CN100535048C - Block copolymer compositions for overmolding any nylon - Google Patents

Abstract

A thermoplastic elastomer (TPE) for overmolding (OM) a nylon substrate with an overmolded layer consists essentially of an inert filler, a plasticizer, preferably a mineral oil, and chosen combinations of ingredients from the following: (i) a functionalized ''high rubber'' SHDS (styrene-hydrogenated diene-styrene) having a functionality of 1%, the ''small end blocks'' together present in an amount in the range from about 8-25% by weight; (ii) hydrogenated SDS or SHDS block copolymer having polystyrene endblocks and a polymerized vinyl aromatic monomer in the poly(conjugated diene) midblock, the polystyrene endblocks together present in an amount in the range from 20-30% by weight of the block copolymer, excluding weight of the polystyrene in the polydiene midblock; (iii) a functionalized ''high rubber'' SHDS having a functionality of >1% but <2%, the ''small end blocks'' together present in an amount in the range from about 8 -25% by weight; (iv) from 0-30% by weight of the composition, of a functionalized polyolefin (F3), the olefin having from 2 to 4 carbon atoms; (v) from 0 -15% by wt of the composition, of a hydrogenated nonfunctionalized hydrogenated polystyrene-poly(conjugated diene)-polystyrene (SHDS) block coplymer; and, (vi) an additive to enhance the useful life of the composition.

Description

The segmented copolymer that is used for overmolding any nylon

The cross reference of related application

The application's case is advocated the right of the date of application of the provisional application case 60/550,354 of filing an application on March 5th, 2004.

Technical field

The invention relates to Overmolded one shaped article that is made of polymeric amide (nylon), it is Overmolded that it has a soft outer thermoplastic elastomer of about 20 to 80 Xiao Shi A hardness usually with one.Use term " elastomerics " in general sense to set forth a kind of rubber-like material.Thermoplastic elastomer (" TPE ") is normally showed the material of those character between between crystal or glassy plastics and mollielast, and described mollielast can be easy to be out of shape because of the pressure between thumb and the forefinger.It is softening when heating a TPE, and is easy under molten state by known treatment technology (for example injection moulding, blowing or extrude) thermoforming.

The Overmolded layer that is formed by TPE of the present invention is (for for simplicity, " OM layer ") allow to handle anchor clamps the part of the handle of handheld tool (for example screwdriver) or power tool shell (for example retained part of drilling machine or circular handsaw) for example with best work efficiency.Can on arbitrary part, provide desirable especially sensory feel (being called " excellent handle ") and " soft touch " now based on the shaped article (regardless of the type of nylon) of nylon and some other polarity substrates (for example, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, polycarbonate, thermoplastic polyurethane, thermoplastic copolyesters and copolyamide).

In addition, can make " sensation " or " feel and sense of touch " of different shaped articles according to the handle on the handle on the different instruments or door lock, the leather trunk and suchlike service requirements adjustment now and variously feel to differ from one another; These of OM layer " sense of touch " reach the physical properties that " sensation " character can be by regulating the indivedual components of admixture and have ratio adjustment by regulating it.

Problem:

Problem is to be difficult to will be bonded to a nylon sock based on the OM composition of rubbery block copolymers with desirable combination (in other words, the stripping strength of 11.73kg/cm (10lb/in)) at least.Described problem has three aspects: (i) make elastomeric OM layer tightly adhere to the hard moulding substrate (harder than Rockwell M60) of a polarity synthetic resins material, especially any durometer level is from the nylon of about Rockwell M60 to M110, and no matter described nylon is whether to use the enhancing of (for example) glass fibre derived from diamines or dicarboxylic acid and/or described nylon; (ii) so can not depend on the tackiness agent between described OM layer and described substrate; And (iii) uneven and durable to guarantee described OM layer, but touch is still softer, has excellent handle and preferable Xiao Shi A between about 20 to 80.But do not need between described OM layer and the described substrate a kind of fusion in described OM composition with the vinylbenzene of segmented copolymer wherein mutually or rubber phase combine the tackifying resin of tackiness agent effect.

Background technology

So far, especially when a kind of useful " soft " elastomerics is on object as described in an OM layer insert moulding directly is overmolded in common the doing on the nylon molding object time, described elastic composition must be suitable for the substrate of concrete nylon, and this depends on the molecular structure of described nylon.For example, when described nylon be During 1703-2 (a kind of) through 25% glass enhanced 6,6-nylon, but need be at a kind of particular combinations that constitutes by each component of OM elastomer layer allotment so that this layer adhere with accepting method and on described specific nylon, bring into play desirable effect; When described substrate is

During A3WG6BK00564 (also being a kind of 6,6-nylon, but have different molecular weight and contain 30% glass fibre), but need be at a kind of various combination that constitutes by each component of OM elastomer layer allotment so that this layer adhere with accepting method and bring into play same function.When the differing greatly of described nylon, the difference of composite will increase.

All terms of this paper " nylon " are common names, are used from any long-chain synthesized polymer vinegar amine with repetition vinegar amine groups as host polymer chain major portion.So far, before present invention disclosed herein, because the specific repeating unit that is not easy to determine Mw and can makes commercially available nylon molding object by thermoforming or alternate manner, so people seek to be used to reach suitable " excellent handle " OM TPE method for compositions of adhering certainly by extensive experiment and it has error.

And, even use " SHDS " rubber (for example Kraton FG1901) (for for simplicity by convention with about 1.5 to 2% functionality when haveing the knack of this operator, use " SHDS " expression a kind of partial hydrogenation at least " vinylbenzene-hydrogenated diene-vinylbenzene ", when its preferable complete hydrogenation) allotment is used for the OM TPE of nylon, even the combination that described OM layer also can not be desirable under high mold temperature is especially for the nylon sock of insert moulding used herein.Abbreviation " SDS " (vinylbenzene-diene-vinylbenzene) is meant linear polystyrene-conjugated diolefine (" polydiene ")-polystyrene block copolymer, polydiene typically refers to polyhutadiene and/or the polyisoprene in the mid-block, but described abbreviation broadly is meant from a monovinyl aromatic and the deutero-SDS of conjugated diolefine institute, monomer whose can mix with the common monomer of other structurally associateds vinylbenzene and a small amount of alpha-methyl styrene of main aromatics component (for example, as).

Described polydiene mid-block (being generally divinyl or isoprene) gives described polymkeric substance its rubber properties, and described polystyrene or poly-(a-vinyl toluene) block constitute the thermoplasticity phase.Because the polydiene block comprises the two keys (aliphatics nonsaturation) to oxidation-sensitive, so the preferable use hydrogenated butadiene of TPE or isoprene unit or both, if be SBS (styrene-butadiene-styrene) segmented copolymer before the TPE hydrogenation therefore, then gained hydrogenation (styrene-ethylene/butylene-styrene) segmented copolymer has the nonsaturation less than 5% usually, and is preferable less than 2%.Similarly, if be SIBS (styrene-isoprene/butadiene-styrene) segmented copolymer before the TPE hydrogenation, then gained hydrogenation TPE is SEEPS (styrene-ethylene/ethylene/propene-vinylbenzene) segmented copolymer.Above-mentioned SHDS comprises basically hydrogenant " high-vinyl " SHDS fully." high-vinyl " is meant that the butadiene midblock of at least 51 moles of % (per-cent) is 1, the polymerization of 2-position, and the isoprene of at least 51 moles of % (if having) be by adding a polar compound " to order about " polymerization 3, the polymerization of 4-position is as knowing in this technology; Usually the maximum value under each situation is 90 moles of %.Described HSBC is called " high-vinyl " HSBC, and no matter whether divinyl or isoprene or both are present in the described mid-block.

Especially need a kind of energy adhesion in the industry and a solid (being mainly the nylon molding object) surface is kept the firm OM TPE that adheres, regardless of the additive of the polymeric amide type that derives described nylon from it or described nylon parcel or processing condition or its aging rule of its moulding, and no matter whether described OM layer is by with compacted under: " injecting Overmolded " (also being called " insert moulding "); Or, " double injection moulding "; Or, with a nylon sock coextrusion; Or, multilayer blow moulding on a nylon sock.

In multiple commercially available related thermoplastic elastomerics, comprise those thermoplastic elastomers based on the physics admixture of polyolefine and rubber, and particularly, be to use wherein fusion to have the TPE admixture of polymeric amide to form the OM layer is firmly secured to the required combination of described substrate.

For example, in No. the 5th, 750,268, the United States Patent (USP) of giving people such as Mace, it is made to be used for " polarity engineering thermoplastic applications " (be called PA6, a kind of 6,6-nylon) of admixture needs 5 to the 50 weight % (" by wt ") of an OM layer.

With polymeric amide be main component identical of views of OM layer, the 5th, 843, No. 577 announcements of United States Patent (USP) of giving people such as Ouhadi are a kind of

The admixture of the reaction product of rubber and functionalised polyolefin and polymeric amide relies on when carrying out moulding the polyamide structure that exists in the described composition to produce the last one combination when the fusion admixture contacts with a nylon sock.

With above-mentioned opposite, OM layer disclosed herein mainly is about a kind of TPE who does not contain the segmented copolymer admixture of polymeric amide that comprises, it is applicable to uniquely and is overmolded in and firmly is adhered to any solid surface based on polymeric amide (" nylon ") usually, regardless of the concrete acid amides repeating unit of described nylon.Described admixture is particularly useful for wherein introducing under about envrionment temperature in the insert moulding of the Overmolded substrate of a desire, and twice moulding of solidified is more difficult hardly more than wherein said substrate with the adhesion on described surface under this temperature.Can adjust described novelty and not contain the adulterant of polymeric amide in the charging basket of forcing machine or injection moulding machine, to provide an OM layer with low, average or hot temperature curve.Have now found that described novel TPE elastomerics can be bonded to the various polarity substrate effectively, and between the layer of described substrate and the formation of OM composition, need not use tackiness agent.

Recently, the handle of the wooden or metal handle of various manipulative devices (for example screwdriver), power tool (for example circular handsaw) reaches all usefulness injection molding nylon handle replacements all of a part of the container that wherein holds instrument.For various reasons, the nylon type of various tool is inequality, and one of them reason is the hard especially core element of desiring to be coated in the nylon in order to hold.Some nylon are to take shape on the firm axle, as screwdriver or carve; Some nylon are to take shape on a door handles of metal or the shank of the key; Some handles are to be made by injection molding by glass fibre enhanced nylon.So far, regardless of concrete nylon anchor clamps, all have the shortcoming of in staff " firmly ", and in other words, it can not provide no matter be the opposing collision or the buffering of vibration.Described nylon anchor clamps are unlike wood more " user close friend ", and can not show a candle to metal user close friend.

A kind of approach that " softens " handle is that the soft thin flexible coverture with a kind of synthetic resin foam material covers described handle.Another approach is to use an insert moulding program that one mollielast is overmolded on the described nylon, the OM6000 that for example present industrial use is provided by GLS Corp. ⁺The Overmolded composition implementer of institute of series.Prior art OM layer uses the SHDS rubber of one " higher functional " and does not consider the morphological specificity of rubber, especially the ability of its " infiltration " described nylon sock under about 540 or lower, common 360 to 500 temperature.

The general knowledge of generally acknowledging is that the functionality of SHDS is high more, and the statistical machine of functional group and the reaction of described nylon sock can be just many more.Yet, even heat also not enough so that described " higher functional " SHDS rubber of described substrate (in other words by contacting with described OM layer, have be slightly larger than 1%, (for example) common 2% or above functionality) " infiltration " described substrate, this be because the amide group in the described substrate not by thermal activation to be enough to rubber on the degree of functional group reactions.

Quite unexpectedly, can judge according to higher combination (peeling off) intensity, when heating described amide group in a similar manner, use one to comprise and have from 1% but can obtain good infiltration less than the hot OM composition of " low functionality " SHDS of 2% functionality.

Reach for simplicity for convenience, and also for fear of the nonspecific property of term " lower ", will having basically hereinafter, the SHDS of 1% functionality is called " non-functionality "; And will have hereinafter＞1% but＜SHDS of 2% functionality is called " higher functional ", this be because 2% and above functionality invalid for present practical application.

The good combination of non-functionality and higher functional SHDS and previous view (that is, the functionality of described rubber is high more, and the chance of reacting between the functional group in the amide group on the described substrate and the rubber is many more) contradict.Described general knowledge has been ignored through the influence to described nylon of the heating structure of functionalized rubber and form; It has also ignored " correctly " structure that needs " little end block " or " high rubber " SHDS (described term is a synonym) provide the polymer chain that constitutes a form, described form make on the rubber functional group at first with the amide group adjacency so that it can more easily react in the surface.

Aforementioned Consideration and some common teachings are added the related prior art reference of mineral filler and are not recognized that also the existence of inert filler may be to form desirable bonded key point in the SHDS composition.Be understandable that, do not provide the weight that does not have the filler of remarkable tackiness agent character in essence that exists in the OM layer in the prior art.Think even have no reason with the concentration range that is defined be present in the SHDS composition microgranular, bat wool provides one also any nylon is had the key point of essential good adhesive " through filling " OM layer under the insert moulding condition according to circumstances, from a practical viewpoint, it is useless not having this tackiness OM layer.

Summary of the invention

(a) inert filler, (b) softening agent reaches (c) combination of segmented copolymer a kind of OM thermoplastic elastomer (" TPE ") composition can be provided, described segmented copolymer is to be selected from the group that is made up of following: (C1), the SDS or the SHDS rubber that have a polystyrene end block at each end of polydiene mid-block, described mid-block comprises the polymerization of vinyl aromatic monomer, common polystyrene, there be (not comprising the polystyrene in the polydiene mid-block) in described polystyrene end block with the amount of about 20% to 30 weight % of described segmented copolymer altogether, and therefore (C1) has one enough high so that 282 ℃ (540) heat-staple weight average molecular weight (" Mw ") down;

(C2) having basically, there be (that is, each end-blocks has more than the low molecular weight of rubber-like mid-block) in functionalized " high rubber " SHDS " (F2) " described " little end block " of 1% functionality jointly with the amount between about 8 to 25 weight %; And

(C3) have＞1% but＜the functionalized SHDS of 2% functionality, the amount of wherein said end-blocks is altogether from＞25% to 35 weight %,

But its arbitrary combination, but may only have (C2) and do not have (C1) with (C3); Provide one to have OM thermoplastic elastomer (" the TPE ") composition that obtains good combination necessary " infiltration ", as by when as described in TPE be overmolded in one based on the substrate of nylon on the time stripping strength of 11.73kg/cm (10lb/in) is illustrated at least, be derived from diamines or dicarboxylic acid monomer or described nylon sock aging or described substrate aged humidity condition how long regardless of described nylon; And, described OM composition under the temperature that is lower than 149 ℃ (300) for fluid, and must be substantially free of polyamide component and unhydrogenation the SDS segmented copolymer the two.

Do not have (C1) when there being (C2) or (C3) time, the amount of 10-40% that (C2) can described composition exists." be substantially free of " and be meant that a composition (if having) exists with the amount less than 5 weight %.

Although (c) more than is provided, but any two kinds combination can obtain the good combination of 11.73kg/cm (10lb/in) at least during only use (C2) and use (C1), (C2) reached (C3), used all combinations of three kinds to obtain the excellent combination of 17.3kg/cm (15lb/in) at least at relative low temperature (hereinafter curve I condition).

If target is not a best combination, the then available hydrogenation not functionalized SHDS segmented copolymer that accounts for described OM composition 0 to 15 weight % replaces (C1), (C2) or a part (C3).

For adjusting the hardness of described composition, it can comprise the functionalised polyolefin " (FP) " of 0 to 30 one or more alkene of weight %, and each alkene has 2 to 8 carbon atoms.

" inert filler " is meant that any component of described filler and described OM layer is neither and has a chemical reactivity.Only refer to have the segmented copolymer of a unhydrogenation mid-block when mentioning " SDS " that can be used for admixture of the present invention together with mono alkenyl arene (vinylbenzene usually) block of a controlled distribution.Be chosen in any SDS that has polystyrene in the described mid-block or SHDS Mw in case under the temperature of substrate moulding, stable down between 182 ℃ to 282 ℃ (360 °F to 540 °F) usually.

More particularly, found a kind of preferable combination of following composition: (A) inert filler " (a) ", its with 5 to 40%, preferable 10 to 35% amount exists; (B) " (C1) ", its amount with 5 to 25% exist and have a weighted average Mw between about 20,000 to 300,000; (C) a high rubber SHDS of non-functionality " (C2) ", it has 1% functionality and exists with 5 to 25% amount; (D) SHDS " (C3) " of a higher functional, it has＞1% but＜2% functionality and exist and have a Mw scope identical with (C1) with 5 to 25% amount; (E) 5 to 25% functionalized poly (C ₂-C ₈) alkene (FP), preferable polyethylene or polypropylene; All above-mentioned and a small amount of (by weight) (with respect to the gross weight of compound admixture) non-reacted softening agent (F) fusion, good embodiment with above-mentioned Overmolded (" OM ") composition is provided, but restricted condition be when (C) when (D) the two all exists, it exists with 5 to 25% amount altogether.In aforementioned, " % " is meant the compound resin of umber/100 parts by weight.It should be noted that the quantity of representing with " parts by weight " of each composition is with respect to 100 parts by weight rubber " phr ".

Because less end-blocks promotes the infiltration of described substrate surface, so best described little end block rubber has the styrene content less than 20%.

Although described TPE can comprise 0 to 35% (FP), but a preferable TPE composite comprises 5 to 20% (FP), and 10 to 30% paraffin oils " (b) ", and supplementary condition are that the amount of non-functionality SHDS is to exist in the amount that is enough under the preferable situation that does not have a solidifying agent under the temperature between 182 ℃ to 282 ℃ (360 to 540) with the amide group reaction of described substrate.With commonly used microgranular or fibrous inertia (be preferably mineral) filler " (a) " the evenly fusion of aforementioned combination, so that the combination of a minimum 11.3kg/cm (10lb/in) is provided for a substrate based on nylon with about 5 to 35% the amount that accounts for the fusion TPE of institute.In addition, described TPE admixture can comprise other these technology additive known improveing the performance of described OM layer, described additive comprise handle in auxiliary agent, antioxidant, antiozonidate, uv photostabilizer and other this technology known be used for described TPE commonly use the interpolation composition.

" (C1) " can be a SDS or SHDS as mentioned above.When being SDS, described polydiene mid-block be derived from butadiene or isoprene or divinyl/isoprene the two; When being SHDS, the hydrogenation polydiene mid-block of described SDS obtains ethylene/butylene (from SBS), ethylene/propene (from isoprene), reaches the mid-block of ethylene-vinyl/propylene and/or ethylene/propene-3-methyl butene (EP3MB) (from SIBS).The polystyrene that controlled distribution is arranged in the block in these.

(C1) with under the temperature that the node configuration of the polymer chain of high rubber SHDS (C2) can make all compositions be heated to when described nylon sock contacts with hot OM composition has compatibility, and critical " infiltration " is provided and can reaches interactional interaction from the teeth outwards, thereby under the relative low temperature of regulation, reach desirable combination.

SHDS of each special not functionalized (if having) and functionalized SHDS (C1) and the Mw that (C2) all has between about 20,000 to 400,000, preferable low relatively Mw between 20,000 to 250,000.This scope provides essence to soak into, itself so that excellent combination with described nylon sock is provided.

The admixture that the present invention has 5% inert filler has unique character, and under every other component and condition of molding kept identical situation, its bonding strength was along with filler quantity increases to 10% and increase.

If expectation, the described novel TPE composition that is not bonded to a substrate self can be used for the soft object of moulding (teething ring or that for example is used for the baby can be chewed the dog bone), can regulate its hardness and deformability at purposes.

And have under the room temperature between about Xiao Shi A20 to 80, the preferable admixture of the desirable hardness of preferable A 35 to A 75 comprises following composition (providing with umber/100 a part admixture of being allocated), it comprises: (i) with the SHDS of not functionalized in 10 to 60 parts of mid-block and polystyrene and (ii) 10 to 45 parts with the fusion of rubber phase bonded softening agent, add (iii) 1 to 25 part of non-functionality hydrogenation SHDS then, and (iv) 0 to 25 part of " higher functional " SHDS is (promptly, have＞1% but＜2% functionality), each functionalized SHDS all has the Mw less than 400,000; (v) an inert mineral filler is dispersed in the described admixture, and (the vi) functionalised polyolefin of a specified quantity of further fusion according to circumstances, so that an OM admixture to be provided, described admixture is being bonded to known commercially available nylon sock with the stripping strength greater than 17.3kg/cm (15lb/in) under the temperature between 204 ℃ to 260 ℃ (400 to 500), and is bonded under 249 ° to 282 ℃ (480 ° to 540 °F)

801 (substrate E, hereinafter).

A kind of method that is used to prepare a shaped article comprise by surpass in regulation under the temperature of about 182 ℃ to 282 ℃ (360 to 540) scopes the Overmolded composition of heating one thermoplastic elastomer with described OM composition be bonded to a nylon, subsequently make institute's heating combination with described nylon combination so that cover at least a portion of described nylon and combining of 11.3kg/cm (10lb/in), preferable 17.3kg/cm at least (15lb/in) at least be provided.

A kind of object of the arbitrary shape that is formed by nylon has the OM composition layer that is formed in its surperficial at least a portion.One preferable lamination object comprises the rigidity rigidity nylon sock of 1Gpa at least, and it uses the moulding of above-mentioned particular composition integral coating and does not use tackiness agent between described substrate and the formed subsequently OM.

Description of drawings

Embodiment

Hanging down in the concrete preferred embodiment Overmolded under the charging basket temperature relatively in curve 1 (hereinafter), described OM TPE is made of following each component basically: (i) 20 to 30% microgranular or fibrous inert filler; (ii) 15 to 25% non-reacted mineral oil; (iii) 10 to 20% have cinnamic SHDS in the polydiene mid-block; (iv) 15 to 25% have the SHDS rubber of 1% functionality basically; (v) 15 to 25% have＞1% but＜the SHDS rubber of functionality between 2%; But restricted condition is when (iv) with (when v) existing simultaneously, it is no more than 25%; (vi) 5 to 10% functionalised polyolefin, described alkene has 2 to 4 carbon atoms; And (vii) at least a other additives are to strengthen the work-ing life of described composition, and described functionalized rubber and functionalised polyolefin each carry out functionalized with a polar group that is selected from the group that is made up of acid anhydrides, carboxyl, carboxylic acid and amine epoxy naturally; And wherein all % do not refer to functionality, and are meant the weight % in described blend composition.

In a preferred compositional, the ratio of selecting each component is to provide the hardness between 30-75 Xiao Shi A.

More than selected ratio under the charging basket temperature of curve I, provide the excellent combination that is higher than 17.3kg/cm (15lb/in).

Under curve I condition, even do not use functionalised polyolefin also can provide between 11.3kg/cm (10lb/in) to the appropriate good combination (referring to the example in the table 5 10) between the 17.3kg/cm (15lb/in).Yet, the excellent combination of under the higher charging basket temperature of curve III, not using functionalised polyolefin also can provide to be higher than 17.3kg/cm (15lb/in) (referring to the example in the table 53,4).

When described substrate is Zytel 801 (although it is heat-staple nylon-6 as Zytel 409AHS, 6), in final charging basket temperature between the expectation combination that obtains 15lb/in under 520 curve III conditions between 540 when Overmolded.Preferably, to be to use maleic anhydride, vinylformic acid or acrylate group to carry out functionalized for described preferable functionalised polyolefin (no matter polypropylene or polyethylene).

The not functionalized rubber (C1) that in the polydiene mid-block, has polystyrene:

Described rubber " (F1) " can be unhydrogenation (SDS) or hydrogenation (SHDS).Each is all by the controlled distribution block increase polarity of mono alkenyl arene (polystyrene) with conjugated diolefine, and described rubber has polystyrene block in the polydiene mid-block.And described rubber must have about 20% to 30% the polystyrene end block that accounts for described rubber weight altogether.Higher polarity is impelled the hot surface of " infiltration " nylon sock.The SDS of described unhydrogenation is with the Styroflex 2G66 person of buying from BASF; Hydrogenation SHDS is with the Kraton A6935 person of buying.The detail file of believing A6935 rubber have been disclosed among laid-open U.S. Patents US2003/0181584 A1 number on September 25th, 2003 and it is as being incorporated herein by reference of setting forth fully.

Functionalized SHDS (C2) reaches (C3):

Functionalized SHDS can prepare by prior art method, and especially those are set forth in United States Patent (USP) the 4th, 174, No. 358; The 4th, 429, No. 076; The 4th, 427, No. 828; The 4th, 628, No. 072; The 465th, No. 791; And person in the 4th, 844, No. 471; It is as being incorporated herein by reference of setting forth fully.Preferable use one unsaturated acid of described mid-block or acid anhydrides hydrogenation and grafting basically in the presence of organo-peroxide are as hereinafter about the elaboration of functionalised polyolefin.Described unsaturated acid or acid anhydrides be with from 1 to amount grafting less than 2 weight %.The preferable use diprotic acid of described SHDS, the best maleic anhydride that uses carry out grafting.

Preferably, for the regulation of described functionalized SHDS except that it is functionalized basically with above identical at given those of the SHDS of not functionalized.

The example of suitable functionalized SHDS be in scope referred to above, preferable from about 30,000 to 150,000 Kraton RP6670, Kraton FG 1901 and Kraton FG 1924.

The preferably is commercially available segmented copolymer, for example those are at present with FG1901 (the styrene/rubber ratio is 30/70) and FG1924X (the styrene/rubber ratio is 13/87 or 16/84) trade name sale person, the former has the functionality from about 1.5% ≈ (to approximately) 2%, usually about 1.7%, the latter is basically 1%, that is non-functionality.

The SHDS of not functionalized (03):

Preferably, described two styrene end blocks substantially the same and each have Mw between 3000 to 60,000; And described mid-block had before hydrogenation between 50, Mw between 000 to 250,000, and in high rubber SHDS used herein, described strictly end-blocks only constitutes sub-fraction, accounts for 8 to 25 weight % of all segmented copolymer weight, preferable 10 to 25 weight %.

The example of other suitable SHDS segmented copolymers is that LLC is with following from Kraton Polymers U.S.

Trade(brand)name G 1650, G 1651, G 1652, G 1654, G 1657, G 1726, GRP 6924 and the GRP6917 person of buying.

Functionalised polyolefin (FP):

The preferably is the multipolymer of functionalized homopolymer and a-alkene ethene and propylene.

One preferable functional group is derived from maleic anhydride, but can use other unsaturated dicarboxylic acid acid anhydride diprotic acid or acid/ester mixtures, and it has following general formula:

Wherein R is an alkylidene group with 0 to 4 carbon atom, Y be preferably hydrogen but can be an organic group (for example the branched-chain or straight-chain alkyl group of 1-12 carbon atom, heterocycle or other organic groups), halogen group (for example chlorine, bromine or iodine) and wherein at least one and two X groups be preferably hydroxyl, but an X group can be alkoxyl group or the aryloxy with 1-8 carbon atom.

For example, the maleic anhydride in the following example can all or part ofly replace with normal other unsaturated dicarboxylic acids of equimolecular or acid anhydrides (for example methylene-succinic acid or acid anhydrides, fumaric acid, toxilic acid and like that).

Graft reaction can carry out in the presence of a peroxide catalyst; described catalyzer is that (for example) dicumyl peroxide, tertbutyl peroxide, benzoyl peroxide, the tertiary butyl are crossed octanoate, Over oxidation di-t-butyl, tertbutyl peroxide, isopropyl benzene hydroperoxide, tertiary butyl perbenzoate or other can capture the radical source of hydrogen, as by alkyl peroxy esters, alkyl peroxide, alkyl peroxide, diacyl peroxide and represented person like that.The amount of catalyzer and reaction conditions should change with selection of catalysts.

The acid anhydrides on grafting on described polyolefine or the amount of diprotic acid between between polyolefinic 0.2 to the 5 weight % of matrix and preferred number obtain desirable result in 0.5 to 4% grafting scope the time.Usually, grafting on quantity on the described polymkeric substance should only account for and 30 to 50% of the graft materials of described polymer reaction.For example, for reaching the grafting of 2% maleic anhydride to the polypropylene, need to load about 6% maleic anhydride.

Softening agent:

Selected softening agent partly depends on the Mw and the specific chemical combination of described Overmolded TPE composition, but described softening agent therein simultaneously must be stable in the temperature range (about certainly 400 to 600) of the described OM layer of moulding on a substrate with described OM formable layer and not be reacted with any composition of described TPE admixture.

Found that useful plasticizing oil comprises oil derived from oil, olefin oligomer and low Mw polymkeric substance, and plant and mineral oil, all these are all relative high boiling point material, only comprise the aromatic hydrocarbons of a small amount of, preferable 10 weight % less than described plasticizing oil.Best oil is paraffin.

A kind of oligopolymer that plays the softening agent effect is preferable to have between about 350 to 10, Mw between 000 and normally poly-(alpha-olefin), for example polypropylene), polybutene, poly-laurylene, hydrogenated polyisoprene, hydrogenated butadiene polymer, the poly-piperylene of hydrogenation, and the hydrogenated copolymer of piperylene and isoprene.Vegetables oil mentioned above comprises the glyceryl ester and the polymerisate thereof of naturally occurring lipid acid.

The best is a paraffin oil, for example 500,

And

352; And viscosity is between 200 to 1000SUS (ASTM D455) or the oligopolymer of Mw between 200 to 1,000, for example

And

Other additives:

The resin mutually relevant with vinylbenzene:

The resin mutually relevant with vinylbenzene also is called " tackifying resin " because of it is compatible with described styrene end block, it is a kind of preferable resin that is selected from by the following group that forms: coumarone-indene, polyindene, poly-(methyl indenes), polystyrene, Vinyl toluene-alpha-methyl styrene, alpha-methyl styrene and polyphenylene oxide, especially gather (2,6-dimethyl-1, the 4-phenylene ether).Described commercial resins is: cumarone indene resin, Cumar series and Cumar LX-509 (Neville); Hydrocarbon resin, Picco 6000 series (Hercules), Nevchem and LX 685 series (Neville); The alpha-methyl styrene resin, Piccotex series, Kristalex series (Hercules) and Amoco 18 series (Amoco); And, polystyrene resin, for example Piccolastic D-150 (Hercules) and LX 1035 (Neville).The preferably is the nonpolar polystyrene resin that softening temperature is sold with " Plastolyn " trade(brand)name between about 120 ℃ to 140 ℃.

The resin relevant with rubber phase:

Except the described resin mutually relevant with vinylbenzene, described admixture also can comprise a resin, because of compatible also can be described as " tackifying resin " of rubber phase of itself and hydrogenation mid-block.The suitable resin relevant with rubber phase comprises polymerization mixed olefins resin, and for example " Super Sta-Tac " (Reichhold); Quintone series (Nippon Zeon); Nevtac series (Neville); Piccotac 95-BHT series (Hercules); " Escorez " 2101 (Exxon); Wingtack series (Goodyear); Escorez 1300 series (Exxon); Super Nevtac 99 (Neville); Piccotac B (Hercules); Sta Tac/R (Reichhold); Hercotac AD (Hercules); And " Betaprene " BC (Reichhold); Polyterpene resin, for example Zonarez 7000 series (Arizona); Zonatac series (Arizona); Nirez 1000 series (Reichhold); Piccofyn A-100 (Hercules); Nirez V-2040 (Reichhold); Piccolyte HM110 (Hercules); Piccolyte A (Hercules); Rosin ester, for example Sylvatac series (Sylvachem); Super EsterA series (Arakawa); Stabelite Ester 10 (Hercules); Foral 85 (Hercules); " Zonester " series (Arizona); Foral 105 (Hercules); And Pentalyn H (Hercules); And the hydrogenate hydrocarbon resinoid, for example, Escorex5000 series (Exxon); Arkon P series (Arakawa) " Regalrez " series (Hercules) and " Super Nirez5000 " series (Reichhold).Preferable resin is that polymerization mixed olefins resin and other are no more than the resin of 300 centipoises in 350 following viscosity.

The example of suitable other additives comprises thixotropic agent; White dyes; Antioxidant; UV absorption agent and hindered amine or the acid amides photostabilizer that is obstructed; Fire retardant; Pigment and tinting material; Handle auxiliary agent, for example lubricant, releasing agent, and antiseize paste; Spices; Defoamer; Antioxidant; Static inhibitor; Biocide; Biocide; Deng.

Inert filler:

No matter described inert filler is microgranular or fibrously all must exist with specified amount, depends on " Overmolded effect " or other end-uses of described TPE admixture at the selected quantity of any concrete nylon.No matter be through enhancing or without enhancing, the size of described filler preferable between 1 micron-150 microns, preferable from 1 to 45 micron.Fiber (for example glass, carbon fiber or carbon fibrils) all can described scope the upper limit use.Lower limit that can described scope use inorganic particles (for example lime carbonate, clay, silicon-dioxide, talcum powder, titanium dioxide, carbon black and like that) and more than the fragment of the fiber mentioned.Some fillers can have more than one function.For example, ANTIMONY TRIOXIDE SB 203 99.8 PCT can be used as filler and (preferable combine with other materials) flame retardant resistance also can be provided.The inert filler of preferable 10 to 30 weight % provides desirable combination in described composition.

In addition, also can comprise thermo-stabilizer in the described OM TPE admixture, for example fortified phenol and phosphite less than 1 weight %.

Nylon sock:

Nylon is by being used to produce its diamines and the amount of carbon atom of diprotic acid is discerned; Therefore, for example nylon 6/6 is a kind of polymkeric substance that produces by the condensation of hexanediamine and hexanodioic acid.Some nylon are to produce by a kind of reactive material of condensation only, and it is usually from lactan production; These nylon are to discern by the quantity of the monomer carbon atom that is used for producing it, and therefore, (for example) poly-(hexosamine) is that the polymerization by hexanolactam produces, and it is called " nylon 6 ".Can use described Overmolded TPE to come Overmolded nylon example is nylon-6; Nylon-6,6; Nylon-6,10; Nylon-4,6; Nylon-6,12; Nylon-11; PA-12; The partially aromatic nylon copolymer, nylon-6/6 for example, T; Nylon-6,6/6,1/6, T; And like that, and these admixture.A kind of typical nylon is nylon-6 or nylon-6,6; These and other polymeric amide mainly be by Allied company with

Trade(brand)name, by E.I.duPont de Nemours company with

Trade(brand)name, by BASF AG with

Trade(brand)name; And by Rilsan company with

Trade(brand)name sale person.Described resin is crystal and have high-melting-point normally.These nylon that are used for moulding have at least about 10,000 usually, preferable number-average molecular weight (Mn) between 15,000 to 50,000.

One nylon sock comprises the nylon of big part by weight at least in composite nylon.Described nylon can comprise one and be fibrous or particulate toughener.Useful fiber enhancer includes, but is not limited to glass fibre, carbon and graphite fibre, comprises the polymer fiber of Kevlar shape, boron fibre, ceramic fiber, steel fiber, fibrous magnesium silicate, beryllium fiber, silica fiber, silicon carbide fiber and like that.Described fiber can conduct electricity, and can use these electro-conductive fibers (for example conductive carbon fibre or steel fiber) to be used to conduct electricity with generation or static charge consumption is used or the object of EMI shielding.In these, the preferably is glass fibre, carbon fiber and Kevlar.The method for preparing the thermoplastic resin that comprises these fibers is known by this technology.In one approach, chopped glass fiber bundles is supplied to the melting zone that is used to form through the forcing machine of Reinforced Nylon material.Perhaps, described fiber can be used as in a bite of endless tow or the described forcing machine of bundle introducing.

Toughener can comprise a microgranular inorganic strengthening agent.Suitable inorganic strengthening agent includes, but is not limited to wollastonite, mica, granulated glass sphere (solid or hollow), kaolin and talcum powder.Mica also available (for example) coupling agent (for example silane) is handled to strengthen mechanical properties or to be used for special applications with the nickel coating processing.Preferable inorganic strengthening agent is wollastonite, mica, kaolin and talcum powder.Inorganic strengthening agent is included described resin in by the melting zone that a hopper is fed into forcing machine usually.

Described toughener can be fortifying fibre and the combination that strengthens mineral.Described toughener usually with account for described through the Reinforced Nylon substrate at least about 5% and the amount of at the most 25 weight % exist.

Provide following example to set forth preferred embodiment of the present invention.

Explanation in passing, following symbol is used for the code of following page table:

(a) SEBS of maleinization, φ ≈ 1.5-2; S/EB is than=30/70;

(b) SEBS of maleinization, φ ≈ 1; S/EB is than=13/87;

(c) polyethylene of maleinization, MI 30@190 ℃/2.16kg, maleic anhydride 1%;

(d) " standard " SEBS

(e) BASF styrene block copolymer, styrene monomer in mid-block, unhydrogenation,

(f) 100 parts of non-functionality styrene block copolymers (Kraton, Septon and Styroflex) are used for preparation of compositions as matrix.

(g) Kraton G 1652 replaces Kraton FG 1901

Drakeol 500 is a kind of mineral oil of buying from Penreco

Plastolyn 290 is a kind of thermally-stabilised hydrocarbon resins, and it has Mw=6040, Mn=1670 and Mz＜20,000 melt viscosity together with @230 ℃ of one 10 pool

Kemamide is a kind of fatty acid amide lubricant

Vicron 25-11 is a kind of pure basically calcium carbonate powders.

Table 1 has provided the illustrative example of seven (7) kind compositions, wherein changes the predictive role of each composition with hardness, tensile strength and elongation % after observing the various changes of enforcement to moulding.The physical properties of forming composition is the same important in the good combination that satisfies the purpose that is about to reach to be provided with the performance of described composition at least.

In table 1, example #1 is a prior art composition, and wherein 120phr Kraton FG 1901 (one " higher functional " rubber (about functionality of 1.5% to 2%)) is used in combination with the not functionalized hydrogenation Kraton G1654SBS segmented copolymer of 100phr and the filler particles of 170phr.

In example #2, replace G1654 with Kraton A6935, other compositions have identical ratio basically.

In example #3 to #7, will set forth other variations.

Table 2 has provided a series of four (4) individual additional illustrative examples, in each example A6935 all keep with example #7 in the identical amount of amount; Shown in 5 examples comprise respectively that with non-functionality of variable ratio bonded and higher functional rubber some have filler and some do not have, some have Polybond and some do not have.

Table 3 provides 3 examples, does not wherein have Polybond and does not have functionalized SHDS rubber, and be to use the Styroflex of hydrogenation A6935 or unhydrogenation or the two.

Table 4 has provided the comparison of composition #15 and #16 and prior art #1, to show that the non-functionality FG1924 of Individual existence is effective; And even when wherein half replaced with higher functional FG 1901, it was still effective.

Table 5 provided use hereinafter discerned five (5) plant the various combination degrees that different nylon sock obtained, each nylon sock all is under the condition of molding of different strict degree, advocated that to provide composition is to any nylon sock effective evidences all.

Table 4

Composition	1 phr ％	15 phr ％	16 phr ％
				Kraton A6935(f)
Kraton G1654(d)(f)	100 17.09	100 17.09	100 17.09
				Styroflex 2G66(e)(f)
Drakeol 500	150 25.63	150 25.63	150 25.63
				Kraton 1901(a)	120 20.51		60 10.25
Kraton 1924(b)		120 20.51	60 10.25
				Plastolyn 290	40 6.84	40 6.84	40 6.84
Vicron 25-11	170 29.05	170 29.05	170 29.05
				Polybond 3109(c)
Kemamide B	4 0.68	4 0.68	4 0.68
				Irganox 1010	1.2 0.21	1.2 0.21	1.2 0.21
Hardness, Xiao Shi A	39	35	38
				Tensile strength, psi	500	350	430
Elongation	210	510	520

Referring now to above table 1 and 5, clearly:

(i) contrast admixture #1 makes in conjunction with Kraton1901 (functionality 1.5 is to about 2) with " standard " Kraton G1654 (hydrogenation but not functionalized), and it has superior tensile strength and elongation, even but under curve III condition also can not in conjunction with;

(ii) admixture #2 is by replacing G1654 to make with A6935, and other compositions are substantially the same; Described admixture provides high-tensile and elongation, and quite soft (A41); Yet, only under curve II and III condition, providing good combination, the A6935 that this proof has a higher functional SHDS (about 1.5%) provides good and preferable the combination respectively under curve II and III condition.

(iii) admixture #3 uses the hydrogenation A6935 and the Styroflex 50/50 of unhydrogenation to make and find to provide higher hardness, tensile strength and elongation than independent use A6935; Although the combination under curve II condition is identical with admixture 2 basically, the combination under curve III condition is good more than admixture #2.

(iv) admixture #4 is by replacing the A6935 among the admixture #3 to make with G1654, and the result is that tensile strength is approximately identical and hardness is only low slightly than admixture #3, but elongation reduces basically.Binding ratio admixture #3 under curve II condition is poor slightly, but under curve III condition in conjunction with good.

(v) admixture #5 is to use the combination of Kraton FG1901 and A6935 to make, but does not have non-functionality FG1924.Combination under curve II condition is good, and the combination under curve III condition is better, this is replaced causing tensile strength and elongation and the only slightly low hardness better than admixture 269-007B by Kraton 1901 owing to Polybond to small part, and uses the rubber below 10 parts to show that Kraton 1901 helps favorable mechanical character;

(vi) in admixture #6, non-functionality Kraton FG1924 replaces FG1901 and the Kraton A6935 combination among the admixture #5; As prove that hardness is better than the hardness of admixture #5 through improvement, elongation is identical, but the tensile strength of admixture #6 reduces.Under each situation, use Polybond 3109 to regulate hardness and cause low relatively tensile strength and elongation.Yet admixture #6 all provides excellent combination under all curves.Use standard SEBS (Kraton G1654) replaces the contrast admixture of Kraton A6935 that combination and dead-soft are not provided.

(the vii) only deliquescing a little of admixture #7 by replacing FG1924 to obtain with 50/50 ratio with FG1901, it has identical approximately tensile strength, but has the elongation that reduces basically.#6 is the same with admixture, and being combined under all curves of admixture #7 is all better.

Referring now to table 2 and 5, clearly:

(viii) admixture #8 has used identical inert filler among the admixture #7 below 8.7%, and every other composition is all approximately identical.Surprising result is that the inert filler of low per-cent causes hardness to reduce and elongation increases, but as one might expect, tensile strength reduces.Yet, as admixture #﹠amp; The same, admixture #8 all provides excellent combination under all curves.

(ix) admixture #9 is identical with admixture #8 basically, does not just wherein have inert filler.Hardness, tensile strength and elongation and admixture #8 and no significant difference, but quite surprising, admixture #9 is neither under each curve condition to provide desirable combination.

(x) use the effect of inert filler to remove Polybond simultaneously for determining, so make admixture #9 so that hardness to be provided.In fact described filler makes hardness reduce slightly, makes the essentially no difference of tensile strength and elongation, but quite surprisingly, obtains excellent combination down in curve III condition (data do not write down) under curve 1 and II condition and also.Because weak tensile strength and soft, thus the stripping strength that writes down can not fully reflect the bonded good degree.

(xi) in admixture #11, the two all saves inert filler and Polybond; Described combination depends on the combination of A6935 and non-functionality FG1924 and higher functional FG1901.Hardness, tensile strength and elongation be identical with admixture #10 basically, can provide desirable combination but described admixture is neither under any curved line spare.

Referring now to table 3 and 5, clearly:

(xii), use G1652 to replace the FG1901 among the admixture #2 to cause neither desirable combination under all curves although admixture #12 is the combination of A6935 and inert filler.(xiii) as can estimating, replace among the admixture #12 with Styroflex that 50% A6935 is neither under all curves to provide desirable combination, but make tensile strength and the two raising of elongation.

(xiv) as can estimating, can provide desirable combining with the A6935 among the hydrogenation SHDS replacement admixture #13 of Septon 4044, not functionalized with Styroflex is neither under all curves, and make tensile strength and the two reduction of elongation.

Referring now to table 4 and 5, clearly: (xv) admixture #15 is only made by non-functionality FG1924, do not have A6935, do not have FG1901 and do not have Polybond, but the combination of use inert filler and G1654 is to provide a kind of soft admixture (35A) that can accept tensile strength and good elongation that has.The most surprisingly, FG1924 has the special performance that good combination is provided under curve II and III condition.As previously mentioned, because weak tensile strength and soft, so the stripping strength that is write down can not fully reflect the bonded good degree.

(xvi) in admixture #16,50% FG1924 replaces with FG1901, and only tensile strength obtains improvement a little.Although combining under curve I and II condition is not desirable, under curve III condition in conjunction with good.As previously mentioned, because weak tensile strength and soft, so the stripping strength that is write down can not fully reflect the bonded good degree.

The data that presented in the table 5 are at table 1 cited mean value that each admixture obtained in 5, obtain described admixture and be used for reaching adhesion by the thick layer of Overmolded 1.5mm on each following five kinds of different nylon sock, wherein each nylon sock has different wearing out.

Substrate A: commercially available Capron 8333GHI-glass fibre shape strengthens and through the nylon 6 of shock resistance upgrading.The plate of this substrate A is moulding in 3 months before usefulness test admixture is Overmolded; Described plate is stored in the closed cabinet.Storage (that is, Overmolded preceding 1 month) is after two months taken out described plate and is exposed under about ambient moisture of 70 to 80% in (23 ℃) under the room temperature in described case.

Substrate B: commercially available Zytel 409AHS-is through heat stabilized nylon 6,6.The plate of this substrate B is to make it be that (23 ℃) are aging when about ambient moisture of 70 to 80% exposes 6 months down under the room temperature then through moulding.Then that burn-in board is Overmolded with the test admixture.

Substrate C: commercially available Capron 8333GHI-nylon 6.The plate of this substrate C is through moulding.Then by exposing over 1 month it aging down in (23 ℃) under the room temperature in about ambient moisture of 70 to 80%.Then described burn-in board was soaked in water 24 hours, wipe away dry doubling and make its dry 12 hours of universe under room temperature again, Overmolded with the test admixture afterwards.

Substrate D: commercially available Capron 8333GHS, nylon 6.The plate of this substrate D is through moulding, and is the same with the plate of above-mentioned substrate C aging and soak into, and just it wipes away after doing Overmolded immediately with thin paper.

Substrate E: commercially available Zytel 801AHS-is through heat-staple nylon 6,6.The plate of this substrate E makes it be that (23 ℃) are aging when about ambient moisture of 70 to 80% exposes 3 months down under the room temperature through moulding then.Then that the aged plate is Overmolded with the test admixture.

Peel off test:

This test is to implement on 5564 type Instron tensilometers.Described substrate is clamped in the bed piece of described machine.End with Overmolded layer (1.5mm is thick) is clamped on the vertical anchor clamps then, and described anchor clamps draw described layer with 90 ° of angles vertically upward with the peeling rate of 5.08cm/min (2in/min).

The observed value of clinging power is with the lb/in record.

When clinging power＜11.73kg/cm (10lb/in), think that described combination is too weak and make us dissatisfied;

When clinging power is between 11.73-17.3kg/cm (10-15lb/in), think that clinging power is good; And,

When clinging power＞17.3kg/cm (15lb/in), think that clinging power is good.

At three described admixtures of temperature levels compacted under, wherein use three charging basket temperature curves, under hopper, begin and finish at the nozzle place.First curve is " standard " or " low ", is called curve I; The second curve II is called " medium " or " standard adds "; And the 3rd curve III is called " heat ".

Charging basket temperature among the curve I is as follows: 182,249,260,260.(℃ standard)

Or, 360,480,500,500.(standard)

Charging basket temperature among the curve II is as follows: 182,260,271,271.(a ℃ standard adds)

Or, 360,500,520,520.(standard adds)

Charging basket temperature among the curve III is as follows: 182,271,282,282.(℃ heat)

Or, 360,520,540,540.(heat)

Injection speed is 5.08cm/sec (2in/sec).

Use curve I, II and the III charging basket temperature in each to be shown in all in order in the table 5 at the measured clinging power (representing) of each admixture on each substrate with lb/in.Replace the mark " no " of observed value to show that described Overmolded layer can be used the hand unsticking in each table, this shows in conjunction with not desirable.Mark N/A is used to show because the combination under low charging basket temperature curve is good, and it can not degenerate under curve III condition and be better usually, therefore needn't measure described combination.

Claims (8)

1, a kind of Overmolded one composition for thermoplastic elastomer that is used for based on the substrate of nylon, described composition is made of the admixture that is substantially free of polymeric amide basically,

Described adulterant comprises:

(a) inert filler, it exists with the amount between 5 to 40 weight % of described composition, the size of described inert material is between 1 micron-150 microns, described inert material is selected from: glass fibre, carbon fiber or inorganic particles, and described inorganic particles is selected from: lime carbonate, clay, silicon-dioxide, talcum powder, titanium dioxide, carbon black or ANTIMONY TRIOXIDE SB 203 99.8 PCT;

(b) composition in the softening agent, itself and described composition does not react, and described softening agent exists with the amount between 10 to 40 weight % of described composition;

(c) segmented copolymer, it is selected from the group that is made up of following each thing:

(C1), polystyrene-poly diene-polystyrene block copolymer, or partially hydrogenated at least polystyrene-poly diene-polystyrene block copolymer, described polystyrene-poly diene-polystyrene block copolymer respectively has the polystyrene end block with partially hydrogenated at least polystyrene-poly diene-polystyrene block copolymer, each end in the polydiene mid-block has one, described mid-block comprises the polystyrene block of controlled distribution, described polystyrene end block exists jointly with the amount between 20 weight % to 30 weight % of described segmented copolymer, described amount does not comprise the polystyrene in the described polydiene mid-block, and (C1) have between 20,000 to 300,000 weight average molecular weight

(C2), has functionalized partially hydrogenated at least " high rubber " polystyrene-poly diene-polystyrene block copolymer of 1% functionality basically, " little end block " exists jointly with the amount between 8 to the 25 weight % that account for described segmented copolymer, in other words, each end-blocks has much smaller than the molecular weight of rubber-like mid-block, and

(C3), have＞1% but＜the functionalized partially hydrogenated at least polystyrene-poly diene-polystyrene block copolymer of 2% functionality, wherein said polystyrene end block exists jointly with the amount between 25 weight % to the 35 weight % of＞described segmented copolymer;

It is (C1), (C2) and (C3) in arbitrarily both combination or (C1), (C2) and (C3) three's combination, condition is: when only having (C2) be do not have (C1) with (C3);

(d) account for the functionalised polyolefin of 0 to 30 weight % of described composition, described alkene has 2 to 8 carbon atoms;

(e) account for hydrogenation not functionalized polystyrene-poly diene-polystyrene block copolymer of 1 to 20 weight % of described composition; And,

(f) additive, it is in order to strengthen the work-ing life of described composition.

2, composition as claimed in claim 1, wherein:

In (C1), the polystyrene block of the controlled distribution in the described polydiene mid-block is a polystyrene;

Described polydiene mid-block is selected from hydrogenated butadiene polymer, polyisoprene and poly-(isoprene/butadiene); And

(C1) has molecular weight Mw between 20,000 to 400,000.

3, composition as claimed in claim 2, wherein:

(C2) be to exist with the amount between 5 to 25 weight % of described composition,

And has the molecular weight between 20,000 to 300,000;

(C3) be to exist with the amount between 5 to 25 weight % of described composition,

And has the molecular weight between 20,000 to 300,000.

4, composition as claimed in claim 1, wherein (C1) with (C3) do not exist, and (C2) be that amount with 10 to 40 weight % of described composition exists.

5, composition as claimed in claim 1, wherein saidly have functionalized partially hydrogenated at least " high rubber " polystyrene-poly diene-polystyrene block copolymer of 1% functionality basically and have＞1% but＜the functionalized partially hydrogenated at least polystyrene-poly diene-polystyrene block copolymer of 2% functionality is functionalized by maleic anhydride.

6, composition as claimed in claim 1, wherein said alkene are to be selected from ethene and propylene, and described polyolefine is that the maleic anhydride that existed by the amount with described polyolefinic 0.5 to 4 weight % is functionalized.

7, a kind of method that is used to prepare an object, it comprises the Overmolded composition of thermoplastic elastomer is bonded to nylon sock, described method comprises composition as claimed in claim 1 is heated to temperature between 182 ℃ to 282 ℃, combines so that cover at least a portion of described substrate with described nylon sock through heating combination described subsequently.

8, a kind of object of shaping, it has the composition as claimed in claim 1 at least a portion that one deck takes shape in described article surface.