CN207617255U - Thermoplastic composite lamilate and product prepared therefrom - Google Patents

Abstract

The utility model discloses thermoplastic composite lamilates, it is characterised in that includes sequentially：(a) top layer being made of at least a piece of POLYCARBONATE SHEET, (b) adhesive layer being made of polyurethane film, and the tissue layer that (c) is made of the fabric comprising aromatic polyamide fibre.The product prepared the invention also discloses the product comprising the thermoplastic composite lamilate or by the thermoplastic composite lamilate.

Description

Thermoplastic composite lamilate and product prepared therefrom

Technical field

The utility model is related to the thermoplastic composite lamilates with improved adhesive property and improved impact resistance And product prepared therefrom.

Background technology

Recently, polycarbonate resin has been widely used as the shell or protective cover of luggage case and Electrical connections, this It is attributed to durability, intensity, aesthetic appearance and the light weight of makrolon.In the sports products for requiring higher impact resistance In some applications of industrial products, including the POLYCARBONATE SHEET as shell and the enhancing that is made of aromatic polyamide fibre The composite laminated body of tissue layer seemingly good solution.But an existing technical problem is aromatic polyamide fibre Dimension is surface inactive, especially for POLYCARBONATE SHEET, POLYCARBONATE SHEET and the fabric being made of aromatic polyamide fibre Between adhesion strength it is insufficient, the problem of corresponding composite laminated body shows poor impact resistance and layering.For packet The composite laminated body of the fabric formed containing POLYCARBONATE SHEET and by aromatic polyamide fibre have improved adhesive property and The technical solution of improved impact resistance still has demand.

Utility model content

The utility model provides a kind of thermoplastic composite lamilate, it is characterised in that includes sequentially：

(a) top layer being made of at least a piece of POLYCARBONATE SHEET,

(b) adhesive layer being made of polyurethane film, and

(c) tissue layer being made of the fabric comprising aromatic polyamide fibre,

Wherein,

The tissue layer (c) has first surface and second surface, and

The adhesive layer (b) is incorporated into the first surface of the top layer (a) and the tissue layer (c).

In one embodiment, the aromatic polyamide fibre include poly(p-phenylene terephthalamide) homopolymer, Poly(p-phenylene terephthalamide) copolymer, poly homopolymer, poly are total Polymers, polysulfonamide homopolymer or polysulfonamide copolymer.

In one embodiment, the overall thickness of the thermoplastic composite lamilate be 0.2mm to 10 mm or 0.3mm extremely 5mm or 0.5mm to 3mm.

In one embodiment, the POLYCARBONATE SHEET for forming the top layer (a) is by before aromatic bisphenols and carbonic ester Aromatic copolycarbonate piece made from body；The aromatic bisphenols include：Bis- (4- hydroxyphenyls) propane of 2,2-, bis- (4- hydroxyphenyls) Bis- (4- hydroxyl -3,5- 3,5-dimethylphenyls) propane of bis- (4- hydroxyphenyls) ethane of methane, 1,1-, 2,2-, 4,4' dihydroxy diphenyl, Bis- (4- hydroxyphenyls) cycloalkane, bis- (4- hydroxyphenyls) thioethers, bis- (4- hydroxyphenyls) sulfoxides, bis- (4- hydroxyphenyls) sulfones, bis- (4- oxybenzenes Base) ether, bis- (4- hydroxyphenyls) ketone, hydroquinone, resorcinol or catechols；And the thickness of the POLYCARBONATE SHEET is 0.1mm to 3mm or 0.15mm to 1mm.

In one embodiment, the polyurethane film for forming the adhesive layer (b) includes thermoplastic polyurethane and described The thickness of polyurethane film be 50 μm to 500 μm or 100 μm to 300 μm.

In one embodiment, the fabric for forming the tissue layer (c) has 20g/m²To 660g/m²Surface density.

In one embodiment, the fabric for forming the tissue layer (c) also includes adhesive aid.

In one embodiment, the thermoplastic composite lamilate is by being selected from hot pressing, hot compression molding, autoclave It is prepared by the method for molding and biobelt hot melt compacting.

The thermoplastic composite lamilate of the utility model, it is characterised in that also include：

(d) the second adhesive layer being made of polyurethane film, and

(e) bottom being made of at least a piece of POLYCARBONATE SHEET,

Wherein,

Second adhesive layer (d) is incorporated into the second surface of the bottom (e) and the tissue layer (c),

The polyurethane film for forming second adhesive layer (d) is different with the polyurethane film for forming the adhesive layer (b) Or it is identical, and

The POLYCARBONATE SHEET for forming the bottom (e) is different with the POLYCARBONATE SHEET for forming the top layer (a) or phase With.

The utility model additionally provides the product of the thermoplastic composite lamilate comprising the utility model, it is characterised in that institute The product stated is the shell or protective cover, the shell of luggage case, the decorative element of automobile control panel or cunning of electronic apparatus Snow slab panel.

Description of the drawings

Fig. 1 shows the expansion side view of an embodiment of the thermoplastic composite lamilate 100 of the utility model, tool There is layer structure below：(a) top layer 11, (b) adhesive layer 12 and (c) tissue layer 13, wherein the tissue layer (c) has first Surface 131 and second surface 132, the adhesive layer (b) are incorporated into the first surface of the top layer (a) and the tissue layer (c).

Fig. 2 shows the expansion side view of an embodiment of the thermoplastic composite lamilate 200 of the utility model, tool There is layer structure below：(a) top layer 11, (b) adhesive layer 12, (c) tissue layer 13, (d) second adhesive layer 21 and (e) bottom 22, wherein there is the tissue layer (c) first surface 131 and second surface 132, the adhesive layer (b) to be incorporated into the top layer (a) and the first surface of the tissue layer (c), second adhesive layer (d) are incorporated into the bottom (e) and the tissue layer (c) second surface.

Specific implementation mode

If do not otherwise indicated, all publications, patent application, patent and other references that this specification is previously mentioned Its entirety is expressly incorporated in this specification for all purposes, as having been fully disclosed herein by document by quoting.

Unless otherwise defined, all technologies for using of this specification and scientific terminology have with belonging to the utility model The normally understood identical meaning of those of ordinary skill institute in field.It in case of conflict, will be in this specification Subject to definition.

Unless otherwise indicated, all percentage, number, ratio etc. be all by weight.

As used in this specification, " by ... preparing " this term is synonymous with term "comprising".In this specification Used, term "comprising", " comprising ", " having ", " containing " or their any other modification are intended to covering nonexcludability Inclusion.For example, composition, technique, method, product or instrument comprising a series of elements are not necessarily limited to those elements, But may include not expressly listed other elements either this composition, technique, method, product or instrument it is intrinsic Other elements.

Conjunction " by ... form " do not include any unspecified element, step or ingredient.It is wanted if it is in right It asks in book, other than impurity usually adjoint with it, this conjunction will be such that claims close to cited material. When " by ... form " in the subordinate clause of this phrase characteristic for appearing in claims rather than and then before prelude Timesharing is limited only within element listed in the subordinate clause；Other elements are not precluded except the entirety of claims.

Conjunction " substantially by ... form " is for limiting composition, method or instrument comprising in addition to those words Material, step, feature, component except being discussed on face or element, on condition that these additional material, step, feature, components Or element does not influence the basic and novel feature of claimed utility model substantially.Term is " substantially By ... form " be located at "comprising" and " by ... form " between intermediate range.

Term "comprising" include by " substantially by ... form " with " by ... form " the implementation covered of term Scheme.Similarly, term " substantially by ... form " includes the embodiment that term " consist of " covers.

When quantity, concentration or other values or parameter are as range, preferred scope or preferred upper limit value and preferred lower limit value List when providing, it should be understood that specifically disclose any pair of range limit or preferred value and range lower limit or preferred value institute All ranges formed, no matter whether range is individually disclosed.For example, when enumerating the range of " 1-5 ", disclosed range is answered It is interpreted as including " 1-4 ", " 1-3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc..Numerical value is enumerated in the present specification When range, unless otherwise indicated, the range be intended to include range endpoint and within the scope of all integers and score.

When describing the endpoint of value or range using term " about ", present disclosure should be read to include the specific of meaning Value or endpoint.

In addition, except non-clearly there is an opposite explanation, "or" refers to the "or" of inclusive, rather than exclusive "or".For example, Any one condition for all meeting A "or" B below：A is true (or presence) and B is false (or being not present), A is false (or do not deposit ) and B is true (or presence) and A and B is true (presence).

In the specification and/or claims of the utility model, term " homopolymer " refers to by a kind of repetitive unit It polymerize obtained polymer.For example, term " poly(p-phenylene terephthalamide) homopolymer " refers to substantially repeating list by a kind of The polymer of first " poly P phenylene diamine terephthalamide " composition.

As used in this specification, term " copolymer " refers to comprising obtained by two or more comonomers The polymer of copolymerization units." dimer " refers to the polymer being substantially made of the unit of two kinds of comonomer-deriveds, and " trimer " refers to the copolymer being substantially made of the unit of three kinds of comonomer-deriveds.

As used in this specification, the definition of term " fiber " (fiber) is the object of relatively flexible elongation, is had The height ratio of length and the width perpendicular to the cross section of the length.Fiber cross section can be any shape, such as round, flat Flat shape or ellipse, but it is generally circular.Fiber cross section can be it is solid or hollow, it is preferably solid.In this explanation In book, term " long filament " (filament) or " continuous filament yarn " may be used interchangeably with term " fiber ".Single fiber can only by One root long silk is formed or is formed by plurality of threads.The fiber only formed by a root long silk is referred to as " monofilament " in the present specification Fiber (" single-filament " fiber) (" monofilament " fiber), and existed by the fiber that plurality of threads is formed It is known as " multifilament " fiber in this specification.As used in this specification, term " yarn " (yarn) is defined as by plurality of fibers The single cord of composition.

For the diameter of fiber usually with the line density characterization for being referred to as " danier " or " dtex " (" dtex "), " danier " is 9, The grammes per square metre of 000 meter of fiber, and " dtex " is 10, the grammes per square metre of 000 meter of fiber.

As used in this specification, " layer " is used to describe the general plane of POLYCARBONATE SHEET, polyurethane film and the fabric Arrangement.

In the present specification, term " film " and " piece " are used to refer to the continuous and thin flat structure with uniform thickness.It is logical Often, " film " can be with 1 μm -500 μm of thickness；And " piece " is then thicker, can have the thickness of no more than about 10mm.

The embodiments of the present invention described in the utility model content part of the utility model include this explanation Any other embodiment described in book, and can combine in any way, and subject description in embodiments is not only It is related to the thermoplastic composite lamilate of the utility model, further relates to product prepared therefrom.

The utility model is described in detail as follows.

POLYCARBONATE SHEET

In the present invention, the POLYCARBONATE SHEET for being suitable as the top layer (a) or the bottom (e) includes poly- carbonic acid Ester resin；Or it is substantially made of polycarbonate resin；Or it is made of polycarbonate resin；Or it is standby by polycarbonate resin. In some embodiments, the POLYCARBONATE SHEET for being used as the top layer (a) or the bottom (e) includes aromatic copolycarbonate Resin；Or it is substantially made of aromatic polycarbonate resin；Or it is made of aromatic polycarbonate resin；Or by fragrant adoption It is prepared by carbonate resin.

Aromatic polycarbonate resin used in this specification by aromatic bisphenols and carbonate precursor by solwution method or Fusion method is made, such as reacting or handed over by the ester of aromatic bisphenols and diphenyl carbonate by aromatic bisphenols and phosgene Change those of preparation.A variety of aromatic bisphenols are available comprising：Such as 2, bis- (4- hydroxyphenyls) propane of 2- are (that is, bis-phenol Bis- (4- hydroxyl -3,5- 3,5-dimethylphenyls) propane of bis- (4- hydroxyphenyls) ethane of A), bis- (4- hydroxyphenyls) methane, 1,1-, 2,2-, 4,4' dihydroxy diphenyl, bis- (4- hydroxyphenyls) cycloalkane, bis- (4- hydroxyphenyls) thioethers, bis- (4- hydroxyphenyls) sulfoxides, bis- (4- hydroxyls Phenyl) sulfone, bis- (4- hydroxyphenyls) ethers, bis- (4- hydroxyphenyls) ketone etc..Other aromatic bisphenols, for example, hydroquinone, resorcinol, Catechol etc. can also be used for the utility model.Aromatic bisphenols that this specification is mentioned, xenol can be used alone or group It closes and uses.Include for the carbonate precursor in the utility model：Such as carbonyl halide, carbonyl ester, haloformate, light Gas, xenol bishaloformate, diphenyl carbonate, dimethyl carbonate, diethyl carbonate etc..

In one embodiment, the POLYCARBONATE SHEET for being suitable as the top layer (a) or the bottom (e) includes general formula 1 bisphenol A polycarbonate resin, or be substantially made of the bisphenol A polycarbonate resin of general formula 1, or by the double of general formula 1 Phenol A type polycarbonate resins form, or are prepared by the bisphenol A polycarbonate resin of general formula 1：

Wherein, n is the integer of about 50 to about 200.

This kind of bisphenol A polycarbonate (BPA-PC) resin is known, and can easily by bisphenol-A or its spread out Biology is used as primary raw material, is obtained by conventional phosgenation or ester exchange reaction method.Work for being injection moulded and squeezing out Industry BPA-PC has the weight average molecular weight (M of 15,000-50,000_w)。

Suitable polycarbonate resin can be bought from commercial source, such as：Purchased from Covestro'sPurchased from Sabic'sPurchased from Teijin'sPurchased from DSM'sPurchased from Mitsubishi'sAnd purchased from Trinseo's

Above-mentioned polycarbonate resin can be melted, and by air blowing, curtain coating or it is extrusion coated by be processed into sheet material.By It is known to the skilled in the art in the preparation process of POLYCARBONATE SHEET, for brevity, repeats no more in the present specification.

The POLYCARBONATE SHEET for being suitable as the top layer (a) or the bottom (e) can have about 0.1mm each independently To about 3mm, or about 0.15mm is to the thickness of about 1mm.Although such thickness is preferred, but it is to be understood that can also produce Raw other thickness are fallen into meeting special needs within the scope of the utility model.Form the poly- carbon of the top layer (a) Acid esters piece and the POLYCARBONATE SHEET of the composition bottom (e) can be different or identical.The different makrolon Piece can be standby by different polycarbonate resins；It is either standby by identical polycarbonate resin, but it is with different Thickness.In one embodiment, the POLYCARBONATE SHEET for forming the top layer (a) and the bottom (e) has each independently About 0.1mm is to about 3mm, or about 0.15mm is to the thickness of about 1mm.

In another embodiment, the top layer (a) of the thermoplastic composite lamilate of the utility model and bottom (e) be by Identical POLYCARBONATE SHEET composition.

Polyurethane film

In the present invention, the polyurethane film for being suitable as the adhesive layer (b) or second adhesive layer (d) includes Polyurethane；Or it is substantially made of polyurethane；Or it is made of polyurethane；Or it is prepared by polyurethane.In some embodiments, it fits Share make the adhesive layer (b) or second adhesive layer (d) polyurethane film include thermoplastic polyurethane；Or substantially by heat Plastic polyurethane forms；Or it is made of thermoplastic polyurethane；Or it is prepared by thermoplastic polyurethane.

Polyurethane (Polyurethane is abbreviated as PU) refers to containing amido formate (- NHCOO-) structure in main chain High molecular material is two by containing the compound of at least two isocyanates (NCO) functional group and hydroxyl (OH) functional group What first alcohol or polyalcohol were prepared by polycondensation reaction.Common diisocyanate has toluene di-isocyanate(TDI) (TDI), diphenyl-methane Diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4- dicyclohexyl methyl hydrides two Isocyanates (HMDI), poly methylene poly phenyl poly isocyanate (PAPI), benzene dimethylene diisocyanate (XDI) etc..

Thermoplastic polyurethane (Thermoplastic Polyurethane, be abbreviated as TPU) is one kind (AB) n type blocks Linear polymer, A are the polyester or polyether Glycols of high molecular weight (1000-6000), and B is two of the carbons containing 2-12 Alcohol (or being chain extender), the intersegmental chemical constitution of AB chains is typically to use diisocyanate, such as '-diphenylmethane diisocyanate (MDI) it connects.

Suitable polyurethane film can be bought from commercial source, such as：Purchased from BASF'sPurchased from BAYER'sOrPurchased from Huntsman's OrOr purchased from ten thousand China

In the present specification, the polyurethane film for being suitable as the adhesive layer (b) or second adhesive layer (d) can be each From independently having about 50-500 μm, or about 100-300 μm of thickness.Although such thickness is preferred, should manage Solution, can also generate other thickness to meet special needs, but still fall within the scope of the utility model.Form described The polyurethane film of two adhesive layers (d) and the polyurethane film of the composition adhesive layer (b) can be different or identical.It is described not Same polyurethane film can be prepared by different polyurethane；It is either prepared by identical polyurethane film, but it has difference Thickness.

In one embodiment, the polyurethane film for forming the adhesive layer (b) or second adhesive layer (d) is respectively only On the spot there is about 50 μm to about 500 μm, or about 100 μm to about 300 μm of thickness.

In another embodiment, the adhesive layer (b) of the thermoplastic composite lamilate of the utility model or described second Adhesive layer (d) is made of identical polyurethane film.

Fabric

In the present invention, the fabric for being suitable as the tissue layer (c) includes aromatic polyamide fibre, it includes Poly(p-phenylene terephthalamide) homopolymer, poly(p-phenylene terephthalamide) copolymer, poly are equal Polymers, poly copolymer, polysulfonamide homopolymer, polysulfonamide copolymer or their mixture.

Poly(p-phenylene terephthalamide) homopolymer is originated from the equimolar of p-phenylenediamine (PPD) and terephthalyl chloride (TCl) Polymerization.In addition, poly(p-phenylene terephthalamide) copolymer is originated from mixes other the two of up to 10 moles % in p-phenylenediamine Amine and other diacyl chlorides that up to 10 moles % are mixed in terephthalyl chloride, on condition that other diamines and Diacyl chloride does not have the reactive group of interference polymerisation.The example of other diamines except p-phenylenediamine include but It is not limited to：M-phenylene diamine (MPD) or 3,4'- diaminodiphenyl ethers (3,4'-ODA).Other diacyl chlorides except terephthalyl chloride Example include but not limited to m-phthaloyl chloride, 2,6- naphthalenes dimethyl chloride, chloro paraphthaloyl chloride or dichloro terephthaldehyde Acyl chlorides.

As used in this specification, term " contraposition aromatic polyamide " or refer to poly- paraphenylene terephthalamide couple " to fragrant amide " Phenylenediamine homopolymer and copolymer.

Poly homopolymer polymerize from m-phenylene diamine (MPD) with the equimolar of isophthaloyl chloride.In addition, Poly copolymer be originated from other diamines that up to 10 moles % are mixed in m-phenylene diamine (MPD) and Other diacyl chlorides of up to 10 moles % are mixed in benzene diacid chloride, on condition that other diamines and diacyl chlorination Object does not have the reactive group of interference polymerisation.The example of other diamines except m-phenylene diamine (MPD) includes but not limited to：It is right Phenylenediamine or 3,4'- diaminodiphenyl ethers.The example of other diacyl chlorides except isophthaloyl chloride includes but not limited to Paraphthaloyl chloride, 2,6- naphthalenes dimethyl chloride, chloro paraphthaloyl chloride or dichloro paraphthaloyl chloride.

As used in this specification, term " meta-aromatic polyamide " or " fragrant amide " refer to it is poly- between phenyl-diformyl Phenylenediamine homopolymer and copolymer.

Polysulfonamide homopolymer can be originated from diamines such as 4,4' diaminodiphenyl sulfone (p-DDS) or 3,3'- diamino Diphenyl sulphone (DPS) (m-DDS) polymerize with the equimolar of diacyl chloride such as paraphthaloyl chloride or m-phthaloyl chloride.

Polysulfonamide copolymer includes for example originating from diamines such as p-DDS and paraphthaloyl chloride and other diacyl chlorides The copolymer of the mixture of (for example, m-phthaloyl chloride)；And it is originated from diacyl chloride such as paraphthaloyl chloride and diamines Mixture, such as other diamines (for example, p-phenylenediamine or m-phenylene diamine (MPD)) of p-DDS, m-DDS and up to 10 moles % are total to Polymers.

Preferably, it is 3 that polysulfonamide copolymer, which is originated from molar ratio,:1:4 p-DDS, m-DDS and paraphthaloyl chloride.

If this specification uses, term " PSA " refers to polysulfonamide homopolymer and copolymer.

The polymer or copolymer of above-mentioned aromatic polyamide can be existed by solution-polymerized SBR using polymer or copolymer Polymer solvent is spun into fiber for the solution in another solvent of polymer or copolymer.Fibre spinning can be with porous Spinning head is realized by dry spinning, wet spinning or dry-jet wet-spinning (also referred to as air gap spinning), to generate such as the prior art In known multifilament fiber.Then, as needed, the multifilament fiber after conventional technique processing spinning can be used, so as in With clean, dry or heat treatment of fibre, to prepare stable useful fiber.Illustrative dry spinning, wet spinning or Dry-jet wet spinning process United States Patent (USP) No.3,063,966,3,227,793,3,287,324,3,414,645,3,869,430, 3,869,429, it discloses in 3,767,756 and 5,667,743.

The method of aromatic polyamide fibre is prepared in United States Patent (USP) No.4,172,938,3,869,429,3,819, 587, it discloses in 3,673,143,3,354,127 and 3,094,511.Prepare PSA fibers or the copolymer comprising sulfone amine monomers Specific method discloses in Chinese patent discloses No.1389604A.

Aromatic polyamide fibre is also commercially available, such as purchased from Teijin's (Japan) AndPurchased from Unitika'sPurchased from DuPont's WithPurchased from Kolon Industries, Inc.'sPurchased from Kamensk Volokno The SVM of JSC^TMAnd RUSAR^TM.PSA fibers are also commercially available, such as purchased from Shanghai Tanlon Fiber Co., Ltd.s The TANLON of (China)^TM。

The cost of its thinner manufacture of fiber and braiding is more expensive, but per unit weight can generate the benefit of bigger.It examines Consider efficiency and cost, including the line density that has of every one thread of plurality of fibers is about 145dtex to about 6320dtex, or About 440dtex is to about 2640dtex, or about 1100dtex to about 2200dtex.

In the present invention, the fabric for being used as the tissue layer (c) is woven two-way cloth, unidirectional cloth or non-woven fabrics.

As used in this specification, term " non-woven fabrics " refers to via the chopped strand or staple fiber of more random orientations The other any fabric constructions formed, including felt, cushion and other structures.The method for being used to prepare non-woven fabrics is this field In it is known.For example, combing aromatic polyamide staple fiber with networking, needle pierces the net, and spun lacing under pressure, To make staple fiber be bonded to one another.The average length that the aromatic polyamide staple fiber has is about 5mm to about 150mm, and And the average fineness of monofilament is about 0.5dtex to about 10dtex.

In this specification, unidirectional cloth is the web for including the plurality of fibers arranged with substantially parallel unilateral array. In the preferred unidirectional cloth structure of the utility model, the single tape (unitape) of multiple-level stack is formed, wherein for each list On the longitudinal fiber direction of layer, the parallel fibers of each single layer (single tape) and the parallel fibers of each adjacent monolayer orthogonally cloth It sets.Under heat and pressure, the stacking of overlapping fibre layers can be consolidated, to form the integral member of single layer, in this field In be referred to as single-layer, consolidated network (single-layer consolidated network).The method for preparing unidirectional cloth is this It is known in field.In general, unidirectional cloth includes 1 layer to about 6 layers, but may include up to about 10 according to the needs of a variety of applications Layer is to about 20 layers.The number of plies of unidirectional cloth means that its impact resistance is stronger, but it is heavier to also imply that fabric has.

In general, woven two-way cloth is substantially vertical with the more warp thread being longitudinally extended on woven direction and more In the weft yarn of warp thread extending direction (i.e. laterally).It is, for example, possible to use any machine-knitted structure or pattern, such as plain weave, tiltedly Line tissue, satin weave, basket weave etc..By to one square inch or square centimeter in include yarn, including warp thread and The quantity of weft yarn is counted to indicate the weaving density of woven two-way cloth.

Although the woven two-way cloth to being suitable for the utility model does not weave it specific requirement of compactness, preferably tightly Close weaving.However, to avoid extremely closely weaving, the damage of yarn can be caused so as not to extreme close-woven.It is commercially available woven Two-way cloth usually has the weaving densities such as 17 x, 17,20 x, 20 or 34 x 34 per square inch.

In an embodiment of the utility model, the fabric that is used as the tissue layer (c) is woven two-way cloth, unidirectional Cloth or non-woven fabrics.In another embodiment of the utility model, it is woven two-way to be used as the fabric of the tissue layer (c) Cloth.In the another embodiment of the utility model, the woven two-way cloth by identical or different color warp fiber with Weft fiber forms.

In some embodiments, when the POLYCARBONATE SHEET as the top layer (a) is transparent, as tissue layer (c) woven two-way cloth can not only improve the dimensional instability of the thermoplastic composite lamilate, also by described woven double Additional aesthetic effect is assigned to the weaving-pattern and/or color of cloth.It is described in another embodiment of the utility model Woven two-way cloth is made of the warp fiber of different colours with weft fiber.

The thickness of the tissue layer (c) of the utility model according to the final use of the thermoplastic composite lamilate or product and Variation.For example, in the thermoplastic composite lamilate for luggage case shell, the surface density generally allowed for is 500g/m²Extremely 2000g/m², or according to actual needs, or even 2000 g/m can be more than².Correspondingly, it is used as the sheet of the fabric of the tissue layer (c) Body thickness will change corresponding to the quantity of the fibrous layer of the fineness of its single fiber, weaving-pattern and sandwiched unidirectional cloth.

The thickness that woven two-way cloth preferably has be about 0.03mm to about 2mm or about 0.1mm to about 1mm or about 0.15mm to about 0.5mm.

Unidirectional cloth preferably has about 0.01mm to about 1mm or about 0.05mm to about 0.5mm or about 0.075mm to about The preferred thickness of 0.3mm.As used in this specification, single layer unidirectional cloth generally includes at least two layers of bonding course (that is, two lists Band).

The thickness that non-woven fabrics preferably has be about 0.025mm to about 5mm or about 0.05mm to about 2mm or about 0.075mm to about 1mm.

When the fabric of the tissue layer (c) is unidirectional cloth, it usually needs at least 3 layers to 10 layers of unidirectional cloth；When described When the fabric of tissue layer (c) is woven two-way cloth or nonwoven fabric, 1 layer or the woven two-way cloth no more than 10 layers or not generally can be Woven fabric.

In an embodiment of the utility model, the fabric for being used as the tissue layer (c) is at least 1 layer to 10 The fabric of layer, the fabric includes woven two-way cloth, unidirectional cloth, nonwoven fabric or combinations thereof.

In another embodiment of the utility model, the fabric for being used as the tissue layer (c) is 2 layers woven two-way Cloth, and sandwich among described 2 layers of woven two-way cloth at least 1 layer to 10 layers of unidirectional cloth.

In the another embodiment of the utility model, the fabric for being used as the tissue layer (c) is 1 layer woven two-way Cloth.

In one embodiment, the thickness of the tissue layer (c) of the thermoplastic composite lamilate of the utility model is about 0.01mm to about 5mm or about 0.05mm to about 2mm or about 0.1mm to about 1 mm.

In another embodiment, the tissue layer (c) for being used for the thermoplastic composite lamilate of the utility model has about Thickness within the scope of 0.05mm to about 1.0mm.

In one embodiment, the surface density of the tissue layer (c) of the thermoplastic composite lamilate of the utility model is about 20g/m²To about 660g/m²Or about 100g/m²To about 580g/m²Or about 180g/m²To about 500g/m²。

In the present invention, the fabric for being used as tissue layer (c) can also include adhesive aid, for improving fabric and top Adhesive property between layer (a) or the POLYCARBONATE SHEET of bottom (e).Suitable adhesive aid is selected from silane, epoxides and different Cyanate；It is preferred that adhesive aid is silane.

Silane suitable for the utility model can be commercially available acquisition, such as γ-trimethoxy silane methacrylic acid third Ester (A-174), γ-glycidol ether propyl trimethoxy silicane (A-187), β-(3,4- epoxies Butylcyclohexane) ethyl trimethoxy silane (A-186), γ mercaptopropyitrimethoxy silane (A- 189), N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane (Silquest A-1120), γ-carbamyl propyl front three Oxysilane (A-1524) or γ-trimethoxy silane propyl isocyanate (A-link 35), it is aforementioned Silane is manufactured by Mai Tu high performance materials company (Momentive Performance Material Co.).

In the utility model, the fabric as tissue layer (c) can be prepared by method comprising the following steps：I) it will apply Cloth composition is applied on untreated fabric and ii) temperature in the range of between environment temperature to about 220 DEG C It is lower dry moist through handling fabric about 1 minute to about 60 minutes.

The coating composition used in the utility model contains adhesive aid and solvent, wherein the solvent can be water, have Or mixtures thereof solvent.The example of suitable organic solvent includes methanol, ethyl alcohol, butoxy ethanol, normal propyl alcohol, isopropyl Alcohol, n-butanol, isobutanol, 2- butanol, ether, n-butyl ether, tetrahydrofuran, formic acid, acetic acid, toluene or dimethylbenzene.

Suitable applying method includes but not limited to impregnate, impregnate, spray or combinations thereof.

In one embodiment, the fabric of tissue layer (c) is prepared by method comprising the following steps：It will be without place The fabric of reason is immersed in the coating composition containing adhesive aid and solvent；Drying is most to remove at ambient temperature Solvent；And optionally in an oven in the range of about 50 DEG C to about 250 DEG C at a temperature of be further dried.

Soaking time is not particularly limited, premise is that fabric is substantially immersed in coating composition.Implement at one In scheme, soaking time is about 0.05 hour to about 18 hours, is preferably from about 0.1 hour to about 12 hours, is even more preferably about 0.2 Hour was to about 8 hours.Soaking temperature is about 10 DEG C to about 40 DEG C, is preferably environment temperature.

Oven drying temperature is about 50 DEG C to about 250 DEG C, is preferably from about 70 DEG C to about 150 DEG C.The oven drying time is about 0.5 minute to about 1.5 hours, preferably from about 1 minute to about 1 hour.

In one embodiment, the fabric for being used as tissue layer (c) in the present invention includes adhesive aid, Yi Jisuo It is γ-glycidol ether propyl trimethoxy silicane to state adhesive aid.

In yet another embodiment, it is processed fabric to be used as tissue layer (c), it includes the amount of adhesive aid, with It is about 0.1-10 weight %, or about 0.1-5 weight % through handling the total weight of fabric.

The preparation of thermoplastic composite lamilate

In some embodiments of the utility model, the thermoplastic composite lamilate 100 includes sequentially：(a) Top layer 11, (b) adhesive layer 12 and (c) tissue layer 13, wherein the tissue layer (c) has first surface 131 and second surface 132, and the adhesive layer (b) is incorporated into the first surface of the top layer (a) and the tissue layer (c), as shown in Figure 1.

In other embodiments of the utility model, as shown in Fig. 2, the thermoplastic composite lamilate 200 is successively Include sequence：(a) top layer 11, (b) adhesive layer 12, (c) tissue layer 13, (d) second adhesive layer 21 and (e) bottom 22, wherein institute Stating tissue layer (c), there is first surface 131 and second surface 132, the adhesive layer (b) to be incorporated into the top layer (a) and described The first surface of tissue layer (c), and second adhesive layer (d) is incorporated into the of the bottom (e) and the tissue layer (c) Two surfaces.

When be used to describe the structure of thermoplastic composite lamilate in the present specification, oblique line "/" is used to will be each only Vertical layer layer adjacent thereto separates.Therefore, the structure of the thermoplastic composite lamilate of the utility model may be expressed as (a)/ (b)/(c) or (a)/(b)/(c)/(d)/(e).

In the present invention, the method for preparing thermoplastic composite lamilate is not particularly limited, and it can be with It is any conventional known method in the art.It is used to prepare the suitable of the thermoplastic composite lamilate of the utility model Method includes hot pressing, hot compression molding, autoclave molding, biobelt hot melt compacting (double-belt hot melt pressing).The technological parameter of the thermoplastic composite lamilate of the utility model, such as temperature, pressure are used to prepare with timely Between, generally depend on the material and preparation method of POLYCARBONATE SHEET, polyurethane film and fabric.Those skilled in the art can be with Correspondingly determine suitable technological parameter.

In one embodiment, the thermoplastic composite lamilate of the utility model is standby by hot pressing.

Hot pressing can usually carry out under following temperature, if the temperature is at least than forming the adhesive layer (b) and depositing Second adhesive layer (d) polyurethane film fusing point it is high, and the temperature unlike the top layer (a) and if there is The fusing point of POLYCARBONATE SHEET of the bottom (e) exceed 20 DEG C or more.

In one embodiment, hot pressing carries out being at about 100 DEG C to about 300 DEG C or about 150 DEG C to about 250 DEG C At a temperature of；Under pressure in the range of about 0.2MPa is to about 17.4MPa or about 0.5MPa to about 5MPa；And about 0.5 point In 40 minutes or about 1 minute to the about 20 minutes times of Zhong Zhiyue.

After hot pressing, the thermoplastic composite lamilate of the utility model usually has about 0.2mm to about 10mm or about The overall thickness of 0.3mm to about 5mm or about 0.5mm to about 3mm.The overall thickness of the thermoplastic composite lamilate of the utility model can With by being used as the POLYCARBONATE SHEET of the top layer (a) and/or the bottom (e) and as the fabric of the tissue layer (c) Thickness in monolayer adjusted with its number of plies.

The adhesive property of the thermoplastic composite lamilate of the utility model can by between tissue layer (c) and top layer (a), Or in the presence of the second adhesive layer (d) and bottom (e), peel strength between tissue layer (c) and bottom (e) is evaluated. Adjacent layer is peeled away if necessary to numerical value larger peel strength, it means that the adhesive property between these layers is preferable. As used in this specification, term " peel strength " refers to by cutting separation the top layer (a) or the bottom from tissue layer (c) Layer (e), is tested according to ASTM D903 standards.

The impact resistance of the thermoplastic composite lamilate of the utility model is according to ASTM D5420 standards, by with again Hammering blow thermoplastic composite lamilate, the intermediate value failure energy for making lamilate sample burst is evaluated.

In view of the simplification of cost and preparation process, in the present invention, when the second adhesive layer (d) is deposited with bottom (e) When, top layer (a) is preferably identical with the POLYCARBONATE SHEET of bottom (e).

Optionally, other extra plays can be applied to the thermoplastic composite lamilate of the utility model, for example, ultraviolet light Layer of protective material can be applied to the top of the top layer (a).

Based on excellent interlaminar bonding performance and impact resistance, including the thermoplastic composite lamilate of the utility model Product, the product being substantially made of the thermoplastic composite lamilate of the utility model, by the thermoplastic composite of the utility model The product of lamilate composition or the product prepared by the thermoplastic composite lamilate of the utility model have the structural integrity of height Property.

The product of the utility model can be used as the shell or protective cover, the shell of luggage case, automobile of electronic apparatus The decorative element or skis panel of control panel.

The example of electronic apparatus includes laptop computer, tablet computer, mobile phone, E-book reader, portable Game station, portable media player or digital camera.The example of mobile phone include but not limited to flip phone, Sliding cover type mobile phone, radio telephone, cellular phone, smart phone etc..

In one embodiment, the product of the utility model is the shell or protective cover of electronic apparatus.

In another embodiment, the product of the utility model is the shell of luggage case.

Without being further described, it is believed that those skilled in the art can fully utilize this reality using description above With novel.Therefore, following Examples should be considered merely as being illustrative, rather than limit in the disclosure in any way Hold.

Embodiment

Abbreviation " E " representative " embodiment ", and " CE " representative " comparative example ", subsequent digital representation prepare the thermoplastic composite The serial number of lamilate example.All embodiments are prepared and are tested with comparative example in a similar way.

Material

POLYCARBONATE SHEET (PC1)：Trade name purchased from SABIC isThe POLYCARBONATE SHEET of 8B35, width are About 100cm, thickness are about 0.5mm, and Vicat softening temperatures are 160 DEG C, and surface density is about 592g/m²。

POLYCARBONATE SHEET (PC2)：Trade name purchased from SABIC isThe POLYCARBONATE SHEET of 8B35, width are About 100cm, thickness are about 0.175mm, and Vicat softening temperatures are 160 DEG C, and surface density is about 220g/m²。

Fabric (U1)：1420 daniers by poly(p-phenylene terephthalamide) yarn (It is purchased from DuPont) the plain prepared as warp thread and weft yarn, weaving density are 7 x, 7 yarn/cm², and its surface density is About 200g/m², it is purchased from Jiangsu Tianniao High Tech.Co..

Fabric (U2)：1200 daniers (1334dtex) by poly yarn ( White is purchased from DuPont) twill that is prepared as warp thread and weft yarn, weaving density is 9 x, 9 yarn/cm², and its Surface density is about 245g/m², it is purchased from Chomarat Co..

Adhesive layer (B1)：Trade name purchased from BASF isThe polyurethane film of SP9324, width are about 1m, thickness are about 0.2mm, and softening temperature is more than 150 DEG C and thermal degradation temperature is higher than 230 DEG C.

Adhesive layer (B2)：By Du PontThe vinyl-vinyl acetate copolymer of the anhydride modification of 21E533 manufactures Film, width are about 50cm, and thickness is about 0.2mm, and fusing point is 83 DEG C and highest processing temperature is 260 DEG C.

Adhesive aid (S)：γ-glycidyl ether oxygen propyl trimethoxy silicane (No. CAS：2530-83-8),A-187 is purchased from Mai Tu high performance materials company.

Coating composition (CC)：Prepared by being uniformly mixed by 25g adhesive aids (S), 2.5g acetic acid and 225g water solution.

The preparation of the thermoplastic composite lamilate of E1-E5 and CE1-CE10

Step A. fabric treatings

Piece of fabric (15cm × 15cm) is immersed at ambient temperature in coating composition CC (about 250-450mL) Last about 30 minutes, it is removed from coating composition then, hangs the wet fabric at ambient temperature until not having liquid Until dripping, then puts it into the baking oven that temperature is 80 DEG C and persistently dry about 60 minutes, the number of treated fabric It is listed in Table 1 below.Its adhesive aid content is the weight through being obtained alleged by processing fabric that will be dried, and subtracts the fabric original weight, It obtains again divided by through handling the weight of fabric.

Table 1

Step B. hot pressing

Thermoplastic layer's zoarium of embodiment E1-E5 and comparative example CE1-CE10 is used equipped with mold by hot pressing (by two pieces The stainless steel plate of 35cm x 35cm x 1.5cm forms) hot press (being made by PHI) prepare.

POLYCARBONATE SHEET for top layer (a) and bottom (e) and the polyurethane film for adhesive layer and the second adhesive layer and Vinyl-vinyl acetate copolymer film is all cut into the square of 15cm x 15cm, and ruler identical as what it is as tissue layer (c) Very little fabric and two release papers (35cm x 35cm) mode as described below stack.

First, mold is preheated to 190 DEG C in hot press.After hot press takes out mold, mold is opened, and will top Plate is placed on one side.First release paper is placed on substrate, the POLYCARBONATE SHEET that will subsequently function as top layer (a) is placed on mold Center.Then, according to the independent stratum for each lamilate sample specified in table 2-4, by adhesive layer (b), it is used as tissue layer (c) Fabric, the second adhesive layer (d) and placed in order as the POLYCARBONATE SHEET of bottom (e).These layers are placed in position Prefabricated component is obtained afterwards, second release paper (35cm x 35cm) is placed on above the prefabricated component, and the top plate of mold is reset With Guan Bi mould.Guan Bi mould is put back in hot press.

Each lamilate sample is in 190 DEG C of pressure hot pressing 10 minutes with 1MPa.After hot pressing, by mold from hot press It takes out, top plate is removed from mold, then removes second release paper.The thermoplastic composite lamilate is moved from mold It removes, is detached with first release paper, and be cooled to environment temperature.

Test method

Thickness measure：The thickness of lamilate sample is measured with micrometer caliper.Each sample measures 6- in different positions 10 times, average gained measured value is simultaneously reported in table 2-4.

Intermediate value failure energy is tested：The impact resistance of the thermoplastic composite lamilate of the utility model is so that lamilate The intermediate value failure energy of sample burst failure is evaluated.First, each embodiment or comparative example by hot pressing for 14-16 A lamilate sample, then (it is purchased from Han ' s Laser Technology Industry Group with laser cutting machine Co.Ltd., model：P060 it) cuts prepared lamilate sample and obtains the test sample of 14-16 10cm x 10cm.Root According to ASTM D5420 standards, each test sample is placed on sample stage, the impact of a diameter of 15.86mm is placed above sample Head, the weight that selection weight is 3.6kg record the numerical value of the failure energy of each test sample fracture failure to impact experiment, The average value of the numerical value is denoted as the intermediate value failure energy (unit：J), it is listed in table 2.

The improvement of impact resistance (Δ I) is calculated by equation as follows：

Δ I%=[(I_n-I₀)/I₀]x 100

Wherein, I₀It is the intermediate value failure energy and I of reference example_nIt is the embodiment or comparative example being compared with reference example Intermediate value failure energy.

Peel strength test：(it is purchased from Han ' s Laser Technology Industry Group with laser cutting machine Co.Ltd., model：P060 each lamilate sample) is cut, 5 test samples (i.e. the rectangle of 15cm x 25.4mm) are obtained. Each test sample is fixed on specimen holder, and it is the steel plate of 15cm (length) x 25.4mm (width) that specimen holder, which has a block size, The top layer (a) of test sample is bonded to thermosetting epoxy resin on steel plate, and epoxy resin is cured at least 24 hours.

According to 180 ° of peel strength test standards in ASTM D903, useMaterial Testing Machine ( Corporation, model：5567), by the specimen holder for posting test sample be locked in upper clamp and bottom jig (2732-008) it Between and clamp, upper clamp is moved with the load of the speed of 6in/min and 5kN, and the power (N) to removing the layer is remembered Record, and peel strength (unit N/25.4mm) is obtained with the Average peel force ÷ Sample Widths of each test sample, then by 5 The data of test sample are averaged, and are denoted as the mean peel strength of the lamilate and are listed in table 3-4.

The improvement of adhesive property (Δ P) is calculated by equation as follows：

Δ P%=[(P_n-P₀)/P₀]x 100

Wherein, P₀It is the peel strength and P of reference example_nIt is the stripping of the embodiment or comparative example that are compared with reference example From intensity.

Table 2

^a"/" is used to separate on each independent stratum layer adjacent thereto；

^b" * " indicates that the comparative example is the reference example for calculating impact resistance improvement.

According to table 2 as a result, following discussion is apparent.

E1, ce1 and ce2 intermediate value failure energy data between comparison, using vinyl-vinyl acetate copolymer film as Compared with the CE1 lamilates not comprising adhesive layer, the impact resistance of CE2 lamilates improves only the CE2 lamilates of adhesive layer About 12%.However, the E1 lamilates using polyurethane film as adhesive layer are compared with the CE1 lamilates not comprising adhesive layer, E1 layers Fit impact resistance unexpectedly improves about 56%.

Table 3

^a"/" is used to separate on each independent stratum layer adjacent thereto；

^b" * " indicates that the comparative example is the reference example for calculating adhesive property improvement.

According to the result of table 3, following discussion is apparent.

In the lamilate sample of CE3-CE6 and E2-E3, the tissue layer is by Fanglun 1414 Woven plain (i.e. U1) or through processing include adhesive aid plain (i.e. SU1) composition.Compare the layer of CE4 and CE3 Fit peel strength data finds peel strength (for its adhesive property of table note of the ancient Chinese) being somebody's turn to do than CE3 lamilate of CE4 lamilates Value improves only about 25%.Similar adhesive property improves also can be by comparing between CE6 and the lamilate of CE5 or the layer of E3 and E2 Peel strength data between zoarium is proved.It is computed, the value of the peel strength ratio CE5 lamilates of CE6 lamilates carries It is high by about 7%；And the value of the peel strength ratio E2 lamilates of E3 lamilates also improves about 6%.It can be seen that using comprising The fabric of adhesive aid has some effectiveness really as tissue layer for the peel strength for improving thermoplastic composite lamilate.

Compare the peel strength data between the lamilate of CE5 and the lamilate of CE3, finds to include ethane-acetic acid ethyenyl Ester copolymer film then considerably improves about 502% as the peel strength of the CE5 lamilates of adhesive layer.It can be seen that bonding The presence of layer has extremely significant effectiveness for the peel strength for improving thermoplastic composite lamilate.

In addition, compare the lamilate of E2, i.e. a specific embodiment of the thermoplastic composite lamilate of the utility model, with Peel strength data between the lamilate of CE3, discovery include peel strength of the polyurethane film as the E2 lamilates of adhesive layer The value than CE3 lamilate obtains improvement (about 633%) further.So laminated with known thermoplastic composite Body is compared, and the thermoplastic composite lamilate of the utility model is adhesive layer by using polyurethane film, not only to its impact resistance It can be significantly increased (referring to table two), also having to its adhesive property obviously improves.

Table 4

^a"/" is used to separate on each independent stratum layer adjacent thereto；

^b" * " indicates that comparative example is the reference example for calculating adhesive property improvement.

According to table 4 as a result, following discussion is apparent.

In the lamilate sample of CE9-CE10 and E4-E5, the fabric of the tissue layer (c) is by between phenyl-diformyl between gathering Twill (i.e. U2) prepared by phenylenediamine yarn includes that the twill (i.e. SU2) of adhesive aid is formed through processing.Compare E4 Lamilate, i.e. a stripping between specific embodiment, and the lamilate of CE7 of the thermoplastic composite lamilate of the utility model From intensity data, find comprising polyurethane film as adhesive layer E4 lamilates than the CE7 lamilates without adhesive layer bonding Performance improves about 530%.The lamilate of the E5 of adhesive aid will be coated with as adhesive layer and tissue layer using polyurethane, i.e., Another specific embodiment of the thermoplastic composite lamilate of utility model, compared with the peel strength between the lamilate of CE7, It has also been found that the adhesive property of E5 lamilate samples further improves about 630%.

In an embodiment of the utility model, the thermoplastic composite lamilate includes sequentially：

(a) top layer being made of at least a piece of POLYCARBONATE SHEET,

(b) adhesive layer being made of polyurethane film,

(c) tissue layer being made of the fabric comprising aromatic polyamide fibre,

(d) the second adhesive layer being made of polyurethane film, and

(e) bottom being made of at least a piece of POLYCARBONATE SHEET,

Wherein,

The tissue layer (c) has first surface and second surface,

The adhesive layer (b) is incorporated into the first surface of the top layer (a) and the tissue layer (c),

Second adhesive layer (d) is incorporated into the second surface of the bottom (e) and the tissue layer (c), and

The aromatic polyamide fibre includes poly(p-phenylene terephthalamide) homopolymer, poly- paraphenylene terephthalamide to benzene two Amine copolymer object, poly homopolymer, poly copolymer, polysulfonamide homopolymerization Object, polysulfonamide copolymer or their mixture.

Although the utility model is able to explanation and description in typical embodiments, the utility model is not intended to Details shown in being confined to, a variety of improvement and replacement for not departing from the Spirit Essence of the utility model are possible.Pass through as a result, Routine experiment, those skilled in the art can it is contemplated that the utility model disclosed in this specification improvement and equivalent, and institute It is considered as in the spirit and scope of the utility model defined by claims to have these to improve with equivalent.

Claims (11)

1. thermoplastic composite lamilate, it is characterised in that include sequentially：

(a) top layer being made of at least a piece of POLYCARBONATE SHEET,

(b) adhesive layer being made of polyurethane film, and

(c) tissue layer being made of the fabric comprising aromatic polyamide fibre,

Wherein,

The tissue layer (c) has first surface and second surface, and

The adhesive layer (b) is incorporated into the first surface of the top layer (a) and the tissue layer (c).

2. thermoplastic composite lamilate as described in claim 1, it is characterised in that the aromatic polyamide fibre includes poly- Poly P phenylene diamine terephthalamide homopolymer, poly(p-phenylene terephthalamide) copolymer, poly homopolymerization Object, poly copolymer, polysulfonamide homopolymer or polysulfonamide copolymer.

3. thermoplastic composite lamilate as claimed in claim 1 or 2, it is characterised in that the thermoplastic composite lamilate it is total Thickness is 0.2mm to 10mm or 0.3mm to 5mm or 0.5mm to 3mm.

4. thermoplastic composite lamilate as claimed in claim 1 or 2, it is characterised in that the thickness of the POLYCARBONATE SHEET is 0.1mm to 3mm or 0.15mm to 1mm.

5. thermoplastic composite lamilate as claimed in claim 1 or 2, it is characterised in that form the poly- ammonia of the adhesive layer (b) Thickness of the ester film comprising thermoplastic polyurethane and the polyurethane film is 50 μm to 500 μm or 100 μm to 300 μm.

6. thermoplastic composite lamilate as claimed in claim 1 or 2, it is characterised in that form the fabric of the tissue layer (c) With 20g/m²To 660g/m²Surface density.

7. thermoplastic composite lamilate as claimed in claim 1 or 2, it is characterised in that form the fabric of the tissue layer (c) It also include adhesive aid.

8. thermoplastic composite lamilate as claimed in claim 1 or 2, it is characterised in that the thermoplastic composite lamilate is logical The method selected from hot pressing, hot compression molding, autoclave molding and biobelt hot melt compacting is crossed to prepare.

9. thermoplastic composite lamilate as claimed in claim 1 or 2, it is characterised in that the thermoplastic composite lamilate is also Including：

(d) the second adhesive layer being made of polyurethane film, and

(e) bottom being made of at least a piece of POLYCARBONATE SHEET,

Wherein,

Second adhesive layer (d) is incorporated into the second surface of the bottom (e) and the tissue layer (c),

The polyurethane film for forming second adhesive layer (d) is different with the polyurethane film for forming the adhesive layer (b) or phase With, and

The POLYCARBONATE SHEET of the POLYCARBONATE SHEET and the composition top layer (a) that form the bottom (e) is different or identical.

10. product, it is characterised in that the product includes the thermoplastic composite lamilate as described in claim 1-9.

11. product as claimed in claim 10, it is characterised in that the product is shell or the protection of electronic apparatus Cover, the shell of luggage case, the decorative element of automobile control panel or skis panel.