered structure including at least two layers (their fusing point is different) can be used.Higher melt material is used in combination with compared with low melting material as a result, (it is typically oriented to).It is usually located on the outer surface of elongated member compared with low melting material, it is possible thereby to melt.It is disclosed that material therefor can be selected from a variety of alternative materials, it further includes higher melt polypropylene homopolymer layer (being especially orientated) that one of particularly preferred combination, which includes propylene-ethylene copolymers as lower melting point material layer,.These layers may include other additives (such as dimethyl silicone polymer or another suitable non-migrating processing aid or surface modifier) as disclosed herein.Such as the higher melt polypropylene homopolymer material of a certain amount of (such as minor amount) can be mixed in the propylene-ethylene copolymers.Alternatively, or in addition to this, the lower melting point propylene-ethylene copolymer of a certain amount of (such as minor amount) can also be mixed in the polypropylene homopolymer.The example of extremely preferred combination of materials includes, with as above and in conjunction with the height isotactic polypropylene homopolymer described in US2004/0122196 and WO2004/033509 (incorporated herein by reference), have and the VERSIFY available from The Dow ChemicalCompany^TMThe lower melting point propylene-ethylene copolymer type of similar characteristics.

More particularly, find out from the above, be used to form multilayered structure, the number of combinations of the material including A-B structure (including microbedding as described herein) is very big.It is not desired to the limitation by following explanation, but as general introduction, disclosure herein is imagined, ethylene propylene copolymer (being free of dimethyl silicone polymer) is selected from compared with low melting point layer (component A), ethylene propylene copolymer (contains dimethyl silicone polymer), heterophasic polypropylene (such as, ADFLEX), ethylene propylene copolymer (being free of dimethyl silicone polymer) containing polypropylene homopolymer, containing random copolymer polypropylene ethylene propylene copolymer (be free of dimethyl silicone polymer) (such as, it can be run after fame with R771 obtained from The DowChemical Company), or any combination of them.For above-mentioned material, the example of optimal ethylene propylene copolymer can be run after fame with VERSIFY obtained from The Dow ChemicalCompany.Furthermore, it is not desired to by following disclosed limitation, but as general introduction, disclosure herein is imagined, higher melt layer (component B) be selected from isotactic polypropylene homopolymer, containing the at most propylene ethylene copolymers of about 20wt% isotactic polypropylene homopolymer (such as, can be run after fame with VERSIFY obtained from The Dow Chemical Company), random copolymer polypropylene (for example, can be run after fame with R771 obtained from The Dow Chemical Company) or any combination of them.Present invention contemplates any combination of component A examples and component B example of the invention.Above-mentioned material, the material determined especially in above-mentioned general introduction is particularly attractive on the way in following use, and the purposes of the elongated member of the twister in tubing reinforcing material or other intermediate forms is used to form including them.

Microbedding

It can be to form the elongated member including one or more layers microbedding including at least the another method for illustrating to be used in combination of the elongated member of component A and B individually or with formation above." microbedding " refers to the relatively small layer of thickness, for example, thickness is lower than about 50 microns, more preferably less than about 20 microns, more preferably less than about 10 microns, even more preferably thickness is lower than about 7 microns, and even more preferably thickness is lower than about 5 microns.In general, when in use, preferably the assembly of coextruded layer (each layer includes polymer, copolymer or their mixture) manufactures microbedding as multiple stack layers.Such as each microbedding may include before for one or both of material described in the layer of component A and B in illustrative A-B combination or yet another component.The quantity of independent microbedding is usually 1 to 4 layer in typical elongated member.More generally, microbedding includes at least 4 layers or 4 layers or more, particularly at least 5 layers or 5 layers or more materials, wherein each layer is preferably adjacent layer difference.

More particularly, as an example, suitable device (such as the die head for passing through the device) is added in a kind of estimated at least one second fluid by least one first fluid and the second melting of the first melting or softening polymeric material or softening polymeric material of method of the microlayered condensate (such as elongated member) of manufacture, pass through co-extrusion herein, such as they are combined by using microlayer melt splitter or hemispherical microlayer co-extrusion feeding section, to which the discrete portions packing of the first polymeric material to be formed to the first polymeric material in the intracorporal multiple belt courses of the second polymeric material base with the second polymeric material, lamellar polymeric body is consequently formed.In general, select and rapidoprint so that they be subjected to when passing through feed tool shearing when, the viscosity of different materials differ less than about 3 times (such as, the viscosity differences of each polymeric layer are less than about 1.5 times, such as about 1.25 times or even about 1 times under feed conditions).Therefore, belt course it is substantially continuous in the first substantially parallel plane of one of the major surfaces of main body (body) and in second plane vertical with first plane it is discontinuous.In addition, the first polymeric material layer can have the major interfaces with the polymeric major surfaces parallel array of gained.

It is not intended to be subject to theory, but in a particular aspects, for the microbedding of this paper, the present invention provides the methods for obtaining continuous polymer material in draw direction, the material have the boundary (confinement) substantially vertical with the draw direction (such as, using being at least partially crystalline the polymer of polymer, and be limited to have compared in the layer of low-crystallinity or region).Due to this restriction, after hardening, material typically exhibits the entanglement amount of reduction, this can be used for improving the stretch capability of the material again, and relatively high rigidity and/or intensity are thus caused in resulting materials.

A kind of method is using the structure for including the multiple microbeddings being interspersed between the different materials of component A and B.For example, this can be expressed as ((A-B)_n- A), wherein n is the integer of two or more.Also contemplating n is 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 (such as 500 to 1000 layers, in some instances it may even be possible to 1000 to 5000 layers or more).Any suitable technology manufacture microlayer elongated members, such as layer multiplication (layer-multiplying) extrusion molding can be used.A kind of method is the co-extrusion multilayer for example using microlayer melt splitter or hemispherical microlayer co-extrusion feeding section.It is optionally possible to be expressed on cooling stick.In addition to extrusion step or with extrusion step in combination, lamination can also be used.In general, selecting the polymer of each layer so that melt viscosity, which approaches, prevents layer unstability or inhomogeneities, therefore polymer used has sufficient interfacial adhesion so that adjoining course will not leafing.Other examples, which disclose, to be seen United States Patent (USP) 5,568,316 (it is also disclosed such as United States Patent (USP) 3,773,882 and 3,884,606；5,269,995；The use of co-extruder described in 5,094,793 and 5,094,788, all aforementioned patents are incorporated herein by reference).It sees also, 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, it is all these incorporated herein by reference.It sees also, the paper of Dooley, " Viscoelastic Flow Effects in MultilayerPolymer Co-extrusion ", Technische Universiteit Eindhoven (2002) (ISBN90-386-2983-4) is incorporated herein by reference；With Rastogi et al., " Heterogeneity inPolymer Melts from Melting of Polymer Crystals ", Nature Materials Vol.4 (in August, 2005) (online publishing on July 24th, 2005), it is incorporated herein by reference；Jin et al., " Structure of Polypropylene Crystallized in Confined Nanolayers ", PPS-20:Polymer Nanotechnology Symposium (20-24 days in June, 2000) is incorporated herein by reference.It should be appreciated that the aspects of the invention is not it is contemplated that the selection of material used herein requires any specific reflection degree in what layer or layer combination in office.Therefore, the estimated reflection of gained elongated member on the object incident visible light less than 40% (or even less than 20%).Similarly, material can be without any colorant to assign the object metal appearance.Their selection can not also consider the respective optical thickness of group stratification or total optical thickness.

Although the adjoining course of microbedding can have identical material type, but more generally, for non-microbedding multilayer embodiment as described herein, the material of adjoining course is different from each other at least one characteristic, such as composition, orientation, crystallinity, molecularly oriented, molecular weight, meltflow ability, highest fusion temperature, glass transition peak, crystallization temperature, sealing initiation temperature, softening point, molecular weight distribution or any combination of them.For example, can be in conjunction with different polypropylene, it can be in conjunction with different polyethylene, it can be in conjunction with different polyethylene terephthalate (PETs), etc..Furthermore, it is possible to by polypropylene in conjunction with polyethylene, PET in conjunction with polypropylene or by polyamide in conjunction with polyethylene, etc..Any thermoplastic material as described herein can be used in microlayer elongated members, and microbedding explanation is not limited to polyolefin polymer.For example, can select each layer choosing of microlayered structure above for polyolefine material described in component A and B.

One or more microbeddings can also include being selected from polycarbonate, polyvinyl chloride, (methyl) acrylonitrile, (methyl) acrylate, polyurethane, thermoplastic elastomer (TPE), thermoplastic olefin, polyamide (such as, nylon 6, nylon 6, 6 or other), polysulfones, polyester, polyalkylene terephthalates (such as, poly- (diethyl terephthalate), poly- (dibutyl terephthalate), poly- (terephthalic acid (TPA) 1, 4- cyclohexanedimethanoester ester) or other), poly- alkylene isophthalate (such as, poly- (ethylene isophthalate)), acronitrile-butadiene-styrene, polyarylene sulfide (such as, polyphenylene sulfide), thermoplastic polyurethane, polyphenylene oxide (PPE), polystyrene or any combination of them are (with copolymer, admixture or form of mixtures) polymer (or being total to including this polymer Polymers).

The example that specific A-B for each microbedding is combined includes, but are not limited to polypropylene homopolymer and polypropylene copolymer；Polypropylene and propylene-hexane co-polymer HDPE and ethylene copolymer；Polyamide (at least partially aromatics or non-aromatic may include copolyamide) (such as nylon 6, nylon 6,6, nylon 46, nylon 11, nylon 12, nylon 6.6T) and polypropylene；Poly- (ethylene terephthalate) and another polyester, for example, it is poly- (butylene terephthalate) and/or poly- (trimethylene terephthalate)；Poly- (ethylidene -2,6- naphthalene) or one of poly- (terephthalic acid (TPA) cyclohexanedimethanol ester) and poly- (ethylene terephthalate), poly- (butylene terephthalate) or poly- (trimethylene terephthalate) or a variety of；Polyolefin homopolymer and copolymer (for example, polybutene and poly- 4- methylpentene (for example, TPX methylpentene copolymer from Mitsui)).

Furthermore, optionally (and other than being only used for microbedding, can be used for multilayered structure herein), can be between the adjoining course of multilayer Elongated Member Materials, such as mating layer or intermediate adhesive (such as adhesive, priming paint or other) layer are used between the adjoining course of microlayer materials.In the case where polyolefinic multi-layer materials, layer is coupled or intermediary adhesive layer generally includes the polyolefin with functional response's group.When the constitutional chemistry of layer is disparate, be coupled layer or intermediary adhesive layer using particularly useful.Such as, when using polyolefin as one layer and using polyester or polyamide as another layer, the layer (for example including coupling agent (such as grafted polypropylene modified dose of the maleic anhydride-that can be run after fame with Polybond obtained from Crompton-Uniroyal Chemical), the polyolefin with epoxy functionalities, the polyolefin with (methyl) acrylate (such as glycidyl methacrylate) or (methyl) acrylic functionalities or other layers) including the polyolefin with functional response's group can be used for improving plunger bond strength.Mating layer or intermediate adhesive including copolymer (it includes polyethylene, polypropylene or their mixture) can also be used.Such as but without limitation, a kind of feasible method, which can be used two layers or two layers or more, to be the microbedding of polyolefin homopolymer (such as polypropylene or polyethylene) and these microbeddings is bonded together with propylene copolymer, ethylene copolymer or their mixture.It will of course be appreciated that it is in the elongated member of microbedding that above-mentioned mating layer or intermediary adhesive layer, which can also be used in not,.

Microbedding is considered showing improved stretch capability, this leads to higher intensity or modulus.By using higher draw ratio in single or multiple drawing process, higher material orientation may be implemented, to improve intensity and toughness.Microbedding also shows improved impact resistance, this is considered as caused by capable of being dissipated as the greater impact as obtained by the biggish independent number of plies.

The microbedding of this paper illustrates not to be strictly limited to be formed the elongated member only selected from fiber, shaft, rope, yarn, band, monofilament or band using microbedding.Other forms are also possible, especially film (such as oriented film, such as biaxially oriented film), such as Biaially oriented polypropylene (BOPP) film.Microlayer elongated members (and other elongated members), which can be also used in, does not require the use of big stretch capability or improved impact resistance on the way, such as stretches preservative film (cling films), Geophysical textiles, raffia, fabric, gunnysack, man-made glass, low-carbon, strap or similar applications.Certainly, microlayer elongated members can be used in intermediate form, such as consolidation as described herein or unconsolidated other elongated members.Microlayer materials can also and other structures, such as metal, timber, fabric, a combination thereof or the like be used in combination.

According to the aforementioned discussion of component A and B, Exemplary microlayer elongated member includes the higher melt material component B of at least about 50wt% (accounting for entire microlayer structures), rest part is lower melting point material component A, the component B of more preferably at least about 60wt%, most preferably from about 70 to 96wt% component B, rest part are component A.Preferably, component A includes about 0 to 100wt% polypropylene copolymer, and propylene-ethylene copolymers (such as aforementioned dedicated propylene-ethylene copolymers, such as VERSIFY^TMCopolymer) it may be constructed about the 5 to 100wt% of component A.Component A can also include account for the component modified (such as the friction reduces) agent of about 0 to 4wt% foregoing non-migrating processing aid or surface (such as, dimethyl silicone polymer, fluoropolymer, such as fluoroelastomer or the like).Component A can also include about 0 to the 8wt% other compositions as described above for accounting for the component.

Component B preferably comprises high rigidity polypropylene and (for example, random copolymer, or accounts for about the 80 to 100wt%) of the component, while further including the propylene-ethylene copolymers at most accounting for the about 10wt% of the component.The rest part of component B can be made of other compositions as described above at most accounting for the about 10wt% of the component.

In order to illustrate above content, and not restrictive, to there are about 100 to 525 layers or more (to be staggered between the layer being made of substantially component A, the substantially layer that is made of component B, and optionally include other polymers component layers) microlayer elongated members the said components A including about 5 to about 25 parts by weight is made, the said components B of about 95 to 75 parts by weight stretches it under the draft temperature more than 150 DEG C (such as 165 DEG C) with about 18 to 28 draw ratio.More specific example includes in the following table.

Wt% component B	Wt% component A	Number of plies #	In 150 DEG C of draw ratio of >
				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

Gained microlayer structures can show at least about 10GPa, particularly the stretch modulus of at least 12GPa (such as 12 to 15GPa) (according to ASTM D-638 or ISO 527).These materials can be used with the draw ratio more than 18 (for being stretched under the draft temperature more than 150 DEG C (such as 165 DEG C)), especially for the lamellar polymeric body at least 4 layers --- it is included at least: the second layer comprising the first polymeric material selected from thermoplastic polymer, thermoplastic copolymer or combinations thereof and the first layer with the thickness less than about 50 microns, and comprising the second polymeric material selected from thermoplastic polymer, thermoplastic copolymer or combinations thereof and the adjoining with the thickness less than about 50 microns.When different from each other in terms of layer each in the first and second polymeric materials is in composition, crystallization degree, molecularly oriented, molecular weight, meltflow ability, highest fusion temperature, glass transition peak, crystallization temperature, seal initiation temperature, softening point, molecular weight distribution or any combination thereof (such as, microbedding including propenyl polymer, with another different adjoining course), this is particularly true.

Such as but without limitation, a kind of feasible two-step stretch method can also be used in the microlayer elongated members (it has the ratio of the component B and component A of about 3: 1 to about 9: 1 (such as about 4: 1)) containing about 3 to 33 layers.First is stretching in about 65 DEG C of completions (about 6.5 draw ratios), and the second stretching step is in about 165 DEG C of completions (about 3 draw ratios).Accordingly for other stretched operations for being used herein to elongated member having with aforementioned operation different characteristic, one-off drawing is carried out under the fusing point higher than one layer but the fusing point lower than another layer (such as restraint layer).It will of course be appreciated that draft temperature can the material according to selected by microbedding and become.Such as but without limitation, elongated member may include polyester (such as PET), and draft temperature can be about 120 DEG C to about 250 DEG C.Furthermore, such as by improving according to Zuo et al., " In Situ Synchotron SAXS/WAXD Studies on Stretching of IsotacticPolypropylene; Poly.Mat ' ls Sci.& Eng.; the Hermans Orientation Function that 93 (2005) 761.n addition are measured; improve the orientation of at least higher melt material during stretching within the scope of disclosure herein, also manufacture combines the microlayer elongated members of polypropylene and PET (i.e. the Lighter C88 from Equipolymers) (such as containing big About 3 to 150 alternating layers, such as 5 to 129 layers).The mating layer for example including maleic anhydride inoculated polypropylene (such as POLYBOND 3002 from Crompton) can be used.Five layer materials arrange as follows: PP- poly thio rubber adhesive-PET- poly thio rubber adhesive-PP, 7/3/80/3/7 ratio.129 layer materials arrange as follows: (PP- poly thio rubber adhesive-PET- poly thio rubber adhesive) n-PP, wherein n is 32, and wherein the ratio of material is identical as in five layer materials.As general introduction, and not restrictive, the present invention relates to the manufacture for the microlayer structures for generally including at least four stack layer, these layers respectively different in terms of at least one characteristic selected from composition, crystallinity, molecularly oriented, molecular weight, meltflow ability, highest fusion temperature, glass transition peak, crystallization temperature, sealing initiation temperature, softening point, molecular weight distribution or any combination thereof relative to its adjoining course with the thickness and each layer for being less than about 50 microns.In one approach, at least one layer of elongated member and may every layer of polymer be propenyl polymer (such as polypropylene homopolymer, such as isotactic polypropylene homopolymer).For example, polypropylene can be used in one or more layers (and even all layers).At least one layer of polymer can also include ethylene.The polymer of at least two adjoining courses may include ethylene (such as selected from propylene-ethylene copolymers, linear low density polyethylene (LLDPE), high density polyethylene (HDPE) or their any mixture).

The various other specific combinations of polyolefine material can be used microbedding.Such as but without limitation, co-extrusion multiple layer combination body can be formed, it includes the polyolefin (such as Natene) that melt index (MI) is lower than about 4, molecular weight distribution less than about 5 and maximum fusing point is at least about 128 DEG C, and maximum polyolefin adjoining course (such as copolymerization of ethylene) of the fusing point less than 125 DEG C.Coextruded layer can be stretched at least once at about 115 to 141 DEG C.Another specific example includes the polyacrylic adjacent microbedding made of Ziegler-Natta catalyst, wherein each adjoining course is respectively the alternating layer of homopolymer, random copolymer or homopolymer and random copolymer.Another feasible combination is estimated using the polypropylene homopolymer layer adjacent with Polyethylene homo nitride layer, or optionally includes middle layer, such as propylene-ethylene copolymers, random polypropylene, ethylene copolymer or their mixture.In general, the polymer of at least two layers adjoining course respectively has difference at least about 5 DEG C of maximum fusion temperature.

Additive or other function material, such as mating layer or intermediary adhesive layer can be used between at least two layers of stack layer.Consistently with the explanation of elsewhere herein, material may include at least one layer of exposed surface selected from siloxanes (such as dimethyl siloxane), halogen polymer, or combinations thereof non-migrating processing aid or surface modifier.

The consolidation and molding of intermediate form

It is desirable in each case but be not enforceable be that abutment structure unit can be movable relative to each other in the opposite early stage (especially before forming intermediate form) of processing.A kind of method for realizing this point is to form intermediate form, but do not carry out consolidation process steps to it, which can make abutment structure unit irreversibly link together, such as by splicing, melting, fastening or otherwise assembles these units.Can be with the void space between fills unit, and intermediate form densities.Correspondingly, this point it will be particularly beneficial that, intermediate form does not consolidate (such as one or more steps of one or more temperature by the way that at least one material to be heated above to fusing point in the form of causing material to melt and fuse), and effectively welds with adjacent unit.This heating can carry out while (constrained) constrained in intermediate form or unfettered.In addition, this heating stepses can at the same time to intermediate form applied force in the case where carry out.

Such as and not restrictive, usual polyolefinic intermediate form (including Geophysical textiles and/or multilayered structure (such as A-B-B structure)) can be consolidated by following one or more steps --- in (such as about 100 to about 175 DEG C of one or more temperature by the form more than the fusing point of the exposed surface of elongated member, more particularly smaller than about 150 DEG C) keep enough time (such as about 1 to about 5 minute) while, apply at least about 50kN (particularly be greater than about 150kN (such as 350kN) power.The longer or short period is also feasible (such as consolidating about 0.25 hour at high temperature, about 0.5 hour, or even higher than about 1 hour).

Gained intermediate form may include or be made of substantially single layer (it optionally may include one or more styles).Also contemplate the part or all of upper intermediate form including multilayer (it optionally may include one or more styles) in each layer surface.Such as, if one or more layers can be different from each other in following one or more aspects using multilayer: whether the heat treatment of composition, elongated member of such as material type, elongated member, the width of elongated member or other dimensions, model type, this layer consolidate, the presence of film layer, thickness, form or any combination of them.In order to for example, selected from film, coating (such as solvent coating, extrusion coating or other), woven form, winding form, knitting form, type of weave, random dispersion form or any combination thereof at least one first layer can abut selected from film, coating (such as solvent coating, extrusion coating or other), woven form, winding form, knitting form, type of weave, form of foam, random dispersion form or any combination thereof at least one second layer.At least one layer is optionally Geophysical textiles or including microbedding.In this example embodiment, at least one layer can consolidate in shown first or second layer.

In the case where intermediate form is single layer, and in the case where a part for needing to use multilayer as intermediate form, one or more layers can be processed to prevent each structural unit and/or each layer from separating.Such as, for single-layer or multi-layer form, one or more layers (for multilayer form, being optionally fixed to one another) can be fixed in a suitable manner (such as by being thermally connected structural unit along one of the form, at least part at two or more edges).Other processing methods can be used, such as mechanical step (such as crimping, fastening, locking (stapling), riveting, suture or other), adhesive Connection Step (such as with drops of adhesive or pearl, adhesive tape or other) or their combination.It is possible thereby to easily handle intermediate form, such as in die cavity or other for conveying, storing, be placed in, while reducing a possibility that each structural unit is separated to the degree of damage intermediate form integrity.

When using multilayer in intermediate form, it can need to select the number of plies according to desired use.It is, for example, possible to use two layers or more, three layers, four layers, five layers or five layers or more.Correspondingly, intermediate form estimated small thickness that is of uniform thickness that can have with elongated member therein under non-concretion state, such as about 0.25 to about 2.5 centimetre or bigger.Correspondingly, under concretion state, intermediate form is estimated to generate about 0.8 millimeter to about 1.5 centimetres or bigger, such as about 0.1 to 0.8 centimetre or bigger, especially from about 0.3 to 0.5 centimetre of thickness.

In another aspect of the invention, before forming final product, by intermediate form (its may include as described above one or more layers) molding to required construction.This molding can be in consolidation step (such as in thermoforming or other high-temperature moldings or hot stamping operation) or even adjoint or be not accompanied by the cold stamping of consolidation or other operations for causing local train hardening and carry out.In consolidation process, intermediate form usually can independently dangle (drapable uponitself) first.After consolidation, which becomes at least semi-rigid, can preferably carry self weight.After molding and consolidation, the intermediate form of the invention usually can long term shape retention, such as more than 2 weeks, particularly more than 1 month, still more specifically more than 3 months.Intermediate form manufacturer can manufacture the form of certain inventory as a result, then can be with long-time storage until needing to be assembled into composite material.

It will recognize, during preparing intermediate form of the invention, these forms (can be reinforced or harden below by way of plastic deformation in the recrystallization temperature range of composite material) with strain hardening.Strain hardening can before consolidation, among or carry out later.If carried out after consolidation, strains elongation and be preferably maintained below about 15%, more preferably less than about 10%.If carried out before or during consolidation, strain elongation can be at least about 10 to 40%.Higher or lower amount is also possible.A kind of specific forming method of intermediate form (no matter single layer or multilayer) includes using resilient structures, and intermediate form is allowed be displaced (such as sliding) in deformation process.Various ad hoc approach are disclosed in the co-pending and jointly owned U.S. Provisional Application 60/718,025 (attorney docket 1062-051P1) (incorporated herein by reference) of entitled " the Apparatus and Process forManufacturing Shaped Plastic Reinforced Composite Articles " that submitted on September 16th, 2005.As an example, it is contemplated that make include multiple thermoplastic elongated members intermediate form deformation, while the intermediate form heated is removably clamped in deformation process.Intermediate form is clamped, so that while applying the power for deforming intermediate form, intermediate form moves freely in indeformable situation in predetermined limits.The thermoplastic elongated member of intermediate form is at least partly consolidated to form the three-dimensional article of the predetermined orientation with elongated member.Optionally, (temperature of such as less than displaceable clamping step, such as be substantially equal to or be lower than room temperature) the punching press intermediate form in the second forming operation.

Certainly, many geometries are feasible, and are deemed within the scope of the present invention.In addition, intermediate form needs not be multilayer form, and it can be single layer.Shaped intermediate form can be further processed as disclosed herein, such as mould another material in the case where being in close contact with shaped intermediate form to form enhancing composite material.As can be seen that shaped intermediate form of the invention generally includes three-dimensional construction.In addition, the shaped intermediate form estimated size or shape conversion that does not generate any vision when processing composite material obtained by formation and can detect in most cases.But according to disclosure herein, can before consolidation, among or later by intermediate form strain hardening (such as no more than about 10% elongation).

After formation or molding, intermediate form optionally can be by changing further heat treatment, coating (such as priming) or other procedure of processings needed for one or more property.Furthermore, it is possible to which optional treatment elongated member and/or the intermediate form being made from it are to assign its degree of functionality.It is, for example, possible to use the surface by changing elongated member and/or intermediate form can and/or the step of chemical property (such as be crosslinked for improving) imparting degree of functionality.Priming paint (such as polyolefin dispersion), which can according to need, to be applied on elongated member and/or intermediate form surface.

Intermediate form of the invention is suitably processed to form resulting product.Many distinct methods can be used.Such as, before or after consolidation, it can be by the form and former (bulk) material (such as aforementioned second thermoplastic material, it can have any suitable form, such as sheet material, mechanograph, plate, tubing, etc.) to form the moulded products of the Material reinforcement of intermediate form to be used, which is molding, unformed or combinations thereof for combination.Any suitable package technique can be used, such as intermediate form can be adhered on raw material, it can be mechanically fastened on raw material, it can be soldered on raw material, it can be impregnated or be permeated with raw material, it can be hot-melted with raw material, be laminated on raw material or any combination of them.

Intermediate form can with raw material thermoforming, vacuum forming, pressure forming, compression molding, blow molding, injection moulding, rotational molding, hot pressing, lamination (such as, extrusion laminate, such as by the way that intermediate form and raw material are fed through roller, wherein intermediate form below raw material and/or top), extrusion-blown modling, profile extrusion, hydroforming or any combination thereof the step of in (this can optionally include constraint raw material and/or intermediate form) assembling (with consolidation, partial consolidation or non-concretion state).Intermediate form can also itself include insert or other elements or carrier, and this assembly is fitted together with raw material.For example, extruded profile can be wound with elongated member, then the assembly and raw material are assembled.

One specific example includes overmolded, and include the following steps: to be formed simultaneously consolidated intermediate form, the intermediate form of molding and consolidation is placed in die cavity, and liquefied bulk material is added in the chamber with intermediate form, wherein after hardening, resulting product includes the solidification raw material for being molded onto intermediate form and being enhanced with intermediate form.More particularly, imagine and the molding for including the first thermoplastic material and consolidated intermediate form are placed in injection moulding die cavity, and by the way that raw material, that is, the injection moulding of the second thermoplastic material are moulded (such as embedded molding or overmolded) second thermoplastic material into the die cavity.

Temperature when die cavity is added in second thermoplastic material is high enough that it leads at least partly intermediate form fusing and with the second thermoplastic material intimate bonding contact resolidification.In this regard, it can control the temperature of the mold of the second thermoplastic material entrance to help control solidification rate.Such as, a kind of method is using fluid-cooled mold, such as liquid (such as water) cold mold, and low about 15 DEG C of minimum fusing point or more, particularly about 30 DEG C or more than the material (such as component A material in A-B or A-B-A profile material) in intermediate form will be maintained at close to the wall temperature of die cavity.

As a more specific example, for by thermoplastic material (such as polypropylene material) injection moulding, to intermediate form is had, (it includes about 3 to 8 layers of A-B-A elongated member (such as band, wherein component A includes the material that fusing point is about 120 DEG C)) die cavity in, the wall around die cavity is maintained at about 80 DEG C using water cooling mold (such as by tool steel, tool steel, PX5, H13, S7 for example including chromium and molybdenum (such as P20) or the like are made).After injection moulding, for the typical component that wall thickness is about 2 to 4 millimeters and total weight is about 0.3 to 1 kilogram, mechanograph is kept about 5 to 60 seconds in a mold before release or more long.For example, the time is more typically about 15 to 35 seconds estimated for product manufactured according to the present invention.The example of suitable moulding press is 300 metric ton Demag injection molding machines.

In another aspect of the present invention, large-size components (such as longest dimension is greater than about 0.5 meter, is particularly greater than about 1 meter) are moulded to include the reinforcing material of the intermediate form of (even if only consolidating down to about 10 volume %) under concretion state.As an example, the automobile buffer assembly (it can also include one or more other components, such as bumper bar) of enhancing can be prepared, or requires to use the other component of large plate (platen) tool.Thus, it is possible to require compression molding to form many components of formed body before this by injection moulding manufacture.

As it appears from the above, being moulded together with intermediate form to manufacture the raw material of enhancing composite article is usually thermoplastic material.This kind of material can be (such as with one or more fibers, microsphere, nanoparticle or other, such as glass, clay, talcum or the like filling) for being not filled by or filling.But in some embodiments, which can be thermosetting plastics (such as urethanes, rubber, epoxy resin or other).Although raw material are preferably the thermoplastic material for having identical logical class with the thermoplastic in intermediate form, not necessary.The material for the second thermoplastic material that can be used in raw material and/or the material that can be made into elongated member include, but are not limited to any material used in the first thermoplastic material of intermediate form, and vice versa.Specific example includes thermoplastic olefins polyolefins, ultra high density polyethylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), very low density polyethylene, ultra high density polypropylene, high density poly propylene, middle density polypropylene, low density polypropylene, extra-low density polypropylene, polycarbonate, polyvinyl chloride, (methyl) acrylonitrile, (methyl) acrylate, polyurethane, thermoplastic elastomer (TPE), thermoplastic olefin, polyamide (such as nylon 6, nylon 6, 6 or other), polysulfones, polyester, polyalkylene terephthalate (such as poly- (ethylene terephthalate), poly- (butylene terephthalate), it is poly- (to dibenzoic acid 1, 4- cyclohexanedimethanol ester) or other), poly- naphthalenedicarboxylic acid alkylene (such as poly- (polyethylene naphthalate)), acronitrile-butadiene-styrene, poly arylidene thio-ester ( Such as polyphenylene sulfide), thermoplastic polyurethane, PPE, polystyrene or any combination of them (either copolymer, admixture or form of mixtures).Also other any or more polymeric materials as described herein can be used.

Such as but unrestrictedly, a kind of ad hoc approach is it is expected that raw material and/or Elongated Member Materials are selected from polyolefin, polycarbonate, polystyrene, vinyl-based, polyamide, polyalkylene terephthalate, polyester, polyphenylene sulfide, (methyl) acrylate or any combination of them.

As can be seen that can choose raw material to allow to coloured molding.Alternatively, can be coated with to obtain required appearance.

Although the fusing point of the raw material in conjunction with intermediate form can be lower than the minimum fusing point of any material in intermediate form, more generally, the estimated peak melting point higher than any material in intermediate form of the fusing point of raw material.For example, the difference of the peak melting point of any material is more than 10 DEG C, particularly 30 DEG C, still more specifically 50 DEG C in the fusing point and intermediate form of raw material.

In another aspect of the present invention, enhancing composite material manufactured according to the present invention shows excellent dimensional stability over a wide temperature range.For example, the linear coefficient (- 40 DEG C to+80 DEG C) of thermal expansion can be about 17 to 24 μm/m- DEG C, more specifically about 19 μm/m- DEG C.

After forming shaped composite article, it can according to need and one or more rear moldings or secondary operation are carried out to resulting product, such as (but not limited to) machining, coating, ultrasonic welding, solvent bonding, hectographic printing, silk screening, drop stamping, engraving, surface treatment, bending, compacting, corona discharge, corona treatment, flame injection, any combination of them or other.

It is also acknowledged that in conjunction with any molding or consolidation step one or more heating stepses can be used to intermediate form.This kind of step or any other heating stepses according to the present invention can be carried out by conduction, convection current, radiation or any combination thereof.Baking oven can be used as heat source.Also radiofrequency heat source and/or microwave heat source can be used.Heating can be carried out in inert atmosphere or in air.In addition, heating stepses may include the step of progress under multiple each comfortable different temperatures, each comfortable different pressures applied.

Referring to Fig. 3, it is shown that the illustrative example of shaped three dimensional article 100.Product has upper surface 102.Although loose fiber or frayed edges may be generated at edge 104 according to procedure of processing, they can eliminate (such as, it is expected that they are removed by suitable punching, finishing or other cutting steps, or the step of edge by being suitable for connecting intermediate form avoids).Shown in multilayer as used band fabric can dangle made of (drapable) form, the inside of product 106 can be consolidated, and relatively, part 108 does not consolidate.Shown loose fiber is exemplary, and it is expected that is removed them by suitable punching, finishing or other cutting steps.

For not yet disclosed degree, it is also contemplated that other variations of the invention.Such as, elongated member can be made of single material (such as thermoplastic such as polyolefin) substantially, or it may include different types of material, such as selected from glass fibre (such as E- glass, S- glass or other), carbon fiber, metallic fiber, different plastic optical fibres (such as aramid fibre), ceramic fibre (such as silicon carbide fibre), natural fiber, their combination or other materials.Elongated member can be applied or uncoated.Intermediate form can be impregnated with suitable chemical agent, polymerizable compound, filler or other impregnating agent.Surface finish agent and/or extra play can be applied in intermediate form or gained moulded products, including for example one or more components for reducing electrostatic, photostability, hydrophily, hydrophobicity, anti-flammability, coloring, conductivity or any combination thereof.

For foregoing teachings, it can be appreciated that the ability for forming beautiful product is another potential benefit of the invention.For example, a kind of embodiment is imagined in intermediate form using with different in width, thickness, color, any combination thereof or other multiple elongated members.Thus, it is possible to obtain required quality, shape, pattern or other feature.Furthermore, it is possible to form complicated formed body and constructed in accordance, such as form rib, filler rod, ripple or other protrusions.

Intermediate form of the invention can also be used in the product that weaving or non-woven fibre (such as continuous or chopped glass or other) felt is used in combination.

It can be using the intermediate form used according to the invention as the substitute of plastic foil in multilayer (such as lamination) product.

In addition to the above, multiple elongated members of the invention can shred and random or controlled dispersion is in intermediate form of the invention.It is referred to United States Patent (USP) 5,872,067 incorporated herein by reference and understands other aspects.

Purposes

Product manufactured according to the present invention shows excellent impact resistance and other machinery performance.Such as, automobile component is estimated to be met in terms of side impact, knee bar and glove box door impact, top cover (header) and rail head impacts and/or bumper property or more than energy management standard, such as United States Federal Motor Vehicle Safety Standard (" FMVSS ") 214, FMVSS 208, FMVSS 201 and/or the standard specifically included in other ways in 49C.F.R.581.

It is referred to existing literature and finds other feasible variants, 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 incorporated herein by reference.

Material of the invention is suitable for many different purposes, to instrument and other purposes from automobile component to construction material.Example includes, but it is not limited to, spare tyre lining (well liner), cargo liner, compartment lining, backrest, fender, fascia, knee bar, glove box, automobile interior decoration, headfast, back seat cover, buffer, spoiler, air diffuser, hood, air dam, fuel tank, sunshading top deflecting plates, automotive preventing stone plate, car body panel, aircraft instrument disk, in wheel lining, overturning switch, switch button, hand-made fixed handle, luggage header tank, door handle, flak jackets, the helmet, shell, floatation device, shipping container, food packaging, luggage, fastener, shin guard, elbow support, knee-pad, chest protector, mask, ornament, tubing, desktop, pressure vessel, protecting screen, down-hole equipment shell, shell, ship components, safety box, lock, fluid container, house and building components, ground Plate, wall or other plates, roof Material, shutter, outcase of refrigerator, washing/drying machine shell, bench, seat, cross bar, handheld tool, prosthese, rectifier, wheelchair or its component, toy, housing of TV set, audiofrequency apparatus shell, portable instrument shell, camera case, consumer electronic products shell, air-conditioner compressor outer housing, crossbeam, crossbeam, instrument board, shutter just, sole or other footwear component (such as toe-cap) or other.

In one aspect, material of the invention is particularly useful for constructing pipeline or container, is especially used as protective cover and/or trandfer fluid pipeline or container.Such as, present invention contemplates be used for heavy-duty industrial applications, such as the manufacturing method of the pipeline for conveying chemical reactant or product or channel, water, sewage or even gas, this kind of pipeline are usually hard or semi-rigid, and are optionally flexible in part or all of its length.

Good physical characteristic, such as improved circumferential stress performance, Zernike annular polynomial performance, durability and low-temperature impact property are shown using tubing made of material of the invention, especially compared with the non-reinforced tubing of similar material.

It can be made of substantially single wall 202 referring to Fig. 4 A-4D construction that can be seen that tubing 200 according to the present invention, or may include two or more walls 204 and 206 as shown in Figure 4 B.When using multi wall, they can be concentric as in Fig. 4 B or they can include wall 210 built in one or more outer walls 208 and one or more (it can be single-layer or multi-layer construction again) as in Fig. 4 C, such as delimiting Zhi Liuguan.They can be straight, or be wrapped in its at least part length.Wall construction may include one or more round, flat or curved sections.Other structures are also feasible.Fig. 4 D shows a kind of example of preferable configuration, wherein in the covering on the structure of fig. 4b of sheath 212.Sheath can be with the embodiment of coverage diagram 4A and 4C.The rectangular structure that sheath is shown as and is in contact with it is adjacent, but can also open at least part inside it with spacing structure below.

The wall 202 for delimiting the pipe of Fig. 4 A is usually made of intermediate form (intermediate form especially consolidated) according to the present invention as described herein substantially.For the tubing of type shown in Fig. 4 B and 4C, at least one wall construction includes the intermediate form (such as being made of aforementioned component A and B) according to disclosure herein.Intermediate form is generally in concretion state, but it can also not consolidated substantially.It does not include that the tube portions of intermediate form may include any material for being suitable for manufacturing pipeline, hose or conduit, and can be metal, plastics, composite material, the single layer made of suitable material, multilayer or other.Preferably, core pipe includes polymer (such as polyolefin), more preferable polyethylene, polypropylene or PET.In one aspect, tube wall can be made of any material as described herein.For example, core pipe can be the extruded member with one or more components (such as said components A and B).In a specific embodiment, tubing includes the polyethylene with the suitable stable package pressure classification with convenient pressure grade (such as equal to or more than the PE 80 measured by ISO 9080).

Elongated member 214 (having width (w)) as can be seen that intermediate form in Fig. 4 E-G surrounds the package of core pipe 216 in a manner of being suitable for manufacture hose or pipeline or winds (such as spiral winding), and optionally consolidates.On the one hand, multiple elongated members can be woven together to cover core pipe, this durability and low-temperature impact resistance that tubing can be caused to improve again.Any suitable angle (α) can be used around the winding of core pipe in elongated member, and wherein angle is in about 30 ° to 90 ° preferably with respect to the vertical axis of tubing.It is highly preferred that winding angle be greater than about 45 °, more preferably greater than 50 °, but be lower than 55 ° (such as about 45 ° to 54 °).On the one hand, in order to realize the particularly attractive combination of axial and circumferential stress performance, angle is about 54.7 °.It should be understood, however, that bigger winding angle be also likely to be it is desirable, be greater than about 60 ° (such as 60 to 75 °), or even greater than about 75 °.Any suitable intermediate form, including twister, fabric or combination can be used.Continuous winding object can be adjacent to each other or be overlapped, or they can be spaced each other with spacing (p), it such as is about 5 to 500 millimeters for diameter (d), 1000 millimeters or even 2000 millimeters, particularly about 10 millimeters to 100 millimeters or bigger of tubing, the spacing can be at most about 10,25 or even about 50 millimeters or 50 millimeters or more.Winding layer number etc., to realize the required performance of gained tubing.For example, winding layer number can be about 1 to 100, or even about 2 to 50.Most about 25 winding layers can be used in some embodiments, some to may include about 10 or less winding layer.

On the one hand, core pipe is by the layer covering of multilayer elongated member, such as two layers, three layers, four layers, five layers or five layers or more.Identical or different material can be used to every layer.In preferred embodiments, core pipe is covered using at least two layers identical material.Every layer inversely winds (counterwound) in the opposite direction with the angle equal relative to vertical axis, can generate the layer structure of balance in this way.It will of course be appreciated that winding angle can be changed between each winding layer, change elongated member composition or other characteristics, change the width or thickness of elongated member, apply film layer, apply coating, change spacing or any combination of them.Winding step can be carried out in room temperature.It can also be carried out at high temperature (for example, at least about 40 DEG C).

Furthermore, it is possible to include optional but preferred sheath on some or all of tubing outer surface.For example, it covers core pipe/intermediate form sub-assembly at least part outermost layer.Sheath can be any material for improving the resistivity that tubing injures abrasion, scuffing, lobe, Chemical exposure, ultraviolet light or other types, and can contain the reagent for the long-time stability for improving the material in other ways.Preferably, sheath includes the polyethylene with suitable pressure rating (such as equal to or more than the PE 80 measured by ISO 9080) pressure classification.

Tubing can consolidate at any point, and usually then in any elongated member portion, compared with its original state, holding form substantially.For example, core pipe can consolidate before being covered by sheath.In a preferred method, after one or more layers covers tube core or after being added to sheath covering, tubing is consolidated.In addition it is possible to use multiple consolidation steps, although it is preferred that only one consolidation step.A kind of favorable method be apply on tubing intermediate form then by intermediate form consolidation (such as by conduction heat, advection heat, radiant heat, or combinations thereof).Consolidation can carry out enough time (such as about 1 to about 5 minute) under about 100 to about 175 DEG C, more particularly smaller than about 150 DEG C of high temperature (for example, for polyolefinic elongated member).The longer or short period is also possible, such as at most about 0.25 hour or more long (as previously described).In consolidation process, it is assumed that the material of the elongated member of intermediate form is at least partly melted and is fused on tubing.Under this approach, the enhancement layer from intermediate form can be fixed on underlying pipe without optional laser welding or other local heat treatmet steps.

Preferably, the tubing constructed according to the present invention meets or exceeds following physical parameter, such as is greater than about 10MPa 50 years circumferential stress performances at 20 DEG C；In 9.2 bars and 80 DEG C, be greater than at least 500 hours, be particularly greater than 1000 hours slow crack propagation (SCG) performance (according to test method ISO 13479)；It is greater than 10 bars rapid crack growth (RCP) performance at 0 DEG C (according to test method ISO 13477)；Or the combination of both characteristics.

In an exemplary embodiment, construct the tubing that co-extrusion band outer layer (they are applied in inner tube not consolidate winding or woven intermediate form first) is consolidated with inner tube (such as thermoplasticity inner tube, such as polyethylene, polypropylene or combinations thereof), two layers.Band at least has A-B component structure as described elsewhere herein.In a specific examples, before band is applied in inner tube, band has been stretched at least 4, and particularly at least 8, the still more specifically draw ratio of at least 12 (such as 16).Every layer of co-extrusion band is applied as follows: at least one elongated member is wound with about 50 to about 60 ° (such as 54 °) of winding angle.Band, by heating at 150 DEG C or more at least 1 minute (such as 160 DEG C 4 minutes), but is preferably shorter than while being located in inner tube and consolidated band greater than 0.25 hour.Compared with core pipe is used alone, this exemplary tubing shows at least 20%, more preferably at least 30% burst strength (according to test method ISO 1167, using the pressure speedup of 1 ba/min of clock until rupture).(80 DEG C and 7MPa are used) when comparing circumferential stress performance (according to test method ISO 1167), and individual core pipe was ruptured at 10 hours, and this exemplary tubing only just ruptures after about 250 hours.Similar to the abovely, the exemplary tubing made of four layers of co-extrusion band does not show any rupture in test at least 500 hours, more preferably at least about 1000 hours.

Find out from the above, present invention further contemplates trade methods, and accordingly, in combination, the first mechanism supplies unconsolidated intermediate form to the second mechanism to the delivering with raw material (such as polypropylene).The intermediate form is consolidated the composite article for then moulding to be formed and wherein having the consolidation form by the second mechanism.Alternatively, in combination with the deliverings of raw material, intermediate form of the first structure to the second mechanism supply consolidation.Second mechanism wherein has the composite article of the consolidation form with rear molding.First or second mechanism can be except molding or replacement moulds ground, will have product vacuum forming, punching press, compacting, the thermoforming of the consolidation form.As can be seen that the first mechanism can supply the intermediate form of shaped form or flat sheets.Intermediate form can also be manufactured by single mechanism and include its gained composite article.

Embodiment 1: using drop-dart impact test (according to ISO 7765-1) in room temperature and 40 DEG C of (-), it will include the performance with the bond pad (1.85 millimeters thick) of the co-extrusion band (being designated as sample X) of the propylene-ethylene copolymers of polypropylene homopolymer co-extrusion disclosed herein (about 0.04 millimeters thick × 3 mm wides), with shown 1.5 and 2.2 millimeters thicks with CURV^TMThe performance of the material (being hereafter denoted as " sample A " and " sample B ") bought of running after fame is compared.Fig. 5 A and 5B show data obtained by preferred embodiment according to the present invention.

Embodiment 2: using polypropylene bulk material, together with three layers of (3L) consolidated twill woven co-extrusion polypropylene ribbon (about 0.04 millimeters thick × 3 mm wides) intermediate form on the polypropylene bulk material side, is injection moulded spare tyre case.Resulting product is wrinkle-free, and in 8MPH in -30 DEG C of impacts, and 400% improvement is shown compared with the 40% long glass fibres composite material with 20% glass filled Polypropylene matrix.Observe the complete ductile rupture not being crushed；The clast flown upward is not observed in impact process.

Embodiment 3: repeating embodiment 2, but intermediate form be placed on the two sides of polypropylene bulk material, shows the rigidity and impact resistance improved compared with 2 composite material of embodiment.

Embodiment 4: repeating embodiment 3, but monolayer polypropylene tape is used in the twills of intermediate form.Resulting product is wrinkle-free, and shows to improve compared with the 40% long glass fibres composite material with 20% glass filled Polypropylene matrix when 8MPH is in -30 DEG C of impacts.Observe the complete ductile rupture not being crushed.

Embodiment 5: the sample of spare tyre case (2.2 centimetres of depths, 15 centimetres wide, 25 centimeter lengths and 2.25 millimeters of wall thickness) composite material is manufactured 6 layers of (6L) intermediate form (about 0.18 millimeters thick of each layer of consolidation) of consolidation made of weaving co-extrusion polypropylene ribbon.Intermediate form is placed in the chest bottom.Impact test is carried out to it and is compared with 30% short glass fiber reinforced polypropylene of baseline blow molded material.The test uses the actuator velocity of 8mph, the fixation device with 5.1 cm round impactor.The test is carried out in room temperature and at -30 DEG C, and hits the chest bottom with intermediate form including eccentric, to make its tension to bear load.As the result is shown in figures 6 a and 6b.

Embodiment 6: as the example of constrained (constrained) consolidation operation of one kind for multi-layered textile intermediate form, the compression molding press manually controlled can be heated to preselected temperature (for example, 110 to 150 DEG C).Woven intermediate form according to the above description is cut into identical with press plates size (such as 30 × 30 centimetres, wherein with machine direction cutting fabric in parallel).It stacks several layers of fabric to be placed between protective layer (such as Mylar film), and the stack is placed between metal plate top and bottom, be transported in press.Press is closed immediately, and applied force (such as applying 150kN 1 minute).Then, it improves power (such as to 350kN 3 minutes).Press heating is cut off, and carries out the spacious water cooling of press while under workpiece is still in pressure.Open press, and withdrawing plate and Mylar film.Gained workpiece shows consolidation (such as density is greater than 95% theoretical density).

Embodiment 7: as the example of a thermoforming operations, it is compression molded press (such as manually operated, equipped with the mold for the box part having a size of 20 × 20 × 4 centimetres).Extruded polypropylene sheet material is pressed into (for example, passing through sheet extrusion) with woven intermediate form on two sides layer by layer.Laminate is heated in press (contact in 5 minutes heat), then thermoforming and before demoulding cooling press under stress.The temperature from 180 to 165 of different samples is differed to 150 DEG C.It observes, at reduced temperatures, height is lower by the leafing of stress angle and near sharp angles.

Embodiment 8: the thermoforming consolidated intermediate form (30 × 30 cm plate surface) on the manual Fonteyne compresion molding press equipped with square cup mold.Initial forming temperature (T formpiston side and cavity side) is 150 DEG C.By contact heat, it is heated 5 minutes in press.Then press is closed, and applied power 1 minute of 50kN.Resulting product shows attractive surface smoothness.

Embodiment 9: it (is operated at 165 (drop in) to 190 DEG C, and die head temperature is 200 DEG C) using extruding machine.Upper roller, central roll and lower roll temperatures are respectively 90,80 and 40 DEG C.Use 0.8-0.10 ms/min of linear speed.Sheet width, 1.0 to 1.2 millimeter polypropylene layers of the raw material with 35 centimetres, and intermediate form is respectively 0.2 millimeters thick and 50cc wide.Intermediate form is fed in the first roller from top, and in a separate operation, intermediate form is fed from below in the first roller.In another operation, the opposite layer of intermediate form is fed from top and bottom in the first roller.Good bonding is obtained, and detects without detection amount of warpage or only unconspicuous amount of warpage.

According to above it will be appreciated that, product manufactured according to the present invention shows many beneficial characteristics, including but not limited to, recyclability, the ability for reducing compared with non-reinforced material wall thickness (and saving along with weight and material cost), good low-temperature impact resistance, in impact without broken, good term creep resistance, good term fatigue resistance, good abrasion resistance, long term dimensional stability or any combination of them.

Such as but without limitation, compared with glass filled Polypropylene material, self-reinforced composite material (such as PP composite material) according to the present invention (density with about 0.8 gram/cc) can reach twice of baseline room temperature toughness and low-temperature toughness, three times or even four times.

It should be realized that, in a particular aspects of the invention, many aforementioned properties are material selection and the combined result of processing conditions --- this combine causes during all procedure of processings before final product is completed, high form in the elongate member of intermediate form keeps degree, such as keeps its orientation substantially.Particularly, a method of the invention is any step for avoiding using consolidated intermediate form before thermoforming, punching press or other intermediate form shaping steps.Current material uses consolidation step before any such intermediate form shaping step.But for many novel embodiments disclosed herein, this orientation retentivity is not enforceable.Therefore, technical staff using the various prior art materials of consolidation step before intermediate form shaping step, it will be recognized that still can be used for manufacturing composite material in these embodiments.In addition it is possible to use multilayer intermediate form, wherein and processing of the not all layer all by being used to keep orientation.

" first " and " second " is not meant to limit in the combination being only made of the first and second parts herein.When so describing, subject of the present invention can uitably include third, 4th or more part." elongated member " is not meant to exclude the coverage area of multiple elongated members.In addition, " (methyl) acrylate " refers to acrylate and/or methacrylate.Unless otherwise specified, as the use of the procedure of processing of " consolidation " or " molding " does not require fully consolidated or molding；It is also contemplated that arriving partial consolidation or molding.The saying of " A-B " component structure is not excluded for the presence of other layers or the other materials different from component A and B.In addition, the saying of "an" or "one" element or step is not excluded for other elements or step.The upper limit was both referred to using term " about " or " approximation " before a certain range or had referred to lower limit and do not limited (for example, " about 1 to 3 " is to include " about 1 to about 3 ") by amount listed in the range.Unless otherwise specified, or as indicated otherwise in text, " mixture " or " combination " of polymer includes the mixture of this quasi polymer, admixture or even copolymer.

Unless otherwise specified, the size of various embodiments as described herein and geometry are not limiting the present invention, and other sizes or geometry are also possible.Multiple structure members can be provided by single integrated morphology or step.Alternatively, single integrated structure step can be divided into individual multiple components or step.However, it is possible to by these function sets to single component or step."comprising", " having " and " comprising " further include more restrictive term " by ... is constituted " and " substantially by ... constitute ".

In addition, this feature can be according to any given purpose in conjunction with one or more of the other feature of other embodiments although a certain feature of the invention may only make description in an exemplary embodiment.Such as, microlayer elongated members can be incorporated in tubing, tubing can be used in combination with raw material and intermediate form, it can include thermosetting material in elongated member, can include microbedding in the elongated member of non-co-extruded band, or about a part of the invention or in terms of the material that refers to can be in other aspects of the invention.According to above it will also be recognized that the manufacture and its operation of the unique texture of this paper also constitute method of the invention.

It is to be understood that foregoing description is only used for illustrating and not restrictive.On the basis of reading above description, many embodiments and many purposes in addition to provided example are apparent to those skilled in the art.Therefore invention scope should not be determined referring to above description, and should be determined referring to the full breadth of the counterpart of appended claims and these claims.The disclosure of all articles and bibliography (including applying and openly) is incorporated herein by reference.Any aspect for the subject matter disclosed herein ignored in following claims does not represent the abstention of this theme, and should not be considered as a part that this theme is not considered as present invention disclosed theme by inventor.

Annex

Without limitation, unless otherwise specified, following content is the example for understanding the test procedure of property cited in described herein and claims.

Crystallinity is measured by differential scanning calorimetry (DSC) using Q1000TA equipment.In the measurement, 10 milligrams of small acrylic polymers samples are enclosed in aluminium DSC disk.Sample is put into the room DSC purged with 25 cc/min nitrogen, and is cooled to about -100 DEG C.By being heated to 225 DEG C with 10 DEG C/min, the standard thermal history of sample is established.By sample 225 DEG C keep 3 minutes to ensure to be completely melt.Then sample is cooled to about -100 DEG C with 10 DEG C/min.Again by sample at -100 DEG C of holding isothermals 3 minutes to stabilize.Then it is reheated to 225 DEG C with 10 DEG C/min.Record observes fusing heat (Δ H for the rescan within the scope of 80~180 DEG C_{Observed value}).The relationship of the fusing heat and crystallinity (accounting for sample, such as the weight percent of polypropylene specimen weight) observed: crystallinity %=(Δ H is established by following equation_{Observed value})/(ΔH_{Isotaxy pp}) × 100, wherein in B.Wunderlich, Macromolecular Physics rolls up 3, Crystal Melting, Academic Press, New York, and fusing heat (the Δ H of isotactic polypropylene is had recorded in 1960, p 48_{Isotaxy pp}), it is 165 joule/gram polymer (J/g).As above the highest crystallization temperature of melt is measured with 10 DEG C/min of cooling rate by DSC.Pass through the peak value measurement fusion temperature of melting transition.Similar analysis is suitable for the material other than polypropylene, changes the Δ H value into other materials.

Molecular weight distribution (MWD) (such as polypropylene homopolymer) is measured as follows by gel permeation chromatography (GPC).It are being furnished with 4 linear mixed bed columns, analyzing polymers on the Polymer Laboratories PL-GPC-220 high temperature chromatographic unit of 300 × 7.5 millimeters (Polymer Laboratories Plgel Mixed A (20- micron granularity)) by gel permeation chromatography (GPC).Furnace temperature is 160 DEG C, and Autosampler hot-zone is 160 DEG C, and warm area is 145 DEG C.Solvent is 1 containing 200ppm 2,6-di-tert-butyl-4-methylphenol, 2,4- trichloro-benzenes.Flow velocity is 1.0 ml/mins, and injection volume is 100 microlitres.By the way that sample is dissolved 2.5 hours in 1 containing 200ppm 2,6-di-tert-butyl-4-methylphenol that nitrogen purges, 2,4- trichloro-benzenes at 160 DEG C under mild agitation, 0.2wt% sample solution of the preparation for injection.

Their elution volume, deduced molecular weight measurement are combined using 10 Narrow Molecular Weight Distribution polystyrene standards (come from PolymerLaboratories, EasiCaI PS1,580-7,500,000 gram/mol).Use Mark-Houwink coefficient (such as Th.G.Scholte appropriate, 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 (such as E.P.Otocka, R.J.Roe, N.Y.Hellman, P.M.Muglia, Macromolecules, 4,507 (1971) are described, incorporated herein by reference) in 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) equivalent weight of sample polymer (such as polypropylene), is measured.

Unless otherwise specified, for material listed in this article, 1% Secant flexural modulus is measured by ASTM D790-00；Density is measured according to ASTM D792；Fusion temperature is estimated according to ISO 11357-3 by differential scanning calorimetry；And bending modulus is measured according to ISO 178.

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

By the way that 4+/- 0.1000 grams of sample is dissolved into 250 milliliters of Erlenmeyer flasks and adds 200 milliliters of inhibited dimethylbenzene by pipette, xylene soluble part is measured.In order to inhibit dimethylbenzene, 18.35 grams of Irganox 1010 are added in 200 milliliters of dimethylbenzene in beaker, and are stirred until dissolution.After the dissolution of Irganox 1010, solution is poured into 4.9 gallons of diformazan benzos and is sufficiently mixed solution.It is put into stirring rod, water-cooled condenser is placed on flask and flask assembly is placed on magnetic stirrer/hot plate.It is vigorously stirred and adjusts heating to obtain mild boiling, until sample is completely dissolved.Blanket of nitrogen should be kept on condenser in this procedure.After sample dissolution, flask assembly is removed from magnetic stirrer/hot plate, takes out stirring rod, then cover.Flask is allowed to be cooled to close to room temperature (30 DEG C, cooling to spend about 1 hour).On flask plus sets lead ring and be immersed in water bath with thermostatic control.After temperature in flask reaches 25+/- 0.5 DEG C, more than 30 minutes are stood again in water.In cooling procedure, insoluble partly precipitated.Filtering solution；Then 100 ml aliquots samples of filtrate are placed in aluminium dish and are evaporated to dryness under nitrogen flowing.By the way that residual polymer is weighed, existing soluble matter is measured.

Five unit group percentage of isotaxy, three unit group percentage of isotaxy and isotaxy five unit groups/tri- unit group ratios are measured as follows by those of ordinary skill in the art:¹³C nuclear magnetic resonance (NMR) provides the direct measurement of the steric regularity of poly- (propylene) homopolymer.The end of the chain and reversion (inverse) insertion are ignored in analysis used herein.For three unit group names (mm, mr and rr), " m " represents meso, and " r " represents racemic.Three unit group percentage of isotaxy is the measured value of tri- unit group of mm.V.Busico, R.Cipullo, G.Monaco, M.Vacatello, A.L.Segre, Macromolecules 1997,30,6251-6263 describes the method for analyzing measurement isotaxy five unit groups and three unit groups using NMR.

Five unit group of isotaxy/tri- unit group ratios are the ratios of three unit group percentage of five unit group percentage of isotaxy and isotaxy.When measuring five unit group of isotaxy and three unit class value of isotaxy, by the way that 0.5 gram of polypropylene homopolymer to be dissolved in the mixture of 1.75 grams of tetrachloroethanes-d2 (TCE-d2) and 1.75 grams of 1,2- o-dichlorohenzenes, sample is prepared.Sample is heated in heater (block) to promote mix in 150 DEG C of homogenizing and with hot rifle.On VarianUnity+400MHz, at 120 DEG C, NMR experiment is carried out under sample rotates and non-rotary situation using 1.32 seconds acquisition times, 0.7 second duplicate delays, 4000 acquisitions and continuous proton decoupling (fm-fm modulation).Total scanning time used is 2.25 hours.

Claims (50)

1. a kind of method for preparing shaped composite article, includes the following steps:

A. intermediate form is consolidated and is formed, which includes the constitutional repeating unit of at least one elongated member and multiple first thermoplastic materials, which contains the surface portion by melting before adjacent alignment portion；

B. consolidation and molding intermediate form are placed in die cavity；

C. the second thermoplastic material is introduced into die cavity；With

D. enhancing composite article is released from die cavity, which includes the intermediate form and the second thermoplastic material of consolidation.

2. according to the method described in claim 1, further comprising strain hardening intermediate form.

3. method according to claim 1 or 2, wherein the second thermoplastic material is introduced die cavity with molten state.

4. according to the method described in claim 3, wherein carrying out the consolidation and molding of at least partly intermediate form simultaneously.

5. method according to claim 1-4, wherein consolidation and forming step include the following steps: to clamp intermediate form to which while applying the power for deforming the intermediate form, which is moved freely in predetermined limits without deforming.

6. method according to claim 1-5, wherein intermediate form can dangle before any consolidation step.

7. method according to claim 1-6, wherein at least the first thermoplastic material include the non-migrating processing aid or surface modifier that quantity is less than Elongated Member Materials about 10wt%.

8. according to the method described in claim 7, wherein non-migrating processing aid or surface modifier include being selected from siloxanes, polyolefin, halogenated polymer, or any combination thereof reagent.

9. according to the method described in claim 8, wherein reagent includes high molecular weight silicone.

10. method according to claim 9, wherein reagent includes alkylsiloxane.

11. according to the method described in claim 10, wherein reagent includes dimethyl siloxane.

12. -11 described in any item methods according to claim 1, wherein the first thermoplastic material and the second thermoplastic material come from polymer of the same clan.

13. -12 described in any item methods according to claim 1, wherein the first thermoplastic material and the second thermoplastic material are polyolefin.

14. according to the method for claim 13, wherein the first thermoplastic material and the second thermoplastic material include propenyl polymer.

15. -14 described in any item methods according to claim 1, wherein intermediate form includes multiple layers.

16. according to the method for claim 15, wherein at least two layer At at least one aspect, as whether material type, the composition of elongated member, the heat treatment of elongated member, the width of elongated member, model type, this layer consolidate, the presence of film layer, thickness, form or any combination of them it is different from each other.

17. method described in 5 or 6 according to claim 1, wherein at least part of this layer along one edge of intermediate form is connected to each other.

18. method according to claim 15 or 16, wherein fixing step includes at least two edges thermal connection structural unit along form.

19. -18 described in any item methods according to claim 1 further comprise the enhancing composite article of circulation acquisition without separating material therein.

20. -19 described in any item methods according to claim 1, wherein elongated thermoplastic member is selected from fiber, shaft, rope, yarn, band, monofilament, band or any combination thereof.

21. -20 described in any item methods according to claim 1 further comprise the first thermoplastic material for being coextruded at least two polyolefin polymers to prepare elongated member.

22. -21 described in any item methods according to claim 1, wherein constitutional repeating unit be originated from single elongated element or be originated from multiple elongated members and package assembly unit to limit woven form, in the form of winding, the form of knitting form, type of weave, random dispersion form or any combination thereof.

23. -22 described in any item methods according to claim 1, wherein form is consolidated at room temperature substantially by punch steps.

24. -22 described in any item methods according to claim 1, wherein intermediate form is formed before consolidation.

25. -24 described in any item methods according to claim 1, wherein preparing elongated member by the method included the following steps: film is cut into strip and stretches the strip cut by extrusion film.

26. -25 described in any item methods according to claim 1, wherein intermediate form does not have inorganic reinforcement phase.

27. -26 described in any item methods according to claim 1, wherein intermediate form includes geophysical textile material.

28. -27 described in any item methods according to claim 1, wherein intermediate form includes at least one elongated member, which contains at least three kinds of different components for realizing at least A-B-C type structure.

29. wherein only partial consolidation and/or part form intermediate form according to the described in any item methods of preceding claims 1-28.

30. consolidating the thermoplastic repeating structural unit to show wrinkle-free surface and the part in the cells with relatively high reservation crystallinity together including introducing according to the described in any item moulded plastic products of preceding claims 1-28.

31. a kind of method for preparing shaped composite article, includes the following steps:

A. the first thermoplastic material and at least one elongated member containing surface portion are provided, which can melt before the fusing of adjacent or interior section；With

B. elongated member is processed into intermediate form, the form includes multiple usually relative to the constitutional repeating unit moved freely with each other, wherein form can be processed to form shaped composite article, which is wrinkle-free on the expose portion of the form in the composite article of acquisition and in the cells with relatively high reservation crystallinity.

32. according to the method for claim 31, wherein procedure of processing (b) includes at least one procedure of processing chosen from the followings: thermoforming, vacuum forming, pressure forming, compression molding, blow molding, injection molding, rotational molding, hot pressing, lamination, extrusion-blown modling, profile extrusion or any combination thereof.

33. the method according to claim 31 or 32, wherein being coextruded the first thermoplastic material to include the layer containing propylene-ethylene copolymers and the adjoining course containing isotactic polypropylene homopolymer.

34. wherein at least one elongated member further comprises the non-migrating processing aid or surface modifier that quantity is less than Elongated Member Materials about 10wt% according to claim 31-33 described in any item methods.

35. method described in claim 34, wherein non-migrating processing aid or surface modifier include being selected from siloxanes, polyolefin, halogenated polymer, or any combination thereof reagent.

36. according to the method for claim 35, wherein reagent includes high molecular weight silicone.

37. according to the method for claim 36, wherein reagent includes alkylsiloxane.

38. according to the method for claim 37, wherein reagent includes dimethyl siloxane.

39. product made of -38 described in any item methods according to claim 1.

40. the purposes of product made of -38 described in any item methods according to claim 1.

41. a kind of method for preparing enhancing composite article, includes the following steps:

(a) intermediate form including geophysical textile material is provided；With

(b) intermediate form is overmolded with thermoplastic.

42. further comprising according to the method for claim 41, following steps: intermediate form is clamped to which while applying the power for deforming the intermediate form, which is moved freely in predetermined limits without deforming.

43. the method according to claim 41 or 42, wherein intermediate form includes multiple layers.

44. wherein intermediate form is made of geophysical textile material substantially according to the described in any item methods of claim 41-43.

45. according to the described in any item methods of claim 41-44, the grasping tensile strength (according to ASTM D4632) that wherein geophysical textile material is shown is at least about 0.5 to about 3kN, it is at least about 15% with the elongated rate of tensile strength (according to ASTM D4632) is grasped, Maron formula bursting strength (according to ASTM D3786) is about 2000 to 10,000kPa and puncture intensity (according to ASTM D4833) are about 0.25kN to about 0.80kN.

46. wherein geophysical textile material is made of polyolefin substantially according to the described in any item methods of claim 41-45.

47. wherein geophysical textile material is made of propenyl polymer substantially according to the described in any item methods of claim 41-46.

48. according to the described in any item methods of claim 41-47, wherein the thermoplastic for overmolded step includes polyolefin.

49. according to the described in any item methods of claim 41-48, wherein the thermoplastic for overmolded step is made of propenyl polymer substantially.

50. according to the purposes of product made of the described in any item methods of claim 41-49 or product.

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