CN204172454U

CN204172454U - Thermoplastic composite lamilated body and the goods manufactured by it

Info

Publication number: CN204172454U
Application number: CN201420287591.0U
Authority: CN
Inventors: 杜敏; 黎学东; 宋涛
Original assignee: EI Du Pont de Nemours and Co
Current assignee: DuPont Safety and Construction Inc
Priority date: 2014-05-30
Filing date: 2014-05-30
Publication date: 2015-02-25
Anticipated expiration: 2024-05-30

Abstract

The utility model relates to the goods that thermoplastic composite lamilated body is manufactured by it.Described thermoplastic composite lamilated body comprises successively: the top layer that (a) is made up of at least one thermoplastic film; (b) first tack coat; C tissue layer that () is made up of the fabric comprising aromatic polyamide fibre and surfactant; (d) second tack coat; And the bottom that (e) is made up of at least one thermoplastic film; The mean peel strength comparison of wherein said thermoplastic composite lamilated body improves 25% or more than the mean peel strength of lamilated body.The invention also discloses the goods comprising described thermoplastic composite lamilated body or manufactured by described thermoplastic composite lamilated body, wherein said goods are shell or the protective cover of mobile electronic device.

Description

Thermoplastic composite lamilated body and the goods manufactured by it

Technical field

The utility model relates to the thermoplastic composite lamilated body with high bonding strength, and by its manufacture can be used for the shell of mobile electronic device or the goods of protective cover.

Background technology

By thermosetting resin and the shell or the protective cover that are widely used as sport-specific products, industrial products and Electrical and Electronic equipment with the composite laminated body that the enhancing tissue layer that aromatic polyamide fibre is made forms.In order to obtain the composite laminated body between fabric and matrix with enough bonding strengths, in general, be using thermosetting resin as matrix, fabric is embedded wherein.But the solidification of thermosetting resin will take a long time, therefore make its time production cycle elongated.In order to shorten the production cycle of composite laminated body, a kind of solution uses thermoplastic resin to replace thermosetting resin as matrix.Such as, International Patent Application Publication No. WO2010/036406A2 discloses a kind of method being soaked with the aromatic polyamide fibre compound of thermoplastic resin in advance for the manufacture of can be used as anti-stab and shellproof composite construction.Described thermoplastic resin is selected from ionomer, polyethylene, polyester, polyamide, polyimides, Merlon, polyurethane, polyether-ether-ketone (PEEK) and phenol-modified resin and its combination.

A technological challenge is that aromatic polyamide fibre is surface inactive, especially for thermoplastic polymer if polyamide and Merlon are surface inactive.Because the bonding strength between thermoplastic resin and the fabric be made up of aromatic polyamide fibre is not enough, so thermoplastic composite lamilated body may show poor engineering properties and lamination problem compared with thermoset composite zoarium.

U.S. Patent Application Publication No. 20110171867A1 discloses and is applicable to manufacture rubbery product as the laminated composite of flexible pipe, it comprises the yarn fabric of at least one deck elastomer and one deck aromatic polyamide fibre composition, and the surface-treated with silane of wherein said yarn fabric is to improve its cohesive to elastomer matrix.

Technique scheme to represent all separately towards it for the progress of target.But none technical scheme describes the certain aspects of composite laminated body of the present utility model, and none technical scheme meet the utility model all needs of meeting.

Utility model content

May show poor engineering properties and lamination problem compared with fit with thermoset composite with the fibrous composite laminated body made with aromatic polyamide fibre by thermosetting resin, the utility model is intended to solve this technical problem.The utility model provides thermoplastic composite lamilated body, and it comprises successively:

The top layer that a thermoplastic film that () is made up of polyamide, Merlon or its mixture at least one forms;

B the first tack coat that () is made up of the vinyl-vinyl acetate copolymer of vinyl-vinyl acetate copolymer, chemical modification, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer or its mixture;

C () is by the tissue layer comprising the aromatic polyamide fibre that is made up of poly-(to phenylene terephthalate amine) homopolymers, poly-(to phenylene terephthalate amine) copolymer, poly-(metaphenylene isophthaloyl amine) homopolymers, poly-(metaphenylene isophthaloyl amine) copolymer, polysulfonamides homopolymers, polysulfonamides copolymer or its mixture and form for the fabric of the surfactant in silane, epoxides or isocyanates;

D the second tack coat that () is made up of the vinyl-vinyl acetate copolymer of vinyl-vinyl acetate copolymer, chemical modification, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer or its mixture; And

The bottom that e thermoplastic film that () is made up of polyamide, Merlon or its mixture at least one forms;

Wherein, tissue layer (c) has first surface and second surface;

First tack coat (b) is the first surface being bonded in top layer (a) and tissue layer (c), and the second tack coat (d) is the second surface and the bottom (e) that are bonded in tissue layer (c);

The mean peel strength of the described thermoplastic composite lamilated body measured according to the method for ASTM D6862 is than not having the mean peel strength of equivalent beds's zoarium of described first tack coat (b) and described second tack coat (d) to improve 25% or more using undressed fabric as described tissue layer (c).

Do not have tack coat (b) to compare with the mean peel strength of equivalent beds's zoarium of (d) with using undressed fabric as tissue layer (c), thermoplastic composite lamilated body of the present utility model demonstrates the mean peel strength that improve 25% or more.

Also providing package is containing the goods of thermoplastic composite lamilated body of the present utility model for the utility model, and wherein said goods are shell or the protective cover of mobile electronic device.

accompanying drawing explanation

Fig. 1 shows an embodiment of the present utility model, the enlarged side view of composite laminated body 100, described composite laminated body has with lower-layer structure: (a) top layer 11, (b) first tack coat 12, (c) tissue layer 13, (d) second tack coat 14 and (e) bottom 15, wherein tissue layer (c) has first surface 131 and second surface 132, first tack coat (b) is the first surface being bonded in described top layer (a) and described tissue layer (c), and the second tack coat (d) is bonded in the second surface of described tissue layer (c) and described bottom (e).

Fig. 2 shows the enlarged perspective of composite laminated body sample 200 of the present utility model, and described sample is for peel strength test.Described sample has with lower-layer structure: (a) top layer 21, (b) first tack coat 22, (c) tissue layer 23, (d) second tack coat 24 and (e) bottom 25; And along the strip release liners 26 that edge is on one side placed between described top layer (a) and described first tack coat (b).Shown parallel dotted lines is the line of cut of display test sample.

Detailed description of the invention

Unless otherwise indicated, its full content adds herein by all publications herein, patent application, patent and other bibliography by reference clearly, is entirely disclosed in this article as by them.

Unless otherwise defined, all scientific and technical terminologies used herein have the identical implication usually understood with the utility model one of ordinary skill in the art.In conflict situation, be then as the criterion with the definition of this description.

Unless otherwise directed, whole percentage, number, ratio etc. are by weight.

In this article, term " by ... obtained " be equal to " comprising ".Term used herein " comprises (comprises; comprising) ", " comprising (includes; including) ", " having (has; having) " or " containing (contains, containing) " or its other variant any are intended to cover comprising of non-exclusive.Such as, comprise the composition of a series of key element, technique, method, goods or equipment and be not only confined to these key elements, but also can comprise these compositions, technique, method, goods or equipment clearly do not enumerate or intrinsic other key element.

Conjunction " by ... composition " do not comprise any key element, step or the composition clearly do not enumerated.If in the claims, described conjunction does not comprise making described claim be limited to described material the material do not described, but still comprises the impurity usually relevant to the material described by those.When conjunction " by ... composition " appears at the characteristic of claim, but not when following preamble closely, then it only limits the key element described in this characteristic; Other key elements are not got rid of by from claim entirety.

Conjunction " substantially by ... composition " for definitions section compound, method or equipment; it comprises and also comprise other material, step, feature, component or key element except literal described those materials, step, feature, component or key element, and prerequisite is essential characteristic and the novel features that these other material, step, feature, component or key elements substantially do not affect utility model required for protection.Term " substantially by ... composition " be in " comprising " and " by ... form " between intermediate zone.

Term " comprise " be intended to comprise term " substantially by ... composition " and " by ... form " embodiment that contains.Similarly, term " substantially by ... composition " is intended to comprise the embodiment that term " by ... composition " is contained.

When providing quantity, concentration or other numerical value or parameter with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is interpreted as and specifically discloses by any paired any range limit or preferred value and any range lower limit or preferred whole scope of being formed of value, and no matter whether described scope is disclosed respectively.Such as when describing the scope of " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc.Mentioning range of digital values part, unless otherwise directed, otherwise this scope is intended to comprise its end points and the whole integer be within the scope of this and mark.

When using term " about " to describe value or ends of range point value, described disclosed content should be understood to comprise mentioned occurrence or end value.

, unless specifically stated, otherwise " or (or) " represents " or (or) " of " or (or) " of inclusive instead of removing property in addition.It is one of any that such as condition A "or" B meets below: A is true (or existence) and B is vacation (or not existing), A is false (or not existing) and B is true (or existence), and A and B is true (or existence).

" mol% " or " % by mole " refer to molar percentage.

In description of the present utility model and claims, term " homopolymers " refers to the polymer derived from a kind of repetitive of polymerization.Such as term " poly-(to phenylene terephthalate amine) homopolymers " refers to substantially by the polymer of a kind of repetitive for forming phenylene terephthalate amine.

In this article, term " copolymer " refers to the polymer comprising the copolymerization units (comonomer-derived unit) formed by two or more comonomers (comonomer) copolymerization." bipolymer " refers to the polymer be substantially made up of the unit of two kinds of comonomer-derived, and " terpolymer " represents the copolymer be substantially made up of the unit of three kinds of comonomer-derived.

In this article, term " fiber " (fiber) refers to a kind of slender bodies of relative flexibility, and its length is at least be greater than 10 with the ratio perpendicular to the width of the cross section of this length.Described fiber cross section can be any shape such as circle, pancake or ellipse, but normally circular.Described fiber cross section can be solid or hollow, preferably solid.Single fiber can only by a threads (filament) or formed by plurality of threads.The fiber only formed by a threads is called " individual thread " fiber or " monofilament " fiber herein, and the fiber formed by plurality of threads is called " multifibres " fiber herein.As used herein, term " yarn " (yarn) refers to the sub-thread wire harness be made up of plurality of fibers, can be non-twist (i.e. flat yarn) or have sth. made by twisting.Term " yarn " can be used alternatingly with term " fiber ".

The thickness of fiber characterizes with the line density being called " dawn " or " dtex " usually; " dawn " is the weight (by gram) of 9000 meters of fibers and " dtex " is the weight (by gram) of ten thousand metres fiber.

In this article, " layer " describes a kind of overall arrangement in plane of thermoplastic film, (being total to) polymer film (as described tack coat) or fabric.

The embodiment of the present utility model (comprising any other embodiment described herein) described in utility model content can merge by any way mutually, and in embodiment, composite laminated body of the present utility model is not only suitable for for the description of variable, but also is suitable for the goods obtained by it.

Below describe the utility model in detail.

thermoplastic film

In the utility model, be suitable for the thermoplastic film making top layer (a) or bottom (e) and comprise polyamide, Merlon and its mixture; Or be substantially made up of polyamide, Merlon and its mixture; Or be made up of polyamide, Merlon and its mixture; Or manufactured by polyamide, Merlon and its mixture.

Derived from the fatty polyamide of monoreactant as the copolymer of lactams, aminocarboxylic acid ester or these components, be called AB type polyamide, comprise polyamide 6 (poly-ε-caproamide), polyamide 10 (poly-ω-decyl amide), polyamide 12 (poly-ω-lauramide) with and composition thereof or copolymer.The fatty polyamide prepared by diamines and diacid condensation, be called AABB type polyamide, comprise polyamide 66, polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (nylon 612), polyamide 46 (nylon 46), polyamide 1010 (nylon 1010) and polyamide 1212 (poly-dodecane two acyl dodecamethylene diamine).Also other semiaromatic polyamide composition being AABB type polyamide is also suitable, as polyamide MXD6 (poly-(m xylylene adipamide)), polyamide 6 T (poly-hexamethylene terephthalamide), polyamide DT (poly-(2-methyl pentamethylene terephthalate amine)), polyamide 6 I (polyhexamethylene isophthaloyl amine) or polyamide M5I (poly-(2-methyl pentamethylene isophthaloyl amine)).

In one embodiment, polyamide 6 I/6T, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012 or its blend is comprised for the top layer (a) of the utility model thermoplastic composite lamilated body or the PA membrane of bottom (e).In another embodiment, polyamide 6 I/6T is comprised for the top layer (a) of the utility model thermoplastic composite lamilated body or the PA membrane of bottom (e); Or be substantially made up of polyamide 6 I/6T; Or be made up of polyamide 6 I/6T; Or manufactured by polyamide 6 I/6T.

The commercially available acquisition of various polyamide as herein described, such as, manufactured by E.I.Du Pont Company's (E.I.du Pont Nemours and Company.Inc.) (being abbreviated as hereinafter " Du Pont ") 3462.

In the utility model, be suitable for the Merlon making top layer (a) or bottom (e) is with solwution method or melt method derived from dihydric phenol and carbonate precursor, as by the reaction of dihydric phenol photoreactive gas or by the ester exchange of dihydric phenol and diphenyl carbonate obtained Merlon.Available various dihydric phenol, comprise such as 2,2-two (4-hydroxyphenyl) propane (i.e. bisphenol-A), two (4-hydroxyphenyl) methane, 1, two (4-hydroxyphenyl) ethane, 2 of 1-, two (the 4-hydroxyl-3 of 2-, 5-3,5-dimethylphenyl) propane, 4,4'-dihydroxybiphenyls, two (4-hydroxyphenyl)-cycloalkanes, two (4-hydroxyphenyl) oxide, two (4-hydroxyphenyl) sulfide, two (4-hydroxy-pheny) sulfone, two (4-hydroxyphenyl) sulfoxide, two (4-hydroxyphenyl) ether, two (4-hydroxy-pheny) ketone etc.Other dihydric phenol such as quinhydrones, resorcinol, catechol etc. also can be used for the utility model.The dihydric phenol mentioned herein can be used alone or combinationally uses.Comprise such as carbonylic halide, carbonyl ester, haloformate for carbonate precursor of the present utility model, be in particular phosgene, xenol two haloformate, diphenyl carbonate, dimethyl carbonate, diethyl carbonate etc.

Suitable Merlon can available from commercial sources, as the MAKROLON of Beyer Co., Ltd (Bayer) ^tM, husky uncle's radical innovations Plastics Company (SABIC Innovative Plastics) di Ren company (Teijin) dSM's mitsubishi (Mitsubishi) and the Dow Chemical Company (Dow)

Film forming is processed by blowing painting, cast coat or extrusion coated by above-mentioned polyamide, Merlon and its mixture melt.Because those skilled in the art know the manufacturing process of PA membrane and polycarbonate membrane, so omit its disclosure at this for simplicity.

In one embodiment, in thermoplastic compound of the present utility model, the thermoplastic film as described top layer (a) and described bottom (e) is identical.

With the total weight of thermoplastic composite lamilated body, be about 5 % by weight to about 40 % by weight as described top layer (a) and the combination weight of the thermoplastic film of described bottom (e).

In one embodiment, the thickness of described top layer (a) and described bottom (e) is about 0.01mm to about 1.5mm independently of one another.

tack coat

" tack coat " used herein refers to the polymeric material layer between thermoplastic film and described fabric (c) being positioned at described top layer (a) or described bottom (e), and expects that it can improve the bonding strength between its adjacent layer.Those skilled in the art can be suitable for according to the Material selec-tion of adjacent layer the polymeric material making tack coat.

In the utility model, described first tack coat (b) and described second tack coat (d) comprise vinyl-vinyl acetate copolymer (EVA), the vinyl-vinyl acetate copolymer of chemical modification, ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA) or its mixture independently of one another; Or be substantially made up of the vinyl-vinyl acetate copolymer of vinyl-vinyl acetate copolymer (EVA), chemical modification, ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA) or its mixture; Or be made up of the vinyl-vinyl acetate copolymer of vinyl-vinyl acetate copolymer (EVA), chemical modification, ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA) or its mixture; Or manufactured by the vinyl-vinyl acetate copolymer of vinyl-vinyl acetate copolymer (EVA), chemical modification, ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA) or its mixture.

EVA is the copolymer of ethene and vinyl acetate, and wherein the percentage by weight of vinyl acetate can from about 10 % by weight to about 40 % by weight.The vinyl-vinyl acetate copolymer of chemical modification is preferably the EVA of sour modification, and wherein EVA carries out modification with the acid being selected from maleic acid, itaconic acid and its acid anhydride.

EMAA is the copolymer of ethene and methacrylic acid, and wherein the percentage by weight of methacrylic acid can from about 1 % by weight to about 50 % by weight.

EAA is ethene and acrylic acid copolymer, and wherein acrylic acid percentage by weight can from about 1 % by weight to about 50 % by weight.

Aforementionedly be used as the commercially available acquisition of various polymeric materials of described first tack coat (b) or described second tack coat (d), such as Du Pont manufactures with

In one embodiment, in thermoplastic composite lamilated body of the present utility model, described first tack coat (b) and described second tack coat (d) comprise the vinyl-vinyl acetate copolymer of anhydride modification independently of one another; Or be substantially made up of the vinyl-vinyl acetate copolymer of anhydride modification; Or be made up of the vinyl-vinyl acetate copolymer of anhydride modification; Or by the vinyl-vinyl acetate copolymer manufacture of anhydride modification.In another embodiment, in thermoplastic composite lamilated body of the present utility model, described first tack coat (b) and described second tack coat (d) comprise ethylene-methacrylic acid copolymer independently of one another; Or be substantially made up of ethylene-methacrylic acid copolymer; Or be made up of ethylene-methacrylic acid copolymer; Or manufactured by ethylene-methacrylic acid copolymer.In still another embodiment, be identical as the first tack coat (b) of thermoplastic composite lamilated body of the present utility model and the polymeric material of the second tack coat (d).

In one embodiment, with the total weight of thermoplastic composite lamilated body, the combination weight of described first tack coat (b) and described second tack coat (d) is from about 5 % by weight to about 30 % by weight.

In one embodiment, the thickness of described first tack coat (b) and described second tack coat (d) is about 0.01mm to about 0.5mm independently of one another.

tissue layer (c)

In this article, term " undressed fabric " refers to and will be used for tissue layer (c), but not yet with the fabric of surfactant process.

In the utility model, described undressed fabric comprise by poly-(to phenylene terephthalate amine) homopolymers, poly-(to phenylene terephthalate amine) copolymer, poly-(metaphenylene isophthaloyl amine) homopolymers, poly-(metaphenylene isophthaloyl amine) copolymer, polysulfonamides homopolymers, polysulfonamides copolymer, and composition thereof the fiber that produces.

The p-phenylenediamine (PPD) that poly-(to phenylene terephthalate amine) homopolymers is is 1:1 by mol ratio and paraphthaloyl chloride are polymerized produced.And, poly-(to phenylene terephthalate amine) copolymer is produced by the paraphthaloyl chloride of the p-phenylenediamine (PPD) of other diamines being mixed with no more than 10mol% with other diacid chlorides being mixed with no more than 10mol%, and prerequisite is the reactive group that other diamines described and other diacid chlorides do not have its polymerisation of interference.The example of the diamines except p-phenylenediamine (PPD) includes but not limited to m-phenylene diamine (MPD) or 3,4'-diamino-diphenyl ether.The example of the diacid chloride except paraphthaloyl chloride includes but not limited to isophthaloyl chloride, 2,6-naphthalene diacid chlorides, chlorine paraphthaloyl chloride or dichloro paraphthaloyl chloride.

In this article, term " to fragrant acid amides " refers to poly-(to phenylene terephthalate amine) homopolymers and poly-(to phenylene terephthalate amine) copolymer.

The m-phenylene diamine (MPD) that poly-(metaphenylene isophthaloyl amine) homopolymers is is 1:1 by mol ratio and isophthaloyl chloride carry out being polymerized produced.And, poly-(metaphenylene isophthaloyl amine) copolymer is produced by the isophthaloyl chloride of the m-phenylene diamine (MPD) of other diamines being mixed with no more than 10mol% with other diacid chlorides being mixed with no more than 10mol%, and prerequisite is only other diamines described and other diacid chlorides do not have the reactive group disturbing its polymerisation.The example of the diamines except m-phenylene diamine (MPD) includes but not limited to p-phenylenediamine (PPD) or 3,4'-diamino-diphenyl ether.The example of the diacid chloride except isophthaloyl chloride includes but not limited to paraphthaloyl chloride, 2,6-naphthalene diacid chlorides, chlorine paraphthaloyl chloride or dichloro paraphthaloyl chloride.

In this article, term " a fragrant acid amides " refers to poly-(metaphenylene isophthaloyl amine) homopolymers and poly-(metaphenylene isophthaloyl amine) copolymer.

Polysulfonamides homopolymers can by mol ratio be 1:1 containing sulfuryl diamines such as 4,4'-diamino diphenyl sulfone (p-DDS) or 3,3 '-diamino diphenyl sulfone (m-DDS) carries out being polymerized with diacid chloride such as paraphthaloyl chloride or isophthaloyl chloride and produces.

Polysulfonamides copolymer comprises the copolymer such as generated by the mixture containing sulfuryl diamines such as p-DDS and paraphthaloyl chloride and other diacid chlorides (such as isophthaloyl chloride); With the copolymer formed with the mixture of other diamines (such as p-phenylenediamine (PPD) or m-phenylene diamine (MPD)) containing sulfuryl diamines such as p-DDS, m-DDS and no more than 10mol% by diacid chloride such as paraphthaloyl chloride.

Preferred polysulfonamides copolymer is p-DDS, m-DDS and the paraphthaloyl chloride of 3:1:4 derived from mol ratio.

In this article, term " PSA " refers to polysulfonamides homopolymers and polysulfonamides copolymer.

The polymer of above-mentioned fragrant acid amides or copolymer can use solution spinning to be spun into fiber, and described solution can with the polymerization solvent of this polymer or copolymer or another solvent.Fibre spinning can be carried out dry-spinning, wet spinning or dry-jet wet-spinning (also referred to as air gap spinning) by porous spinneret and produce multifilament, and this is known in the art.Fiber after spinning can as required, uses routine techniques to carry out neutralizing, cleans, dry or to heat this fiber stable with fiber that is practicality to produce.Exemplary dry-spinning, wet spinning and dry-jet wet-spinning method have been disclosed in U.S. Patent number 3063966; 3227793; 3287324; 3414645; 3869430; 3869429; 3767756; In 5667743.

The method of producing aramid fiber has been disclosed in U.S. Patent number 4172938; 3869429; 3819587; 3673143; In 3354127 and 3094511.Manufacture and be disclosed in Chinese patent application publication No. 1389604A and 1631941A derived from containing the PSA fiber of sulfuryl diamine monomer or the concrete grammar of copolymer.

Aramid fiber also can be commercially available, such as, derive from Teijin's (Japan) with derive from Unitika's derive from E.I.deNemours DuPont's (U.S. is hereinafter abbreviated as " DuPont ") with derive from Akzo's derive from Kolon Industries, Inc.'s (Korea S) derive from the SVM of JSC Kamenskvolokno (Russia) ^tMand RUSAR ^tM, derive from the ARMOS of JSC Tver ' khimvolokno (Russia) ^tMdeng.PSA fiber can derive from the TANLON of Shanghai Tanlon Fibre Co., Ltd. (China) ^tM.But aramid fiber is not limited to above-mentioned product.

The thinner cost that it manufactures and weaves of fiber is more expensive, but per unit weight can produce larger benefit.Consider benefit and cost, the line density that the per share yarn comprising plurality of fibers has, preferably from about 200 dawn (220 dtex) to about 3000 dawn (3300 dtex), is more preferably from about 400 dawn (440 dtex) to about 2400 dawn (2640 dtex) and is most preferably from extremely about 2000 dawn (2200 dtex) at about 1000 dawn (1100 dtex).

In the utility model, the fabric as tissue layer (c) can comprise wovenly knits two-way cloth, the unidirectional cloth of multilayer tablet or non-woven fabrics.In this article, described " non-woven fabrics " means, by multiple randomly-oriented any other fabric construction fibroplastic, to comprise felt, pad and other structures.

In an embodiment of the present utility model, the fabric as tissue layer (c) is woven two-way cloth, unidirectional cloth or non-woven fabrics.In another embodiment of the present utility model, the fabric as tissue layer (c) is woven two-way cloth.

Woven two-way cloth has multiple warp thread extending longitudinally on woven direction usually, and is multiplely substantially perpendicular to the weft yarn that the direction of warp thread extends.The woven two-way cloth of any woven construction or pattern can be adopted, such as plain weave, twill-weave, satin weave, basket weave etc.

Although be suitable for woven two-way cloth of the present utility model there is no specific requirement for woven elasticity, but to avoid extremely weaving closely, because it can cause fibre damage.

The weight per unit area of undressed fabric is between about 20g/m ²to about 660g/m ²; Preferably, between about 40g/m ²to about 300g/m ²; More preferably, between about 60g/m ²to about 200g/m ².

In the utility model, the fabric as tissue layer (c) also comprises surfactant.Expect that described surfactant can improve the bonding strength between the thermoplastic film of fabric and top layer (a) or bottom (e).Suitable surfactant is selected from silane, epoxides and isocyanates.

Be applicable to silane of the present utility model and there is general formula as follows:

G _x-((CH ₂) _ysi (OR ¹) _m(OR ²) _n) _kor Si (OR ³) ₄

Wherein G is vinyl, methacrylic acid, dehydration glycerin ether, expoxycyclohexyl, sulfydryl, octanoylthio, sulphur, halogen, amino, ethylenediamine, isobutylamino, aniline, urea or isocyanates;

X is the integer from 1 to 4;

Y is the integer from 0 to 6;

R ¹the alkyl containing 1 to 4 carbon atom or ether;

R ²and R ³containing the alkyl from 1 to 3 carbon atoms independently of one another;

M, n and k are the integers from 1 to 3.

The commercially available acquisition of various silane as herein described, such as γ-(methacryloxypropyl) propyl trimethoxy silicane ( a-174), γ-glycidol ether propyl trimethoxy silicane ( a-187), β-(3,4-epoxycyclohexyethylSiOi alkyl) ethyl trimethoxy silane ( a-186), γ mercaptopropyitrimethoxy silane ( a-189), N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (Silquest A-1120), γ-carbamyl propyl trimethoxy silicane ( a-1524) or γ-NCO propyl trimethoxy silicane ( a-link35), it is manufactured by Mai Tu high performance material company (Momentive Performance Material Co.).

Be applicable to epoxides of the present utility model and include but not limited to phenols glycidol ether compound, aromatic glycidyl ether compounds, glycerine poly epihydric alcohol ether compound, glycidol aminated compounds and alicyclic ring same clan epoxides.

Various epoxides as herein described can be commercially available, and such as, manufactured by Chang Lai chemical company (Nagase Chemical), commodity are called 1, the 3-diglycidyl glycerin ether of EX-313.

Be applicable to isocyanates of the present utility model and include but not limited to hexamethylene diisocyanate (HDI); IPDI (IPDI), 2,4-toluene di-isocyanate(TDI)s (2,4-TDI), 2,6-toluene di-isocyanate(TDI)s (2,6-TDI) and 4,4'-methyl diphenylene diisocyanate (MDI).

Various isocyanates as herein described can be commercially available acquisition, and such as, manufactured by Dow Chemical, commodity are called PAPI ^tMthe MDI of 27.

In one embodiment, the fabric being used as tissue layer (c) in the utility model comprises and is selected from following surfactant: γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-glycidol ether propyl trimethoxy silicane, β-(3,4-epoxycyclohexyethylSiOi alkyl) ethyl trimethoxy silane, γ mercaptopropyitrimethoxy silane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-carbamyl propyl trimethoxy silicane, γ-NCO propyl trimethoxy silicane; Phenols glycidol ether compound, aromatic glycidyl ether compounds, glycerine poly epihydric alcohol ether compound, glycidol aminated compounds, alicyclic ring same clan epoxides; Hexamethylene diisocyanate; IPDI, 2,4-toluene di-isocyanate(TDI)s, 2,6-toluene di-isocyanate(TDI)s and 4,4'-methyl diphenylene diisocyanate.

In one embodiment, the fabric of described tissue layer (c) is used as: i) be applied to by coating composition on undressed fabric to obtain wet fabric by the method preparation comprised the following steps, and ii) at the temperature in room temperature to the scope of about 220 DEG C, dry described wet fabric about 1 minute to about 60 minutes, the amount of wherein said surfactant is about 1 % by weight to about 20 % by weight of the gross weight accounting for described coating composition.

The coating composition used in the utility model contains surfactant and solvent, and wherein said solvent can be water, organic solvent or its mixture.The example of the organic solvent be applicable to comprises methyl alcohol, ethanol, butoxy ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, 2-butanols, ether, n-butyl ether, oxolane, formic acid, acetic acid, toluene, dimethylbenzene.

The applying coating composition be applicable to includes but not limited to dipping to the method on described undressed fabric, soaks and spraying.

In one embodiment, the method by comprising the following steps prepares the fabric of tissue layer (c): be immersed in by undressed fabric in the coating composition containing surfactant and solvent; At room temperature dry with the solvent of vaporizes most; And it is optionally dry further under high temperature in an oven.

Be not particularly limited for soak time, its prerequisite is for be fully immersed in undressed fabric in coating composition.In one embodiment, the time of immersion is little of about 18 hours or little of about 12 hours or little of about 8 hours from about 0.2 from about 0.1 from about 0.05.The temperature of described immersion is from about 10 DEG C to about 40 DEG C, is preferably room temperature.

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

In an embodiment of the present utility model, the amount that the fabric as tissue layer (c) comprises surfactant is account for described fabric gross weight about 0.5 % by weight to about 15 % by weight.

In one embodiment, the weight of described tissue layer (c) is about 30 % by weight to about 90 % by weight of the gross weight accounting for described thermoplastic composite lamilated body.

In one embodiment, in thermoplastic composite lamilated body of the present utility model, the thickness of described tissue layer (c) is from about 0.05mm to about 1.0mm.

preparation thermoplastic composite lamilated body

Thermoplastic composite lamilated body 100 of the present utility model comprises successively: (a) top layer 11, (b) first tack coat 12, (c) tissue layer 13, (d) second tack coat 14, and (e) bottom 15, wherein tissue layer (c) has first surface 131 and second surface 132, first tack coat (b) is the first surface being bonded in top layer (a) and tissue layer (c), and the second tack coat (d) is the second surface and the bottom (e) that are bonded in tissue layer (c), as shown in fig. 1.

In this article, be each different layers is adjacent by "/" the structure that layer separates to describe this composite laminated body.So the structure of thermoplastic composite lamilated body of the present utility model can represent with (a)/(b)/(c)/(d)/(e).

In the utility model, the method preparing thermoplastic composite lamilated body is not particularly limited, and described method can be the known method of any routine in this area.

The method being applicable to prepare thermoplastic composite lamilated body of the present utility model comprises that hot pressing, hot compression are shaping, autoclave molding and biobelt hot melt pressure.

For the preparation of the technological parameter of thermoplastic composite lamilated body of the present utility model, as temperature, pressure and time, depend on material and the preparation method of thermoplastic film, tack coat and fabric.Those skilled in the art correspondingly can determine the technological parameter be applicable to.

In one embodiment, thermoplastic composite lamilated body of the present utility model passes through hot pressing.

Hot pressing usually can at least higher than be used as the first tack coat (b) and the second tack coat (d) polymeric material fusing point and not higher than be used as top layer (a) and bottom (e) thermoplastic fusing point on carry out at the temperature of 20 DEG C.

In one embodiment, from about 100 DEG C to about 250 DEG C, be preferably from about 125 DEG C to about 225 DEG C, be more preferably from the temperature of about 150 DEG C to about 200 DEG C; To the pressure of about 5MPa, hot pressing is being carried out from about 0.5MPa from about 0.2MPa to about 17.4MPa, preferably; And continue about 0.5 minute to about 40 minutes, preferably about 1 minute to about 20 minutes.

Thermoplastic composite lamilated body of the present utility model generally has from about 0.1mm to about 5mm after hot-pressing preferably from about 0.5mm to the gross thickness of about 3mm.The gross thickness of thermoplastic composite lamilated body of the present utility model is by using the thermoplastic film for described top layer (a) and described bottom (a) of various thickness and easily regulating for the fabric of described tissue layer (c).

The bonding strength of thermoplastic composite lamilated body of the present utility model is evaluated by the mean peel strength between described tissue layer (c) and described top layer (a) or between described tissue layer (c) and described bottom (e).If it is higher to need larger power adjacent layer to be peeled away the bonding strength meant between these layers.Term used herein " mean peel strength " refers to the method according to ASTM D6862, by by described top layer (a) or described bottom (e) together with or not together with described adjacent tack coat (b) or (d) from the mean force measured by described tissue layer (c) strip off.This is because during stripping process, described adjacent tack coat (b) or (d) may be attached to the thermoplastic film of described top layer (a) or described bottom (e) or described tissue layer (c).

Consider cost and ease of manufacturing, in the utility model, described top layer (a) is preferably identical with the material of described bottom, and the polymeric material of described first tack coat (b) and described second tack coat (d) is also identical.Therefore, can only can only carry out in the side of described tissue layer (c) the peel strength test of described thermoplastic composite lamilated body.

Do not have described first tack coat (b) to compare with the mean peel strength of equivalent beds's zoarium of described second tack coat (d) with using undressed fabric as tissue layer (c), thermoplastic composite lamilated body display of the present utility model improves the mean peel strength of 25% or more.

Optionally can other layer one or more be coated on thermoplastic composite lamilated body of the present utility model, such as, UV protection material layer can be coated on described top layer (a).

The goods comprising the goods of thermoplastic composite lamilated body of the present utility model, the goods be substantially made up of thermoplastic composite lamilated body of the present utility model, the goods be made up of thermoplastic composite lamilated body of the present utility model or manufactured by thermoplastic composite lamilated body of the present utility model, due to the plunger bond strength of its excellence, therefore there is higher structural intergrity.In addition, compared with thermoset composite zoarium, thermoplastic composite lamilated body of the present utility model does not improve process efficiency (i.e. cost savings) by means of only shortening cycle time, and provides the chance of carrying out as required during application in the future reprocessing.

Goods of the present utility model are suitable for the shell or protective cover of making mobile electronic device, and its mean peel strength is preferably greater than 65N/25.4mm or 85N/25.4mm or 100N/25.4mm or larger.The example of described mobile electronic device comprises palmtop computer, panel computer, mobile phone, electronic reader, game machine, portable electronic device or digital camera.The example of mobile phone (i.e. mobile phone) includes but not limited to clamshell phone, slide phone, radio telephone, cell phone, smart phone etc.

Without the need to further detailed description, believe that those skilled in the art use aforementioned specification can utilize the utility model fully.Therefore, the following examples should be construed as merely illustrative, not limit the utility model by any way.

embodiment

Abbreviation " E " expressions " embodiment " and " CE " expression " comparative example ", in conjunction with numeral thereafter in the example illustrated prepared by described thermoplastic composite lamilated body.All embodiments and comparative example are prepared all in a similar fashion and test.

material

Thermoplastic film (A1): by available from Du Pont the polyamide 6 I/6T film that PA3426 is manufactured by curtain coating; The wide 50cm of film, thick about 0.16mm, and its fusing point is 250 DEG C.

EVA film (B1): by available from Du Pont the vinyl-vinyl acetate copolymer film of the anhydride modification that 30E671 is manufactured by curtain coating; The wide 50cm of film, thick about 0.06mm, and its fusing point is 99 DEG C.

EMAA film (B2): by available from Du Pont the 599 ethylene-methacrylic acid copolymer films manufactured by curtain coating; The wide 50cm of film, thick about 0.06mm, and its fusing point is 98 DEG C.

Undressed fabric (U1): be by warp thread and weft yarn be the twill-weave that poly-(the metaphenylene terephthalate amine) yarn at 1200 dawn (1334 dtex) manufactures fabric ( in vain, can obtain from Du Pont), size: 9 × 9 terminations/cm ², weight per unit area: about 245g/m ², spin purchased from section and strangle extraordinary textile (granary) Co., Ltd.

Undressed fabric (U2): be by warp thread and weft yarn be poly-(to the phenylene terephthalate amine) yarn at 1500 dawn (1670 dtex) manufacture tabby fabric ( can available from Du Pont), size: 7 × 7 terminations/cm ², weight per unit area: 200g/m ², purchased from Jiangsu Tian Niao new and high technology Co., Ltd.

Surfactant (S1): γ-glycidyl ether oxygen propyl trimethoxy silicane (No. CAS: 2530-83-8), a-187, purchased from Mai Tu high performance material company.

Surfactant (S2): glycerine polyglycidyl ether (No. CAS: 13236-02-7), eX-313, purchased from Chang Lai chemical company.

Surfactant (S3): 4,4 '-diphenyl-methane-4,4-vulcabond (No. CAS: 9016-87-9), PAPI ^tM27, purchased from Dow Chemical.

Coating composition (CC1): the solution prepared by 25.3g surfactant (S1), 2.5g acetic acid and 225g water.

Coating composition (CC2): the solution prepared by 8.8g surfactant (S2), 1.52g2-butyl cellosolve, 2.24g dioctyl sodium sulfosuccinate and 387.3g water.

Coating composition (CC3): the solution prepared by 158g surfactant (S3) and 285g toluene.

manufacture the preparation method of the thermoplastic composite lamilated body of embodiment 1-5 and comparative example 1-5

Steps A. fabric treating

By undressed for a slice fabric (15cm × 15cm) at room temperature, to be immersed in coating composition (about 250mL to about 450mL) about 30 minutes, then to take out from coating composition.At room temperature, by hanging described wet fabric about 30 seconds until under there is no fluid drips, to remove excessive coating composition; And/or placement is spent the night with the solvent of vaporizes most to continue drying; And at high temperature dry further by temperature and time specified in table 1.

Table 1

Step B. hot pressing

Stainless steel mould (being made up of two pieces of 35cm × 35cm × 1.5cm corrosion resistant plate) is applied to shaping.The temperature of hot press (being manufactured by PHI) is set to 175 DEG C.Mould is preheated to 175 DEG C in hot press.Take out mould from hot press and open.Then, release liners (Tian Niao new and high technology Co., Ltd provides by Jiangsu, 35cm × 35cm) is put in the base plate of mould with help after hot-pressing, from mould, finally take out the lamilated body prepared.

Thermoplastic film as top layer (a) and bottom (e), the film as the first tack coat (b) and the second tack coat (d) are cut into the square of 15cm × 15cm, and are used as tissue layer (c) available from the treated fabric of steps A and stack with under type.

First, the thermoplastic film as top layer (a) is taped against the center with mould in the first release liners.Then, place the film, the fabric as tissue layer (c), the film as the second bonding tunic (d) that are used as the first tack coat (b) in order and be used as the thermoplastic film of bottom (e), to form the different layers as each lamilated body sample specified in table 2-3.

Preparation for comparative example is then saved two tack coats (b) and (d) and is replaced being used as tissue layer (c) with undressed fabric.When these different layers are placed in position with after obtaining prefabrication, the second release liners (35cm × 35cm) is placed on described prefabrication, and closes described mould.

For the preparation of peel strength sample, after the described prefabrication of acquisition, a release liners (wide 2.54cm and long 20cm) is placed between top layer (a) and the first tack coat (b), and along edge leave a non-lamination area of fritter so that attach it on test machine.

After the assembling of prefabrication, close this mould and put back in hot press, then at 175 DEG C with the pressure hot pressing 10 minutes of 1MPa.After hot-pressing, mould is taken out from hot press; Take away its upper cover from mould, then remove described second release liners.Take out this thermoplastic composite lamilated body from mould, the first release liners is peeled off from it, and is cooled to room temperature.

method of testing

Thickness measure: the thickness measuring lamilated body sample with micrometer callipers pincers.Each sample is measured 6 to 10 times at difference, gets the mean value of acquired results and is reported in table 2-3.

Peel strength test: employing laser cutting machine (Dazu Laser Science & Tech Co Ltd, Shenzhen City (Han ' s Laser), model: P060) and cut each lamilated body sample to obtain 5 tests sample (i.e. the rectangle of 127.0mm × 25.4mm).Fig. 2 is the schematic diagram of the lamilated body sample for peel strength test.

By means of thermosetting epoxy resin adhesive tape, each test sample is fixed on sample fixed head, the steel plate of its to be a chip size be 160mm (L) × 120mm (W), to carry out 90 ° of peel strength tests.The top layer (a) of described test sample is contacted with epoxy ribbons and at 120 DEG C hot pressing 1 little of making this epoxy resin cure.Use material testing machine (by company manufactures, model: 5567) put in position by the sample fixed head being attached with sample, and is clipped in crosshead by (b)-(e) layer of the openend at lamilated body sample.According to the method for ASTM D6862, the speed of crosshead 100mm/min and the load of 5kN, measure and record it and move 90 ° of peel strengths between 60mm.Its mean peel strength records with unit N/25.4mm and lists in table 2-3.

The raising (Δ P) of peel strength: the raising being calculated mean peel strength below by shown equation:

ΔP％＝[(P _n-P ₀)/P ₀]×100

Wherein P ₀for the mean peel strength of reference example; With

P _nfor the mean peel strength of comparative example.

Table 2

^a" * " represents that this comparative example is the reference example improved for calculating peel strength.

^b"/" is used for each different layers and adjacent layer to separate; And "-" expression does not comprise corresponding tack coat (b) or tack coat (d).

According to the result of table 2, it is apparent for below discussing.

The mean peel strength data of CE2 and CE1 both not having tack coat (b) and tack coat (d) are compared, relative to the lamilated body of tissue layer (c) for the CE1 of undressed fabric (U1), tissue layer (c) there is no improvement for the lamilated body of the CE2 of treated fabric (F1).Its result shows that carrying out simple process with surfactant to the fabric be made up of aromatic polyamide fibre can not make the bonding strength between fabric and thermoplastic film improve.

In addition, CE3 is compared to the laminate structure of CE1, the former has extra tack coat (b) and (d), so expect to see that the bonding strength that the lamilated body of CE3 can demonstrate between fabric and the thermoplastic film being used as top layer (a) has some to improve.But compared to the mean peel strength of the lamilated body of CE1, the mean peel strength of CE3 unexpectedly reduces 20%.Its result shows between fabric and thermoplastic film, have the bonding strength raising that extra tack coat can not obtain expectation.

Unexpectedly, compared to the mean peel strength of the lamilated body of CE1-CE3, the thermoplastic composite lamilated body of E1-E4 is by adding extra tack coat (i.e. B1 or B2) and making its mean peel strength significantly improve for tissue layer (c) in the fabric (i.e. F1, F2 or F3) with surfactant process.The remarkable bonding strength provided by thermoplastic composite lamilated body (E1-E4) of the present utility model improves may owing to the synergy between the fabric with surfactant process and the polymeric material for tack coat.In an embodiment of the present utility model, thermoplastic composite lamilated body comprises successively:

The top layer that a thermoplastic film that () is made up of polyamide at least one forms;

B the first tack coat that () is made up of vinyl-vinyl acetate copolymer or the ethylene-methacrylic acid copolymer of chemical modification;

C () is by the tissue layer comprising the aromatic polyamide fibre that is made up of poly-(metaphenylene isophthaloyl amine) homopolymers or poly-(metaphenylene isophthaloyl amine) copolymer and form for the fabric of the surfactant in silane, epoxides or isocyanates;

D the second tack coat that () is made up of vinyl-vinyl acetate copolymer or the ethylene-methacrylic acid copolymer of chemical modification; And

The bottom that e thermoplastic film that () is made up of polyamide at least one forms;

Wherein

Tissue layer (c) has first surface and second surface;

First tack coat (b) is incorporated into the first surface of top layer (a) and tissue layer (c), and the second tack coat (d) is incorporated into second surface and the bottom (e) of tissue layer (c).

Table 3

According to the result of table 3, it is apparent for below discussing.

The mean peel strength data of CE5 and CE4 compared, its result shows that carrying out simple process (i.e. F4) with surfactant to the fabric be made up of aromatic polyamide fibre can not make the bonding strength between fabric and thermoplastic film improve.

In addition, by extra tack coat (b) and tack coat (d) being inserted in the laminate structure of CE4 to form the lamilated body of CE6, really see that the bonding strength between fabric and thermoplastic film has appropriate increase (namely 17%).

By contrast, compared with the mean peel strength of the lamilated body of CE4-CE6, as the lamilated body of the E6 of an embodiment of the present utility model, it is by inserting extra tack coat (b) and tack coat (d) (i.e. B1) and making its mean peel strength improve (about 77%) more significantly for tissue layer (c) in the fabric (i.e. F4) with surfactant process.The significant bonding strength provided by thermoplastic composite lamilated body (E5) of the present utility model improves may owing to the synergy between the fabric with surfactant process and the polymeric material for tack coat.More particularly, significantly improving in E5 may owing to the synergy between the silane in the middle existence of treated fabric (i.e. F4) and the vinyl-vinyl acetate copolymer as the anhydride modification of tack coat.

In an embodiment of the present utility model, thermoplastic composite lamilated body comprises successively:

B the first tack coat that () is made up of the vinyl-vinyl acetate copolymer of chemical modification;

C () is by the tissue layer comprising the aromatic polyamide fibre that is made up of poly-(to phenylene terephthalate amine) homopolymers or poly-(to phenylene terephthalate amine) copolymer and form for the fabric of the surfactant of silane;

D the second tack coat that () is made up of the vinyl-vinyl acetate copolymer of chemical modification; And

Wherein

Tissue layer (c) has first surface and second surface;

First tack coat (b) is the first surface being bonded in top layer (a) and tissue layer (c), and the second tack coat (d) is the second surface and the bottom (e) that are bonded in tissue layer (c).

Although illustrate and describe the utility model in a typical implementation, its intention is not intended to be confined in shown details, because may to have various amendment under spirit of the present utility model and substitute not deviating from.Thus, when those skilled in the art by means of only routine test just can obtain with amendment of the present utility model disclosed herein and etc. simultaneously, then believe all such modifications and to be equivalently included in as defined in the claims within spirit and scope of the present utility model.

Claims

1. a thermoplastic composite lamilated body, is characterized in that comprising successively:

The top layer that the thermoplastic film be made up of polyamide or Merlon at least one forms;

The first tack coat be made up of the vinyl-vinyl acetate copolymer of vinyl-vinyl acetate copolymer, chemical modification, ethylene-methacrylic acid copolymer or ethylene-acrylic acid copolymer;

By the tissue layer comprising the aromatic polyamide fibre that is made up of poly P phenylene terephathalamide homopolymers, poly P phenylene terephathalamide copolymer, poly-metaphenylene isophthaloyl amine homopolymers, poly-metaphenylene isophthaloyl amine copolymer thing, polysulfonamides homopolymers or polysulfonamides copolymer and form for the fabric of the surfactant in silane, epoxides or isocyanates;

The second tack coat be made up of the vinyl-vinyl acetate copolymer of vinyl-vinyl acetate copolymer, chemical modification, ethylene-methacrylic acid copolymer or ethylene-acrylic acid copolymer; And

The bottom that the thermoplastic film be made up of polyamide or Merlon at least one forms;

Wherein

Described tissue layer has first surface and second surface;

Described first tack coat is the described first surface being bonded in described top layer and described tissue layer, and described second tack coat is bonded in the described second surface of described tissue layer and described bottom.

2. thermoplastic composite lamilated body as claimed in claim 1, is characterized in that described thermoplastic film is PA membrane.

3. thermoplastic composite lamilated body as claimed in claim 1, is characterized in that the gross thickness of described thermoplastic composite lamilated body is from 0.1mm to 5mm.

4. thermoplastic composite lamilated body as claimed in claim 1, is characterized in that the weight per unit area of described undressed fabric is from 20g/m ²to 660g/m ².

5. goods, is characterized in that comprising thermoplastic composite lamilated body as claimed in claim 1, and wherein said goods are shell or the protective cover of mobile electronic device.