CN100572049C - Composite shaped body, its manufacture method and resin for bonding - Google Patents

Abstract

The invention discloses a kind of composite shaped body, the resin component that wherein contains the non-carbamate resins of thermoplasticity directly bonds mutually with the another kind of resin component that contains TPU.This composite shaped body is characterised in that: (Ia) the non-carbamate resins of thermoplasticity (Ib) contains at least a polyamide component (as aliphatic polyamide resin and aliphatic polyamide elastomer) with aliphatic series ring and the material with compound (as polyamide oligomer as well as) of amino group of being selected from, and perhaps non-carbamate resins of (IIa) thermoplasticity (IIb) and TPU contain the resin with polyether segment respectively.Resin combination (Ib) can be the resin combination (Ib-2) that contains the non-carbamate resins of thermoplasticity and have amino compound.Can prepare this composite shaped body by heating non-carbamate resins of at least a thermoplasticity and TPU and it being bondd mutually.According to the present invention,, also can make it directly with bonding with TPU parts securely by simple method with different performance even resin component contains as the non-carbamate resins of the thermoplasticity of matrix resin.

Description

Composite shaped body, its manufacture method and resin for bonding

Technical field

The present invention relates to a kind of attachable or resin (or resin combination attachable or can be bonding) that can be bonding, this resin or resin combination are applicable under adhesive-free and link into an integrated entity with the resin component that contains thermoplastic polyurethane, the invention still further relates to the composite article (perhaps composite molding) and the manufacture method thereof of moulding, wherein the resin component that contains above-mentioned resin is connected on the TPU parts and becomes one.

Background technology

For improving design or decorate properties or good sense of touch or quality (for example Rou Ruan quality), perhaps higher functional in order to give, proposed in conjunction with compound (moulding composite article) with various kinds of resin, wherein each resin has different hardness, moulding composite article for example, wherein at least a portion resin formed article is coated with thermoplastic elastomer (TPE).This moulding composite article is normally made by the bonding a plurality of moulding sections of adhesive.For example, Japanese patent application is not examined open No.267585/1996 (JP-8-267585A) (patent document 1) and is disclosed a kind of resin formed article, be adhesive wherein, a plurality of resin formed articles that form with polyamide or other resin mutually combined or bonding by finishing agent such as urethane polymer or carbamate.Yet the method for this use adhesive is not only because complicated step and uneconomical, and for example also has the problem of environmental pollution that is brought by organic solvent or other etc.And, very little or need under the situation of fine pattern at this resin formed article bond area, be difficult to commercial or industrial this resin formed article of large-scale production, because not only the coating step of adhesive becomes very complicated, and the adhesion strength of resin formed article or bonding stability are not enough.

On the other hand, consider, adopted the method for the direct hot melt of a plurality of moulding sections from the rationalization or the point of view of environment protection of production method.The moulding composite article that obtains by hot melt is normally produced by molding methods, as double-colored molding or insert molding (insert molding).Yet substance classes is different and be that the combination of acceptable material is very limited to hot melt, and most situations of combination only limit to the material of identical type.And, be not easy to set up the condition of moulding that obtains enough adhesion strengths.Therefore, for strengthening the part of fusion, except hot melt or thermal, also used such method, as on the zone of the moulding section that will bond, prepare the method for sags and crests (or part) for mechanical connection, by Corona discharge Treatment etc. and the method on chemical activation moulding section surface, the method lacquer coat of primer coating or other material is easy to form fracture owing to crooked on the zone that will bond.And these methods are tended to need complicated moulding section structure, perhaps increase the production stage number.The result is that such method has many shortcomings on product quality and economic factor.

For addressing these problems, studied and used the material of thermoplastic polyurethane as the resin component that constitutes the moulding composite article.This is goodish on adhesive property for a thermoplastic polyurethane.For example in shoemaking was used, the moulding compound plastic goods that contain polyamide and thermoplastic polyurethane were used as sole practically.For example Japanese patent application is not examined the barycenter body that open No.248201/1997 (JP-9-248201A) (patent document 2) has proposed a kind of cycling shoes, it comprises the sole part that is formed by the polyamide that strengthens as insert with glass fibre, and wherein the sidewall of sole part is by the polyurethane resin moulding.Yet owing to such purposes is exposed to the barycenter body under the mechanical exacting terms, so this list of references describes that in an embodiment the mechanical connection for sole part and polyurethane resin side wall portion needs through hole at the polyamide sole part.And Japanese patent application is not examined open No.308205/1995 (JP-7-308205A) (patent document 3) and has been proposed a kind of sole that strengthens by the heel that replaces at least a portion to be made of polyurethane resin with fibre-reinforced polyamide sheet.The document discloses to obtaining tolerating the bonding or the switching performance of the heavy bending of sole, and polyamide contains the mixture of polyamide and polyolefin (ionomer).Can be clear that by these documents, for being used in sole or other goods that need good mechanical properties or anti-bending or flex fatigue performance, now having turned one's attention to TPU and the superior polyamide of mechanical performance that itself to have the bonds well performance and be used in combination.Usually, because being resin itself, thermoplastic polyurethane has to a certain degree agglomerability for polyamide-based resin, so under enough conditions, under material sticking temperature or other condition, the composite formed body that can obtain to have the adhesion strength that can tolerate actual use.Yet, for bonding surface, needing under the situation of higher anti-bending or flex fatigue performance, perhaps under the very harsh situation of the environment for use of adhesive segment, adhesion strength that just need higher than above-mentioned composite formed body (a high grade (one-step higher)).That is to say that the adhesive property (intensity) of the part that obtains by hot melt or thermal is not enough, need further exquisite design or improve.

In these sole manufacturing fields, in sport footwear such as football, baseball or basketball shoes field, as sole is to obtain the higher flexibility and the strong cohesive property of storeroom, be extensive use of in conjunction with polyurethane resin and polyamide-based elastomeric composite formed body, wherein polyamide-based elastomer not only has high flexibility and toughness but also has good caking property (promptly having softened a kind of elastomer of polyamide-based resin by introducing polyether component).

For example, the careful open No.505333/1996 (JP-8-505333A) (patent document 4) of Japanese patent application discloses by the polyamide elastomer that will contain blowing agent and has been injected in the mould, in mould, embed or put into the moulding article of thermoplastic resin such as polyetheramides, polyether ester or polyurethane, and thermoplastic resin molded article (non-light-weighted plasticity thing) and elastomer (light-weighted thermoplastic elastomer (TPE)) is bonding and lightweight sole that obtain.Japanese patent application is not examined open No.125155/1995 (JP-7-125155A) (patent document 5) and is disclosed a kind of composite formed body, non-rigid (or soft) the plasticity thing that wherein will contain thermoplastic polyurethane and plasticizer by hot melt, be coated to hard plastic forming that the blend by polypropylene and polyamide forms partly on.Yet even in such composite formed body (for example using the composite formed body of polyurethane resin), the adhesion strength of two kinds of storerooms (for example with respect to the adhesion strength of polyamide elastomer as mating section) is still not enough.Therefore, such compound not only is subjected to molded condition or the influence of the material condition (production batch) that will use, and be subjected to the influence of the environment for use of product (composite formed body), caused the adhesion strength of composite formed body or the instability of durability (the particularly durability of bounding point).

In polyurethane resin and polyamide-based elastomeric being used in combination, no matter be in the practical application or the embodiment of patent documentation 4 on the market, the polyurethane that all uses polyethers system is as polyurethane resin, and to contain polyester be polyurethane resin and polyamide-based elastomeric compound and in fact do not make.Yet, be that polyurethane resin is compared with polyethers, polyester is that polyurethane resin has favorable mechanical performance and economy.Therefore, be not limited to sport footwear market, in the field of the compound of all use polyurethane series resins and polyamide-based resin, with regard to technology and market, a very big problem is, in the technical development of compound, polyethers is that polyurethane resin and polyester are that polyurethane resin has not used with being made any distinction between.

Moreover, Japanese patent application is not examined open No.273826/2002 (JP-2002-273826A) (patent document 6) and is disclosed a kind of compound that is combined with vulcanized rubber part and resin component, rubber is generated the reagent sulfuration by free radical in the vulcanized rubber part, and resin component contains the thermoplastic resin that has at least two hydrogen or sulphur atom in the average per molecule, and wherein the rail interaction of hydrogen or sulphur atom energy coefficient S is for being not less than 0.006.Yet owing to need crosslinking agent bonding two parts, this method need be by heating (typical temperature is not less than 160 ℃) two parts certain hour (being not less than 7 minutes usually), and makes two parts force each other to contact.Therefore in fact, in the product preparation of some resulting composite, this method is not suitable for the low material of hear resistance, and particularly the deformation temperature under the 0.45MPa load by the ISO definition is no more than 100 ℃ material.And, have in use under the situation of material of relative superior heat resistance, owing to stand the condition of HTHP for a long time, cause physical deformation in composite formed body as expanding and shrinking inevitably, therefore be difficult to obtain having the composite formed body of high dimensional accuracy.

Patent documentation 1:JP-8-267585A (claim)

Patent is offered 2:JP-9-248201A greatly

Patent documentation 3:JP-7-308205A

Patent documentation 4:JP-8-505333A

Patent documentation 5:JP-7-125155A (claim)

Patent documentation 6:JP-2002-273826A

Summary of the invention

The technical problem that invention will solve

Therefore an object of the present invention is to provide significantly improved composite formed body of a kind of adhesion strength and preparation method thereof, even wherein using the non-carbamate of different in kind is that resin component and thermoplastic polyurethane are resin component, these two parts also can directly also link together under adhesive-free securely.

Another object of the present invention provides and a kind ofly contains polyamide-based resin component and thermoplastic polyurethane is composite formed body of resin component and preparation method thereof, no matter wherein employed thermoplastic polyurethane is the kind of resin, these two parts all can connect or bond together securely.

Another object of the present invention provides a kind of attachable resin (or resin combination), no matter whether contain non-carbamate based thermoplastic resin as matrix resin, this attachable resin all can be under adhesive-free is that resin component is connected or bonds with thermoplastic polyurethane securely.

A further object of the present invention provides a kind of attachable resin (or resin combination), no matter the kind of matrix resin, it all can improve with the thermoplastic carbamate is the connectivity (or switching performance) of resin component.

A further object of the present invention provides a kind of attachable resin (or resin combination), and it can be securely is that resin component is connected and does not damage the performance of matrix resin with the thermoplastic carbamate.

A further object of the present invention provides a kind of method for preparing composite formed body, wherein in mode easily by the hot melt of short time, and do not need to experience complicated preparation process, be that resin component and TPU parts link together securely with non-carbamate.

The mode of technical solution problem

The inventor has done deep research and has reached above-mentioned purpose for achieving the above object, and final the discovery, (I-1) at least a portion polyamide component that constitutes polyamide-based resin, introduce alicyclic ring (or aliphatic series ring), compare with the polyamide-based resin that contains general aliphatic acid amides component, can realize that much higher and thermoplastic polyurethane are the adhesion strength of resin, no matter and the kind of polyurethane series resin, guaranteed that with polyethers be that polyurethane resin similar (or comparable) is connected degree, polyamide-based resin is firm or strong being connected of polyurethane resin with polyester; (I-2) the non-carbamate based thermoplastic resin (resin combination) that contains amino-compound has shown with thermoplastic polyurethane to be the high connectivity of resin, the resin component that contains non-carbamate based thermoplastic resin thus with contain the resin component bonding or be connected mutually securely that thermoplastic polyurethane is a resin; And (II) the two all has the polyamide-based resin of polyether segment and the combination that thermoplastic polyurethane is resin, because the enhancing of these two kinds of interlaminar resin affinity, can realize the firm connection or the bonding of these two kinds of resin components.

That is to say, composite formed body of the present invention is wherein to contain the resin component of non-carbamate based thermoplastic resin and contain the direct interconnective composite formed body of resin component that thermoplastic polyurethane is a resin, wherein non-carbamate based thermoplastic resin is non-carbamate based thermoplastic resin (resin (Ib)) or (resin (IIb)), and non-carbamate based thermoplastic resin and thermoplastic polyurethane are that resin satisfies following requirement (Ia) or (IIa), (Ia): non-carbamate based thermoplastic resin (Ib) contains at least a compound that has the polyamide component of alicyclic ring and contain amino, and perhaps (IIa): each non-carbamate based thermoplastic resin (IIb) and thermoplastic polyurethane are that resin all has polyether segment.Concomitantly, non-carbamate based thermoplastic resin can comprise the mode of non-carbamate based thermoplastic resin, and contains non-carbamate based thermoplastic resin and the mixture mode that contains amino compound.For example, non-carbamate based thermoplastic resin (Ib) can be the resin that (Ib-1) contains the polyamide component with alicyclic ring, and perhaps (Ib-2) contains non-carbamate based thermoplastic resin and the resin combination that contains amino compound.

In non-carbamate based thermoplastic resin (Ib), the polyamide component with alicyclic ring can be at least a alicyclic polyamide-based resin and alicyclic polyamide elastomer.And the polyamide component with alicyclic ring can contain alicyclic polyamide component (as alicyclic polyamide-based resin, alicyclic polyamide elastomer or alicyclic polyamide oligomer as well as) and non-alicyclic polyamide component (is that resin or aromatic polyamides are resin as aliphatic polyamide).Polyamide-based resin with alicyclic ring can be the polyamide component by using alicyclic diamine to obtain as diamine components.Non-carbamate based thermoplastic resin (Ib) can contain polyamide-based resin, in constituting all polyamide components of polyamide-based resin, the ratio (mol ratio) of alicyclic monomer residue and other monomer residue can be for the former/latter=about 100/0～0.1/99.9.

Non-carbamate based thermoplastic resin (Ib) can be that (Ib-2) contains the amino compound and the resin combination of non-carbamate based thermoplastic resin, and non-carbamate based thermoplastic resin can to contain at least a polyamide-based resin, polyester based resin, polycarbonate-based resin, polyphenylene sulfide be that resin, polysulfones are that resin, TPI are that resin, polyether-ketone are resin, olefin-based resin, phenylethylene resin series, (methyl) acrylic resin and halogen-containing vinyl resin.Contain amino compound and can in molecule, have a plurality of primary amino radicals.The amino group concentration that contains amino compound is 40～1000mmol/kg.Contain amino compound and can be number-average molecular weight and be 500～10000 and amino group concentration be the polyamide oligomer as well as of 50～700mmol/kg.With respect to the non-carbamate based thermoplastic resin of 100 weight portions, the ratio that contains amino compound can be about 0.01～20 weight portion.Resin combination (Ib-2) can contain and is selected from the non-carbamate based thermoplastic resin that polyamide-based resin, polyester based resin, polycarbonate resin and polyphenylene sulfide are resin; And the compound that contains amino.

The amino group concentration of non-carbamate based thermoplastic resin (Ib) can be to be not less than 10mmol/kg.

Thermoplastic polyurethane is that resin can be polyester urethane elastomer or polyethers urethane elastomers.In composite formed body (Ia), contain the resin component that the resin component of non-carbamate based thermoplastic resin (Ib) can be directly with to contain at least a thermoplastic polyurethane that is selected from polyester urethane elastomer and polyethers urethane elastomers be resin and be connected.

In composite formed body (IIa), the non-carbamate based thermoplastic resin (IIb) with polyether segment can contain and has polyoxy C _2-4The alkylidene fragment is as soft section polyamide elastomer.Non-carbamate based thermoplastic resin with polyether segment can contain the polyamide elastomer of polyamide fragment and polyether segment, and the polyamide fragment with respect to the ratio (weight ratio) of polyether segment can for, the former/latter=about 9/1～2.5/7.5.Thermoplastic polyurethane with polyether segment is that resin can contain and has polyoxy C _2-4The alkylidene fragment is as soft section thermoplastic polyether urethane elastomers.And, be that at least one of resin can contain at least a polytetramethylene glycol (polytetramethylene ether unit) at non-carbamate based thermoplastic resin and thermoplastic polyurethane.With respect to whole resin, the ratio of polyether segment in non-carbamate based thermoplastic resin (IIb) can be for about 10～90 weight %, and with respect to whole resin, thermoplastic polyurethane is that the ratio of polyether segment in the resin can be about 10～90 weight %.

Composite formed body of the present invention is suitable for part or the mechanical part (for example roller) make sole.

Of the present invention connect resin be a kind of can be the non-carbamate based thermoplastic resin that resin is connected directly with thermoplastic polyurethane, they are non-carbamate based thermoplastic resins (Ib) or (IIb), and non-carbamate based thermoplastic resin (Ib) contains at least a compound that has the polyamide component of alicyclic ring and contain amino, perhaps non-carbamate based thermoplastic resin (IIb) contains the non-carbamate based thermoplastic resin with polyether segment, and can be that resin directly is connected with the thermoplastic polyurethane with polyether segment.Non-carbamate based thermoplastic resin (Ib) can have the amino that concentration is not less than 10mmol/kg.

And the present invention also comprises a kind of method for preparing composite formed body, and this method comprises that non-carbamate based thermoplastic resin of heating and thermoplastic polyurethane are at least a resin in the resin, and these two kinds of resins are interconnected.For example, by heating non-carbamate based thermoplastic resin and thermoplastic polyurethane is that at least a resin in the resin is to fusion, and the resin of at least a molten condition contacted with other resin, two kinds of resins can be interconnected (and bonding) to together.And, perhaps can be by the heating thermoplastic polyurethane series resin to fusion, and be that resin contacts with a part of resin component that contains non-carbamate based thermoplastic resin with the thermoplastic polyurethane of molten condition, perhaps can be by the non-carbamate based thermoplastic resin of heating to fusion, and be that a part of resin component of resin contacts with the non-carbamate based thermoplastic resin of molten condition with containing thermoplastic polyurethane, carry out above-mentioned connection.And, can also be resin by heating each non-carbamate based thermoplastic resin and thermoplastic polyurethane, and be that resin contacts with the non-carbamate based thermoplastic resin of molten condition with the thermoplastic polyurethane of molten condition, carry out above-mentioned connection.And, can be by being selected from the forming method of thermoforming, injection moulding, extrusion molding and blow molding, making non-carbamate based thermoplastic resin and thermoplastic polyurethane in forming process is that resin interconnects.

Incidentally, in whole specification, the meaning of term " resin " comprises " resin combination " sometimes.And in whole specification, term " bonding " is meant the technology that a plurality of parts is combined with each other by adhesive, and term " connection (or bonding) " is meant that the technology that a plurality of parts is combined with each other without adhesive, these two terms are differences mutually.Fusion (or hot melt) is a kind of embodiment that connects.

The invention effect

Among the present invention, because polyamide-based resin contains the polyamide component with alicyclic ring, the composite formed body that therefore contains polyurethane series resin parts and polyamide-based resin component guarantees to have significantly improved adhesion strength (or bonding strength) between two kinds of resin components.And, not relying on the kind that the thermoplastic polyurethane that will use is a resin, two kinds of resin components can be interconnected or be bondd securely.Therefore, for example, contain the polyurethane series resin parts with good mechanical properties and the composite formed body of polyamide-based elastomer portion, also be applicable to the flexibility that needs whole composite formed body or the sport footwear field of plasticity.

And, because the present invention has used the non-carbamate based thermoplastic resin composition that contains amino compound, therefore whether no matter use non-carbamate based thermoplastic resin as matrix resin, non-carbamate based thermoplastic resin composition all can be without adhesive is that resin component is connected firm or powerfully or bonds with the thermoplastic carbamate.And, no matter the kind of matrix resin contains amino compound and can realize that all non-carbamate based thermoplastic resin and thermoplastic carbamate are the improvement of resin component connectivity energy.And when resin combination contained polyamide oligomer as well as, under the performance of not damaging matrix resin, resin combination can be that resin component is connected with the thermoplastic carbamate securely.In composite formed body of the present invention, above-mentioned resin combination is that combining of resin can be guaranteed under adhesive-free with thermoplastic polyurethane, non-carbamate is that resin component is direct and powerful being connected or bonding of resin component with thermoplastic polyurethane, even above-mentioned resin component performance difference.

And, according to the present invention, because having the polyamide-based resin of polyether segment is resin-bonded with the thermoplastic polyurethane with polyether segment, therefore even polyamide-based resin and thermoplastic polyurethane are that the performance of interlaminar resin is different, by reinforced polyamide is that resin and thermoplastic polyurethane are the affinity of interlaminar resin, can realize under adhesive-free that polyamide-based resin component and thermoplastic polyurethane are the direct and powerful bonding of resin component or are connected.

And, according to method of the present invention, the composite article that can prepare molding wherein need not to experience complicated preparation process, and the hot melt by plain mode can be that resin component and thermoplastic polyurethane are that resin component links together securely with non-carbamate.The composite article that particularly, also can prepare molding at short notice.

The specific embodiment

[composite formed body]

Composite formed body of the present invention is so a kind of composite formed body, wherein contain the resin component of non-carbamate system (perhaps based on it) thermoplastic resin (perhaps not the thermoplastic resin of amido-containing acid ester), directly interconnect with the resin component that contains thermoplastic polyurethane system (perhaps based on it) resin.In composite formed body, non-carbamate based thermoplastic resin is non-carbamate based thermoplastic resin (resin (Ib) and (IIb)), and non-carbamate based thermoplastic resin and thermoplastic polyurethane are that resin satisfies following requirement (Ia) or (IIa)

(Ia): non-carbamate based thermoplastic resin (Ib) contains at least a compound that has the polyamide component of alicyclic ring (polyamide component that contains alicyclic ring) and contain amino, perhaps

(IIa): each non-carbamate based thermoplastic resin (IIb) and thermoplastic polyurethane are that resin all has polyether segment.Requiring the composite formed body of (Ia) can be such composite formed body (Ia-1), wherein resin (Ib) contains a kind of resin (resin (Ib-1)) of the polyamide component with alicyclic ring, perhaps can be so a kind of composite formed body (Ia-2), wherein resin (Ib) contains a kind of resin combination (resin combination (Ib-2)) of non-carbamate system's (perhaps based on it) thermoplastic resin and the compound that contains amino.

And, the present invention can comprise a kind of can be directly with thermoplastic polyurethane be the resin non-carbamate system that is connected (or based on non-carbamate, amido-containing acid ester not) thermoplastic resin (or resin combination).This non-carbamate based thermoplastic resin can be (Ib) a kind of resin that contains at least a polyamide component with alicyclic ring and contain amino compound, and perhaps (IIb) is a kind of has polyether segment and can be the resin that resin is connected with the thermoplastic polyurethane with polyether segment directly.Resin (Ib) can be resin (Ib-1) or resin combination (Ib-2).

(non-carbamate based thermoplastic resin)

(I-b) contain the non-carbamate based thermoplastic resin of polyamide component with alicyclic ring

The non-carbamate based thermoplastic resin (Ib-1) that constitutes above-mentioned composite formed body (Ia-1) contains the polyamide component (alicyclic polyamide component) with alicyclic ring, and is generally the polyamide-based resin (or resin combination) that contains the polyamide component with alicyclic ring.As such polyamide component, the alicyclic polyamide component that has (a) to use separately that can exemplify, as alicyclic polyamide-based resin or alicyclic polyamide elastomer, perhaps its alloy or blend (mixture), and the polyamide-based resin combination that (b) contains alicyclic polyamide component (as alicyclic polyamide-based resin, alicyclic polyamide elastomer or alicyclic polyamide oligomer as well as) and non-alicyclic polyamide component, described non-alicyclic polyamide component is that resin or aromatic polyamides are resin for aliphatic polyamide for example.

(a) use alicyclic polyamide component or its mixture separately

Alicyclic polyamide component can be independent a kind of alicyclic polyamide-based resin or elastomer, or the alloy or the blend component of wherein alicyclic polyamide-based resin and the mixing of alicyclic polyamide elastomer.

The alicyclic polyamide-based resin that has alicyclic ring on main chain that alicyclic polyamide-based resin is a molecule or the side chain, and in main chain, have alicyclic ring usually.As alicyclic polyamide-based resin, for example can use by being selected from alicyclic diamine and alicyclic dicarboxylic acid as the obtainable alicyclic polyamide of the alicyclic monomer of monomer component with at least a.Alicyclic polyamide can be homopolyamide or copolyamide.

Alicyclic polyamide-based resin can be by the obtainable polyamide of the polymerization of alicyclic monomer, perhaps can obtain by the polymerization of alicyclic monomer and other copolymerizable monomer.Other copolymerizable monomer can be aromatic monomer such as aromatic diamine or aromatic dicarboxylic acid, considers preferred aliphatic series monomer such as aliphatic diamine and/or aliphatic dicarboxylic acid from the angle of flexibility or plasticity.And, according to the connectivity energy, preferably use alicyclic diamine as alicyclic monomer, particularly preferably be the mixture of alicyclic diamine and aliphatic dicarboxylic acid.The alicyclic polyamide-based resin that is obtained together by alicyclic monomer and aliphatic monomers is high transparent, is known as so-called transparent polyamide.

As alicyclic diamine, what can exemplify has a saturated alicyclic diamine [diaminourea cycloalkanes (preferred diaminourea C for example _5～12Cycloalkanes),, 4-DACH, 1,3-DACH, 1, the naphthylenediamine of 2-DACH, diaminourea cycloheptane or hydrogenation as diaminourea pentamethylene, 1], unsaturated cycloaliphatic diamines [diaminourea cyclenes (preferred C for example _5～12Cyclenes),, 2-diaminourea cyclohexene or 1,3-diaminourea cyclohexene as 1], the biphenyl of hydrogenation is diamines [two (amino cycloalkyl) alkane (preferred two (amino C for example _5～8Cycloalkyl) C _1～6Alkane), as 4,4 '-diaminourea hydrogenation biphenyl, two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, two (4-amino-2-methyl cyclohexyl) methane, or 2,2-two (4-aminocyclohexyl) propane; Two (the amino cycloalkanes of 4-) cycloalkane (preferred two (amino C _5～8Cycloalkyl) C _5～12Cycloalkane), as two (4-aminocyclohexyl) cyclohexane; Two (4-aminocyclohexyl) ketone; Two (4-aminocyclohexyl) sulfoxide; And 4,4 '-diaminourea dicyclohexyl ether], crosslinked cycloalkanes diamines (for example two-or three-ring C _7～10Alkane-diamines is as bornylane diamines, norbornane diamines or adamantane diamines), crosslinked cyclenes diamines (for example two-or three-ring C _7～10Alkene-diamines is as bornylene diamines, ENB) and other etc.These alicyclic diamines can be used alone or as a mixture.In these alicyclic diamines, preferably contain amino C _5～10The diamines of cycloalkanes, particularly C _6～8Cycloalkanes diamines or two (C _6～8Cycloalkyl) C _1～4The alkane diamines.

Diamine components can also comprise aliphatic diamine or aromatic diamine.Aliphatic diamine can comprise, for example C _4～16Alkylenediamine (preferred C _4～14Alkylenediamine, particularly C _6～12Alkylenediamine), as tetra-methylenedimine, hexamethylene diamine or dodecane diamines.Aromatic diamine can comprise, for example MXDP and phenylenediamine etc.These diamine components can be used alone or as a mixture.In these diamine components, consider the preferred aliphatic series diamines from the angle of flexibility or plasticity.

As the alicyclic dicarboxylic acid, what can exemplify has a saturated alicyclic dicarboxylic acid [cycloalkanes dicarboxylic acids (preferred C for example _5～12The cycloalkanes dicarboxylic acids), as pentamethylene dioctyl phthalate, cyclohexane-1,4-dioctyl phthalate, cyclohexane-1,3-dioctyl phthalate, cyclohexane-1, the 2-dioctyl phthalate or go back the heptane dioctyl phthalate], unsaturated cycloaliphatic dicarboxylic acids [cyclenes dicarboxylic acids (preferred C for example _5～12The cyclenes dicarboxylic acids),, 2-dioctyl phthalate, cyclohexene-1,3-dioctyl phthalate as cyclohexene-1], the biphenyl of hydrogenation is dicarboxylic acids [two (carboxyl cycloalkyl) alkane (preferred two (carboxyl C for example _5～8Cycloalkyl) C _1～6Alkane), as the biphenyl-4 of hydrogenation, 4 '-dioctyl phthalate, two (4-carboxyl cyclohexyl) methane, two (4-carboxyl-3-methylcyclohexyl) methane, two (4-carboxyl-2-methylcyclohexyl) methane or 2,2-two (4-carboxyl cyclohexyl) propane; Two (4-carboxyl cyclohexyl) ketone; Two (4-carboxyl cyclohexyl) sulfoxide; And 4,4 '-dicarboxyl dicyclohexyl ether], crosslinked cycloalkanes dicarboxylic acids (two-or three-ring C _7～10The alkene dicarboxylic acids is as bornylene dioctyl phthalate or ENB dioctyl phthalate), and other etc.In these alicyclic dicarboxylic acids, preferably contain C _5～10The dicarboxylic acids of cycloalkanes, particularly C _6～8Cycloalkanes dicarboxylic acids or two (C _6～8Cycloalkyl) C _1～4The alkane dicarboxylic acids.

The dicarboxylic acid component can also comprise aliphatic dicarboxylic acid or aromatic dicarboxylic acid.As aliphatic dicarboxylic acid, for example can mention alkane dicarboxylic acids (preferred C with 4～20 carbon atoms _4～16Alkane dicarboxylic acids, particularly C _6～14The alkane dicarboxylic acids), as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid (suberic acid), azelaic acid, decanedioic acid, dodecanedioic acid.Aromatic dicarboxylic acid for example comprises terephthalic acid (TPA), M-phthalic acid, phthalic acid and other etc.These dicarboxylic acid components can be used alone or as a mixture.In these dicarboxylic acid components, consider the preferred aliphatic series dicarboxylic acids from the angle of flexibility.

In alicyclic polyamide-based resin, the alicyclic monomer residue with respect to the ratio (or mol ratio) of other copolymerizable monomer residue is, [alicyclic monomer residue/copolymerizable monomer residue]=about 100/0～0.1/99.9, preferred about 90/10～0.5/99.5 (as 70/30～1/99), more preferably from about 60/40～3/97 (particularly about 50/50～5/95).With regard to connectivity, the ratio of alicyclic monomer residue is preferably bigger, but just flexible, the ratio of alicyclic monomer residue is preferably less.Therefore preferably select the suitable proportion of alicyclic monomer residue according to purpose.

And alicyclic monomer can only be added on the end group of polymer.The method that adds can comprise, for example comprise with carboxyl the aliphatic series mentioned later or the end group of aromatic polyamides are carried out end-blocking, and holding the method that adds aliphatic diamine on the carboxyl, perhaps be included in polymerization under a small amount of dicarboxylic acid component's the existence and have the lactams (as caprolactam or omega-lauryl lactan (lauryl lactam)) of about 4～20 carbon atoms, on the end carboxyl, add the method for alicyclic diamine subsequently, and other method.

In these alicyclic polyamide-based resins, as mentioned above, consider that the preferred alicyclic polyamide-based resin that is obtained by alicyclic diamine and aliphatic dicarboxylic acid that uses is for example especially preferably by containing amino C from connectivity and flexible angle _5～10The diamines of cycloalkanes [C for example _6～8The cycloalkanes diamines, as DACH, two (amino C _6～8Cycloalkyl) C _1～4Alkane is as two (4-aminocyclohexyl) methane or two (4-amino-2-methyl cyclohexyl) methane] with have about 4～20 any alkane dicarboxylic acids (as C _6～14The alkane dicarboxylic acids is as azelaic acid, decanedioic acid or dodecanedioic acid) the alicyclic polyamide-based resin that obtains.

Alicyclic polyamide can be used alone or as a mixture.In alicyclic polyamide-based resin, the condensation product of aliphatic dicarboxylic acid and alicyclic diamine (homopolymerization or copolyamide) or other etc. are preferred.

The number-average molecular weight of alicyclic polyamide-based resin is about 6000～100000, and is preferred about 8000～50000, more preferably from about 10000～30000.Can regulate molecular weight by using aliphatic diamine and/or the alicyclic diamine more excessive than amount of calculation in the polymerization.

Alicyclic polyamide elastomer (alicyclic polyamide block copolymer) can comprise that [for example contain polyether segment or block as soft section alicyclic polyamide-polyether block copolymer, described polyether block for example is polyoxygenated C to alicyclic polyamide-polyether block copolymer _2～4Alkylidene (as polyoxygenated tetramethylene (PTMG), polyoxygenated ethylidene or polyoxygenated propylidene)], and other etc.As alicyclic polyamide-block, can use the polyamide-block that constitutes alicyclic polyamide-based resin.Alicyclic polyamide elastomer can be the copolyamide elastomer, different block combination at least a and kind in wherein alicyclic polyamide-block and the polyether block.And alicyclic polyamide-block and polyethers can be respectively copolyamide block and copolyether block.

As alicyclic polyamide-polyether block copolymer, the block copolymer that has alicyclic polyamide-block and copolycondensation by having reactive terminal group to obtain that can mention with polyether block of reactive terminal group, particularly alicyclic polyetheramides (for example, alicyclic polyamide-block and block copolymer with dicarboxyl end group) with polyoxyalkylene block of two amine end groups, polyether ester amides (for example, alicyclic polyamide-block and the block copolymer with polyoxyalkylene block of dihydroxy end group with dicarboxyl end group have the alicyclic polyamide-block of two amine end groups and the block copolymer of the polyoxyalkylene block with dihydroxy end group (for example end group polyoxyalkylene block of dicarboxylic acids esterification)) etc.

The ratio that constitutes the alicyclic monomer of alicyclic polyamide elastomer can be selected from and the identical scope of alicyclic polyamide-based resin.These alicyclic polyamide elastomers can be used alone or as a mixture.

Consider that from the angle of connectivity alicyclic polyamide elastomer preferably uses with above-mentioned alicyclic polyamide-based resin-bonded.When alicyclic polyamide-based resin is used in combination with alicyclic polyamide elastomer, above-mentioned ratio (weight ratio) (alicyclic polyamide-based resin/alicyclic polyamide-based elastomer)=about 99/1～30/70, preferred about 97/3～50/50, more preferably from about 95/5～60/40.

Alicyclic polyamide component can be alicyclic polyamide-based resin and alicyclic polyamide elastomer, can be alicyclic polyamide oligomer as well as in addition.These alicyclic polyamide components can be used alone or as a mixture.

As alicyclic polyamide oligomer as well as, can use the relatively low alicyclic polyamide of molecular weight, they can be by common mode, for example by regulating polycondensation or other condition and using above-mentioned alicyclic polyamide component to make.For example, as the polyamide component of raw material, the mixture that above-mentioned diamines and dicarboxylic acids are arranged that can mention, above-mentioned diamines and/or dicarboxylic acids and the lactams (lactams that for example has 4～20 carbon atoms, as omega-lauryl lactan) mixture, and other mixture.Can by for example exert pressure down and heating under, polymerization lactams and alicyclic diamine obtain alicyclic polyamide oligomer as well as.

The number-average molecular weight of alicyclic polyamide oligomer as well as can be for example about 500～10000, preferred about 1000～10000 (for example about 2000～9000), more preferably from about 3000～8000 (for example about 3000～6000).And, can improve the polyamide-based resin of formation resin component and the switching performance of thermoplastic polyurethane by using the higher relatively alicyclic polyamide oligomer as well as of molecular weight.Can regulate above-mentioned number-average molecular weight by using aliphatic diamine and/or the alicyclic diamine more excessive than the amount of calculation in the polymerization.

In these alicyclic polyamide components, from switching performance, preferred alicyclic polyamide-based resin or alicyclic polyamide oligomer as well as, particularly alicyclic polyamide-based resin.And, consider from the angle of connectivity, preferably use by (for example containing amino C with alicyclic diamine _5～10The diamines of cycloalkanes) polyamide component that obtains is as alicyclic polyamide component.

(b) contain the composition of alicyclic polyamide component and non-alicyclic polyamide component

Polyamide component with alicyclic ring can be the composition that contains alicyclic polyamide component and non-alicyclic polyamide component (polyamide component that does not perhaps contain alicyclic ring).

As non-alicyclic polyamide component, the aliphatic polyamide that has that can mention is that resin and aromatic polyamides are resin, and can use various homopolyamides and copolyamide.

At aliphatic polyamide is in the resin, and homopolyamide can comprise the condensation product of aliphatic diamine component and aliphatic dicarboxylic acid component, and for example polyamide 46, polyamide 66, polyamide 6 10, polyamide 6 12 and polyamide 1010; Lactams [the lactams that for example has about 4～20 carbon atoms (preferred about 4～16), as epsilon-caprolactams or omega-lauryl lactan] or the amino carboxylic acid [amino carboxylic acid that for example has about 4～20 carbon atoms (preferred about 4～16), as the omega-amino-hendecanoic acid] homopolyamide, polyamide 6 for example, polyamide 11 and polyamide 12; And other etc.And copolyamide can comprise by can constituting the monomer component of polyamide, the copolyamide that obtains as the combined polymerization of aliphatic diamine component, aliphatic dicarboxylic acid component, lactams component and amino carboxylic acid component.The example of copolyamide can comprise the copolymer of 6-aminocaprolc acid and 12 amino dodecanoic acid; The copolymer of 6-aminocaprolc acid, 12 amino dodecanoic acid, hexamethylene diamine and adipic acid; The dimer acids of hexamethylene diamine, adipic acid, hydrogenation and the copolymer of 12 amino dodecanoic acid; Polyamide 6/11, polyamide 6/12, polyamide 66/11, polyamide 66/12; And other etc.These aliphatic polyamides are that resin can be used alone or as a mixture.

Aromatic polyamides is that resin can comprise that wherein at least one component that is selected from aliphatic diamine component and aliphatic dicarboxylic acid component contains the polyamide of aromatic component, the polyamide that for example has aromatic component in diamine components [for example, the condensation product of aromatic diamine (as m-xylene diamine) and aliphatic dicarboxylic acid, as MXD-6], the polyamide [condensation product of aliphatic diamine (as trimethylhexamethylenediamine) and aromatic dicarboxylic acid (as terephthalic acid (TPA), M-phthalic acid)] that in the dicarboxylic acid component, has aromatic component, and other etc.These aromatic polyamides are that resin can be used alone or as a mixture.

Incidentally, in non-alicyclic polyamide component, can be used in combination the polyamide that wherein diamine components and dicarboxylic acid component all contain aromatic component [aramid completely for example is as poly-(-phenylene isophthaloyl amine) (as fragrant acid amides)].

Non-alicyclic polyamide component can also comprise and contains the polyamide of dimer acids as the dicarboxylic acid component, wherein by using a spot of multifunctional polyamines and/or polycarboxylic acid component to introduce the polyamide of branched structure, modified polyamide (as the N-alkoxymethyl polyamide), aliphatic series or aromatic polyamides block copolymer, and other etc.

These non-aliphatic polyamide components can be used alone or as a mixture.In these components, just flexible, can preferably use aliphatic polyamide is that resin or aliphatic polyamide block copolymer, particularly aliphatic polyamide are resin.

According to the ratio of alicyclic ring in alicyclic polyamide component, alicyclic polyamide component with respect to the ratio (weight ratio) of non-alicyclic polyamide component can be selected from the former/latter=about 99/1～1/99, consider from the angle of connectivity, this ratio can be for example for the former/latter=about 98/2～30/70, preferred about 97/3～50/50, more preferably from about 95/5～70/30.And when the aliphatic polyamide component contains alicyclic polyamide oligomer as well as, even when a small amount of, it also can guarantee enough connectivities.In view of the above, consider from flexible or other angle, alicyclic polyamide component with respect to the ratio of non-alicyclic polyamide component for example can be the former/latter=about 50/50～0.1/99.9, preferred about 40/60～3/97,30/70～5/95 (particularly about 20/80～5/95) more preferably from about.

Have in the polyamide component of alicyclic ring at these, with regard to connectivity, the component that preferably contains alicyclic polyamide-based resin, (i) alicyclic polyamide-based resin particularly, the mixture of (ii) alicyclic polyamide-based resin and alicyclic polyamide elastomer, (iii) alicyclic polyamide-based resin and aliphatic polyamide are the mixture of resin.

Among the present invention, has the amino that the polyamide component of alicyclic ring can have specific concentrations.Amino is generally free amine group (NH ₂), and usually do not comprise derived from the amido link that constitutes polyamide-based resin backbone, urea key, amino-formate bond and other-NH-(imino group) group and-N＜group.Polyamide-based resin can have free amine group at its side chain or at the end group place of main chain.

With respect to the non-carbamate of 1kg is resin (polyamide-based resin), in having the polyamide-based resin of alicyclic ring, amino content (or concentration) is for being not less than 10mmol (for example about 10～300mmol), preferably be not less than 15mmol (for example about 15～200mmol), more preferably be not less than 20mmol (for example about 20～150mmol), particularly be not less than 30mmol (for example about 30～100mmol).

Polyamide-based resin preferably contains the amino of above-mentioned scope, particularly contains the end amino of above-mentioned scope.Amino can be alicyclic amino, and wherein a part or all end amino are alicyclic amino (for example direct and alicyclic group key amino even is as cycloalkyl amino).And for regulating amino content (concentration), [diamines (as the above-mentioned aliphatic diamine that exemplifies, alicyclic diamine and aromatic diamine) for example, (for example polyalkylenepolyamines is (as many C for polyamines such as aliphatic polyamines can also to add amino-compound _2～3Alkylene polyamine), as diethylenetriamines or trien)] or other compound.

Among the present invention,, especially preferably use alicyclic diamine for amino being converted into alicyclic amino (for example cycloalkyl amino) derived from alicyclic diamine.Have use, improved the connectivity (or adhesion strength) of non-carbamate based thermoplastic resin (polyamide-based resin) and TPU parts derived from the polyamide component of the alicyclic amino of alicyclic diamine.

Incidentally, the concentration with carboxyl in the polyamide component of alicyclic ring has no particular limits, and for example can be about 0.1～200mmol/kg, preferred about 0.5～150mmol/kg, more preferably from about 1～100mmol/kg.

Among the present invention, constituting non-carbamate is in all polyamide components of resin (polyamide-based resin), with respect to other monomer residue, the ratio of alicyclic monomer residue (mol ratio) for the former/latter=about 100/0～0.1/99.9, preferred about 90/10～0.5/99.5, more preferably from about 70/30～1/99.

(Ib-2) non-carbamate based thermoplastic resin (resin combination)

The resin combination (Ib-2) that constitutes above-mentioned composite formed body (Ia-2) contains matrix resin (non-carbamate based thermoplastic resin) and contains amino compound, and by being being connected of resin or bonding, and being applicable to and forming composite formed body (composite molding goods) with the thermoplastic carbamate.

(matrix resin)

For the non-carbamate based thermoplastic resin that is the matrix resin of non-carbamate based thermoplastic resin composition (Ib-2), what for example can exemplify has a polyamide-based resin, polyester based resin, polycarbonate-based resin, polyphenylene sulfide is a resin, polysulfones is resin [for example polysulfones, poly-(an ether sulfone) and gather (4,4 '-bis-phenol ether sulfone)], TPI is a resin, and polyether-ketone is a resin [polyether-ketone for example, polyether-ether-ketone], the olefin-based resin, phenylethylene resin series, (methyl) acrylic resin, halogen-containing vinyl resin, and other etc.These non-carbamate based thermoplastic resins can be used alone or as a mixture.

(a) polyamide-based resin

As polyamide-based resin, the aliphatic polyamide that has that can mention is a resin, and alicyclic polyamide-based resin, aromatic polyamides are resin or other etc., and can use various homopolyamides and copolyamide.

At aliphatic polyamide is in the resin, and homopolyamide can be included in the aliphatic polyamide that exemplifies in non-carbamate based thermoplastic resin (Ib-1) part, just aliphatic diamine component [C for example _4～16Alkylenediamine is as tetra-methylenedimine, hexamethylene diamine or dodecane diamines (preferred C _4～14Alkylenediamine, particularly C _6～12Alkylenediamine)] and the aliphatic dicarboxylic acid component [alkane dicarboxylic acid who for example has about 4～20 carbon atoms is as adipic acid, decanedioic acid or dodecanedioic acid (preferred C _4～16Alkane dicarboxylic acid, particularly C _6～14The alkane dicarboxylic acid)] condensation product.

Alicyclic polyamide-based resin can be included in the alicyclic polyamide that exemplifies in non-carbamate based thermoplastic resin (Ib-1) part, just has at least aly to be selected from alicyclic diamine and alicyclic dicarboxylic acid as the homopolyamide or the copolyamide that constitute component.As so alicyclic polyamide-based resin, for example can use by using alicyclic diamine and/or alicyclic dicarboxylic acid as the diamines of the polyamide-based resin of at least a formation and dicarboxylic acid component's component, and the alicyclic polyamide that obtains.As diamine components and dicarboxylic acid component, above-mentioned aliphatic diamine and/or aliphatic dicarboxylic acid preferably are used in combination (so-called transparent polyamide) with alicyclic diamine and/or alicyclic dicarboxylic acid.

The example of alicyclic diamine can be included in the alicyclic diamine that exemplifies in above-mentioned non-carbamate based thermoplastic resin (Ib-1) part, i.e. diaminourea cycloalkanes such as DACH (diaminourea C for example _5～10Cycloalkanes); Two (amino cycloalkyl) alkane, as two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, or 2,2-two (4 '-aminocyclohexyl) propane [two (amino C for example _5～8Cycloalkyl) C _1～3Alkane]; And other etc.And the alicyclic dicarboxylic acid can comprise the cycloalkanes dicarboxylic acids, as cyclohexane-1, and 4-dioctyl phthalate or cyclohexane-1,3-dioctyl phthalate (C for example _5～10Cycloalkanes-dicarboxylic acids), and other etc.

In alicyclic polyamide-based resin, the condensation product of preferred aliphatic series dicarboxylic acids and alicyclic diamine (homopolymerization or copolyamide) for example.

As aromatic polyamides is resin, and can use the aromatic polyamides that is exemplified in above-mentioned non-carbamate based thermoplastic resin (Ib-1) part is resin, and the condensation product of aromatic diamine (for example m-xylene diamine) and aliphatic dicarboxylic acid for example is as MXD-6; The condensation product of aliphatic diamine (for example trimethylhexamethylenediamine) and aromatic dicarboxylic acid (for example terephthalic acid (TPA), M-phthalic acid); And other etc.

Incidentally, in polyamide-based resin, can be used in combination the polyamide that wherein diamine components and dicarboxylic acid component all contain aromatic component [aramid completely for example is as poly-(-phenylene isophthaloyl amine) (as fragrant acid amides)].

Polyamide-based resin can also comprise and contains the polyamide of dimer acids as the dicarboxylic acid component, wherein by using a spot of multifunctional polyamines and/or polycarboxylic acid component to introduce the polyamide of branched structure, modified polyamide (as the N-alkoxymethyl polyamide), polyamide block copolymer, and their composition and other etc.

The example of polyamide block copolymer can be included in the polyamide elastomer that exemplifies below, contain polyether segment, and polyamide elastomer for example is polyamide-polyether block copolymer (for example contain polyether segment or as polytetramethylene glycol, polyethylene glycol or the polypropylene glycol polyamide-polyether block copolymer as soft section).Polyamide-polyether block copolymer can comprise the block copolymer that obtains by polyamide-block with reactive terminal group and the copolycondensation with polyether block of reactive terminal group, particularly polyetheramides (for example, polyamide-block and block copolymer with diaminourea end group with polyoxyalkylene block of dicarboxyl end group, polyamide-block and block copolymer with dicarboxyl end group) with polyoxyalkylene block of diaminourea end group, polyether ester amides (for example, polyamide-block and block copolymer with dicarboxyl end group with polyoxyalkylene block of dihydroxy end group), and other etc.Incidentally, the obtainable polyamide elastomer of commodity seldom has amino group in most cases usually.

Polyamide-based resin can be used alone or as a mixture.And polyamide-based resin can be the blend or the alloy of multiple polyamide-based resin.

Preferred polyamide-based resin comprises that aliphatic polyamide is a resin, alicyclic polyamide-based resin (particularly transparent polyamide), and other etc.Polyamide-based resin can be separately or with aromatic polyamides be that resin-bonded is used.And polyamide block copolymer also is preferred.

The number-average molecular weight of polyamide-based resin is about 6000～100000, and is preferred about 8000～50000, more preferably from about 10000～30000.

Incidentally, be used as under the situation of matrix resin at polyamide-based resin, is the connectivity of resin component (for example barras parts) for improving non-carbamate based thermoplastic resin component (for example animi resin parts) with thermoplastic polyurethane, the fusion of polyamide-based resin and crystallization enthalpy can be not more than 100J/g (for example about 0～100J/g), preferably be not more than 80J/g (for example about 0～80J/g), more preferably no more than 70J/g (for example about 0～70J/g).According to the present invention,, also can guarantee necessarily and effectively be connected even use the polyamide-based resin of low-crystallinity.Fusion in the polyamide-based resin like this and crystallization enthalpy for example can be selected from the scope that is not more than 30J/g (for example about 0～30J/g), preferably be not more than 20J/g (for example about 0～20J/g), more preferably no more than 17J/g (about 0～17J/g).

" fusion and the crystallization enthalpy " of polyamide-based resin is meant and deducts the resulting value of the crystallization heat that crystallization produced (Δ Hf) that is accompanied by resin from the necessary melting heat of molten resin (Δ Hm).That is to say, in the test of melting heat, if along with the rising crystallization heat and the melting heat subsequently of temperature can both be observed, then the fusion of polyamide-based resin and crystallization enthalpy promptly are considered to deduct from the observation Δ Hm of the melting heat of every gram resin the resulting value of observation Δ Hf of the crystallization heat of every gram resin.Fusion and crystallization enthalpy can pass through Differential Scanning Calorimeter (DSC instrument) and measure with the method for JIS (Japanese Industrial Standards) K 7122.Incidentally, because amorphous polyamide can not be observed crystallization heat fully, therefore the fusion and the crystallization enthalpy of such polyamide are identified as 0J/g.

Have the polyamide-based resin, particularly fusion of such fusion and crystallization enthalpy and the polyamide-based resin (for example transparent polyamide) that crystallization enthalpy is not more than 20J/g, can be with known molding methods by molding.For example can examine open No.239469/1996 (JP-8-239469A) referring to Japanese patent application about the detailed content of so polyamide-based resin, Japanese patent application is examined open No.1544/2000 (JP-2000-1544A) and other etc.

Incidentally, the concentration of carboxyl is not limit to particular value in the polyamide-based resin, for example can be about 0.1～200mmol/kg, preferred about 0.5～150mmol/kg, more preferably from about 1～100mmol/kg.

(b) polyester based resin

Polyester based resin can comprise polyalkylene aromatic ester, for example C _2～4Aklylene glycol terephthalate such as PETG or polybutylene terephthalate (PBT), and C _2～4Aklylene glycol naphthalate such as PEN, perhaps its copolyesters [for example contains diol component and (for example (gathers) oxygen C _2～4Aklylene glycol such as ethylene glycol and polyethylene glycol; Aliphatic series C _5～16Glycol is as 1, the 6-hexylene glycol; Alicyclic diol is as 1, the 4-cyclohexanedimethanol) and dicarboxylic acid component (for example aliphatic dicarboxylic acid such as adipic acid or decanedioic acid; Aromatic dicarboxylic acid such as M-phthalic acid) as the copolyesters of copolymerizable component], [for example based on the polyester elastomer of polyester-polyethers, it contains poly-C to the polyester based elastomers _2～4Alkylidene aromatic ester such as PETG or polybutylene terephthalate (PBT) are as hard section, polyoxy C _2～4Aklylene glycol such as polytetramethylene glycol are as soft section; And based on the polyester elastomer of polyester-polyester, it contains poly-C _2～4The alkylidene aromatic ester is as hard section, and poly-aliphatic (acid) ester is as gathering (6-caprolactone) or poly adipate succinic acid ester as soft section], and other etc.

(c) polycarbonate-based resin

Polycarbonate-based resin can comprise by dihydroxy compounds [alicyclic diol or bisphenol compound (two (hydroxyaryl) alkane (preferred two (hydroxyl C for example for example _6～10Aryl) C _1～6Alkane), as two (4-hydroxy phenyl) methane or bisphenol-A); Also have two (hydroxyl C in addition _6～10Aryl) ether, as 4,4 '-dihydroxy diphenyl ether; Two (hydroxyl C _{6～ 10}Aryl) sulfone, as 4,4 '-dihydroxy-diphenyl sulfone; Two (hydroxyl C _6～10Aryl) sulfide, as 4,4 '-dihydroxy diphenyl sulfide; Two (hydroxyl C _6～10Aryl) ketone,, 4 '-dihydroxy diphenylketone as 4] polymer that obtains of photoreactive gas or carbonic ester (for example diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate) reaction, and other etc.

(d) polyphenylene sulfide is a resin

Polyphenylene sulfide is that resin can comprise linear or crosslinked polyphenylene sulfide, polyphenylene sulfide (as poly--1, the 4-phenylene sulfide) for example, poly-diphenylsulfide (PBPS), polyphenylene sulfide ketone (PPSK) and other etc.

(e) olefin-based resin

Olefin-based resin or polyolefin-based resins can comprise C _2～10The homopolymers of alkene or copolymer (for example polyethylene, polypropylene, poly-1-butylene), ethylene-propylene copolymer, the copolymer of alkene and copolymerizable monomer (ethylene-vinyl acetate copolymer for example, ethene-(methyl) acrylate copolymer), the polyolefin of modification, polyolefin elastomer (contain hard section of polyolefin (for example polyethylene or polypropylene) and contain soft section elastomer of rubber components (as ethylene-propylene rubber (EPR) or ethylene-propylene-dience rubber (EPDM))), and other etc.

(f) phenylethylene resin series

Phenylethylene resin series can comprise polystyrene (GPPS), high impact polystyrene (HIPS), acrylonitritrile-styrene resin (AS resin), acrylonitrile-styrene-butadiene block copolymer (ABS resin), polystyrene based elastomers (s-B-S (SBS) block copolymer for example, styrene-isoprene-phenylethene (SIS) block copolymer), and other etc.

(g) (methyl) acrylic resin

(methyl) acrylic resin can comprise the homopolymers or the copolymer [for example polymethyl methacrylate] of (methyl) acrylic acid or its ester, the copolymer of (methyl) acrylic acid or its ester and other copolymerizable monomer [(methyl) acrylic acid-styrol copolymer for example, (methyl) acrylic styrene copolymer], and other etc.

(h) halogen-containing vinyl resin

Halogen-containing vinyl resin can comprise chloride vinyl resin such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, fluorine-containing vinyl resin, polyvinyl chloride based elastomers, fluorine based thermoplastic elastomer and other etc.

Non-carbamate based thermoplastic resin can separately and mix and use.In non-carbamate based thermoplastic resin, preferred polyamide is that resin, polyester based resin, polycarbonate-based resin, polyphenylene sulfide are resin, polystyrene resin and polyolefin-based resins etc.And, as non-carbamate based thermoplastic resin, can use thermoplastic elastomer (TPE) (for example polyamide-based elastomer, polyester based elastomers, polyolefin elastomer, polystyrene based elastomers, polyvinyl chloride based elastomers and fluorine-containing thermoplastic elastomer (TPE)).

Matrix resin can have or not have in fact amino group.Have under the amino situation at matrix resin, matrix resin can have amino group at the side chain of resin or the end of its main chain.Incidentally, amino group typically refers to free amine group (NH ₂), and do not comprise usually the amido link that is contained in matrix resin (for example polyamide-based resin) main chain and derived from the urea key of carbamate groups ,-NH-(imino group) group and-N＜group.

The content of amino group (or concentration) can be less in the matrix resin, for example about 0～20mmol/kg, preferred about 0～10mmol/kg, more preferably from about 0～8mmol/kg.

(containing amino compound)

As containing amino compound, can use the various compounds that contain amino that can mix, as polyamines [diamines (for example above-mentioned aliphatic diamine (C for example for example with matrix resin _4～16Alkylenediamine is as hexamethylene diamine), alicyclic diamine and aromatic diamine); Also has polyoxy alkylidene diamines (polyoxy C for example in addition _2～4Alkylenediamine is as the polyoxygenated ethylene diamine); Polyamines, aliphatic polyamines for example, as polyalkylenepolyamines, as diethylenetriamines and trien (as many C _2～3Alkylene polyamine)], monoamine, and polyamide oligomer as well as.

As polyamide oligomer as well as, can use the relatively low polyamide of molecular weight, it is by common mode, as by regulating polycondensation or other condition and using above-mentioned polyamide component to obtain.For example, polyamide component as raw material, that can mention has an above-mentioned diamines [aliphatic diamine (for example Alkylenediamine) for example, alicyclic diamine, aromatic diamine] and the combination of dicarboxylic acids (for example aliphatic dicarboxylic acid and aromatic dicarboxylic acid), the combination of above-mentioned diamines and/or dicarboxylic acids and lactams (lactams that for example has about 4～20 carbon atoms is as omega-lauryl lactan), and other combination etc.Polyamide oligomer as well as can by for example in pressurization, heating and under stirring polymerization lactams and aliphatic diamine obtain.

The number-average molecular weight of polyamide oligomer as well as is for for example about 500～10000, preferred about 500～8000 (for example about 1000～7000), more preferably from about 1000～5000, about 2000～6000 (for example about 3000～6000) usually.As polyamide oligomer as well as, for example its number-average molecular weight can be for about 1000～10000, and is preferred about 2000～9000, and more preferably from about 3000～8000.The use of such polyamide oligomer as well as has improved the polyamide-based resin of formation resin component and the connectivity (or switching performance) of thermoplastic polyurethane.

Polyamide oligomer as well as can have free amine group in an end of main chain usually at least, also can have free amine group in two ends of main chain, perhaps can have free amine group on side chain.Containing amino compound can be used alone or as a mixture.

Containing amino compound can be monoamine, and is preferably usually and has the compound that is no less than two amino (for example primary amino radical) in the molecule, polyamide oligomer as well as particularly with regard to connectivity.

The amino group concentration that contains amino-compound for example can be about 40～1000mmol/kg, preferred about 50～700mmol/kg, more preferably from about 100～500mmol/kg.Particularly, contain the end amino that amino-compound preferably has above-mentioned scope.

Matrix resin with respect to 100 weight portions, the ratio that contains amino-compound for example can be selected from about 0.01～20 weight portion, preferably be no more than 10 weight portions (about 0.01～10 weight portion), more preferably from about 0.1～8 weight portion particularly is no more than about 7 weight portions (about 0.5～7 weight portion).Incidentally, excessive contain amino-compound and can damage resin property, particularly when using non-carbamate based thermoplastic resin composition as animi resin.

Because non-carbamate based thermoplastic resin composition (Ib-2) contains amino (amino of the self-contained amino-compound of normally deriving) usually, therefore even matrix resin is non-carbamate based thermoplastic resin, non-carbamate based thermoplastic resin composition also can be directly and is that resin or resin component are connected or bond with thermoplastic polyurethane securely.In the lkg resin combination, the ratio (concentration) of amino group in resin combination for example can be for being not less than 10mmol (for example about 10～300mmol), preferably be not less than 15mmol (for example about 15～200mmol), be not less than about 20mmol (for example about 20～150mmol), particularly be not less than about 30mmol (for example about 30～100mmol).Particularly, resin combination preferably has the end amino of above-mentioned scope.Incidentally, along with non-carbamate based thermoplastic resin or contain amino group concentration in the amino-compound or the ratio of these components changes, concentration amino in the resin combination is suitably adjustable.

(IIb) have polyether segment non-carbamate based thermoplastic resin

The non-carbamate based thermoplastic resin (IIb) that constitutes above-mentioned composite formed body (IIa) has polyether segment, and is generally the polyamide-based resin with polyether segment.

Non-carbamate based thermoplastic resin (polyamide-based resin) comprises have at least one polyether segment [for example, polytetramethylene glycol (PTMG, polytetramethylene ether) fragment or unit, polyoxygenated C _2～4Alkylidene fragment or unit are as polyethylene glycol or polypropylene glycol] polyamide-based resin.Polyamide-based resin and thermoplastic polyurethane are that at least one (the particularly polyamide-based resin) in the resin can have at least one PTMG unit.

Polyamide-based resin like this can comprise that having polyether segment by use [for example, has polyoxygenated C _{2～ 4}The diamines of alkylidene unit, dicarboxylic acids and amino carboxylic acid] component obtain, said components is that polyamide constitutes at least a portion component in the component (for example diamines, dicarboxylic acids and amino carboxylic acid).And, polyamide-based resin with polyether segment can comprise polyamide block copolymer (just having polyether component as soft section polyamide elastomer), above-mentioned polyamide copolymer be by the polyamide component with reactive terminal group (polyamide-block or fragment) with have and can obtain with polyether component (polyether block or the fragment) reaction of the end group of the reactive end radical reaction of above-mentioned polyamide component.

Such polyamide elastomer can also comprise the polyamide that for example obtains by the polyamide component polyether component reaction amino with having end with end carboxyl, react the polyamide that obtains by having the amino polyamide component of end with polyether component with end carboxyl, react the polyamide that obtains by polyamide component with end carboxyl and polyether component with terminal hydroxy group, and other etc.

As polyether component, can use and have the amino component of end [polyoxygenated C for example with reactive terminal group _2～4Alkylenediamine (as the polyoxygenated ethylene diamine)], have component (for example dicarboxylic acids and the polyoxygenated C of end carboxyl _2～4The half ester of aklylene glycol), has the component of terminal hydroxy group, for example polyoxygenated C _2～4Aklylene glycol [as polyethylene glycol, polypropylene glycol, polytetramethylene ether diol, the block copolymer of these polyoxyalkylene glycols (as PEO-PPOX block copolymer); And the alkylene oxide adduct of aromatic diol is (as bisphenol-A-C _2～4The alkylene oxide adduct)].

Above-mentioned polyamide component with reactive terminal group comprises aliphatic polyamide, alicyclic polyamide, aromatic polyamides and other etc., and can use various homopolyamides and copolyamide.

In aliphatic polyamide, homopolyamide can be included in and exemplify in the non-carbamate based thermoplastic resin (Ib-1), i.e. aliphatic diamine component (for example, C _4～12Alkylenediamine is (as C _6～12Alkylenediamine), as tetra-methylenedimine, hexamethylene diamine and 12 carbon alkane diamines) with aliphatic dicarboxylic acid component (C for example _6～14Alkylene dicarboxylic acids is as adipic acid, decanedioic acid and 12 carbon docosandioic acids) condensation product, and other etc.

Alicyclic polyamide can comprise having at least a alicyclic diamine and the alicyclic dicarboxylic acid (C for example that is selected from _5～10The cycloalkanes dicarboxylic acids, as cyclohexane-1,4-dioctyl phthalate and cyclohexane-1,3-dioctyl phthalate) as the homopolyamide and the copolyamide that constitute component.For example, can use so alicyclic polyamide, it obtains as the diamine components and the dicarboxylic acid component of the polyamide-based resin of at least a formation by using alicyclic diamine and/or alicyclic dicarboxylic acid.As diamine components and dicarboxylic acid component, above-mentioned aliphatic diamine and/or aliphatic dicarboxylic acid preferably are used in combination (so-called transparent polyamide) with alicyclic diamine and/or alicyclic dicarboxylic acid.In alicyclic polyamide, the condensation product of preferred aliphatic series dicarboxylic acids and alicyclic diamine (homopolymerization or copolyamide).

The example of alicyclic diamine can comprise diaminourea C _5～10Cycloalkane is as DACH; Two (amino C _5～8Cycloalkyl) C _1～3Alkane, as two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, or 2,2-two (4-aminocyclohexyl) propane; And other etc.

Aromatic polyamides can be included in the aromatic polyamides that is exemplified in the non-carbamate based thermoplastic resin (Ib-1), for example aromatic diamine (for example m-xylene diamine) is as the condensation product of MXD-6 and aliphatic dicarboxylic acid, the condensation product of aliphatic diamine (for example trimethylhexamethylenediamine) and aromatic dicarboxylic acid (for example terephthalic acid (TPA), M-phthalic acid), and other etc.

As polyamide component, can use and have the polyamide of dimer acids as the dicarboxylic acid component, wherein by using a spot of multifunctional polyamines and/or polycarboxylic acid component to introduce the polyamide of branched structure, modified polyamide (as the N-alkoxymethyl polyamide), and other etc.

Incidentally, as polyamide component, can use completely (whole) aromatic polyamides (for example fragrant acid amides) (diamine components and dicarboxylic acid component are all contained the polyamide of aromatised fraction) with aliphatic, alicyclic and/or aromatic polyamides, as poly-(metaphenylene isophthaloyl amine).

These polyamide components can be used alone or as a mixture.Preferred polyamide comprises at least a aliphatic polyamide.

Polyamide-based resin with polyether segment can be used alone or as a mixture.

Number-average molecular weight with polyamide-based resin of polyether segment is about 6000～100000, and is preferred about 8000～50000, more preferably from about 10000～30000.

With respect to whole resin, the ratio of polyether segment in the non-carbamate based thermoplastic resin (polyamide-based resin) that constitutes resin component for example is about 10～90 weight %, preferred about 20～90 weight %, more preferably from about 30～90 weight %.And, in polyamide elastomer, the polyamide fragment is not limited to concrete scope especially with respect to the ratio (weight ratio) of polyether segment (for example PTMG fragment), for example can be the former/latter=about 9/1～2/8, preferred about 9/1～2.5/7.5, more preferably from about 8/2～3/7, particularly about 7/3～4/6.

And, with respect to the thermoplastic polyurethane that constitutes resin component is polyether segment in the resin, the ratio (weight ratio) of the polyether segment in the non-carbamate based thermoplastic resin (for example polyamide-based resin) of formation resin component can be for example about 1/10～10/1, preferred about 1/8～8/1, more preferably from about 1/5～5/1.

Polyamide-based resin with polyether segment have end amino (free amine group ,-NH ₂), perhaps have the end carboxyl.The polyamide elastomer with polyether segment that commodity can get seldom has amino usually.Incidentally, the carboxyl concentration that has in the polyamide-based resin of polyether segment is not particularly limited to concrete scope, for example can be about 0.1～200mmol/kg, preferred about 0.5～150mmol/kg, more preferably from about 1～100mmol/kg.

For example, because the polyamide elastomer that commodity can get seldom has amino usually, so such polyamide elastomer is not enough to improve it sometimes and thermoplastic polyurethane is the connectivity of resin.Under such situation, the connectivity between resin component can be able to be to be incorporated into the component that contains amino and/or imino group in the resin to improve by polyamide-based resin and the thermoplastic polyurethane at least a formation resin component.The example that contains the component of amino and/or imino group comprises that another polyamide-based resin (has the amino polyamide-based resin of end, for example common polyamide-based resin, as the above-mentioned aliphatic series that exemplifies, alicyclic or aromatic polyamides), contain amino compound (the amino compound that contains that for example has high amino group concentration and relatively low molecular weight, as contain amino polyamide oligomer as well as), and other etc.

As containing amino compound, can use various can with the aminated compounds of polyamide-based mixed with resin with polyether segment, for example with in resin combination (Ib-2), exemplify identical contain amino compound.Aminated compounds can be used alone or as a mixture.In these compounds, with regard to connectivity, polyamide oligomer as well as is particularly preferred.Incidentally, the amino group concentration that contains amino-compound can be selected in the above-mentioned scope that exemplifies, and for example is about 10～1000mmol/kg (preferred about 30～700mmol/kg, particularly about 50～500mmol/kg)

With respect to matrix resin (the polyamide-based resin with polyether segment), the ratio that contains amino-compound can be selected in the scope that above-mentioned resin combination (Ib-2) part is exemplified.

In above-mentioned resin (IIb), it is not limited especially to constitute concentration amino in the non-carbamate based thermoplastic resin (or resin combination) of resin component, for example can be about 0～100mmol/kg, preferred about 0～50mmol/kg, more preferably from about 0～30mmol/kg.

Incidentally, among the present invention, when connecting non-carbamate based thermoplastic resin and TPU and prepare the composite article of moulding, because " flexural deformation " with the join dependency connection appears in the difference of moulding contraction factor sometimes between resin component in the product.Particularly, when diastrophic degree of correction is big, breaking or forming stress cracking of coupling part might appear in each resin component.Therefore, non-carbamate based thermoplastic resin preferably has lower degree of crystallinity.

For example, in polyamide, final degree of crystallinity (average final degree of crystallinity) advantageously is no more than 50% (for example about 5～50%), preferably is no more than 40% (for example about 5～40%), more preferably from about is no more than 30% (for example about 10～30%).

When using polyamide homopolymer as an example and during more final degree of crystallinity, finally degree of crystallinity diminishes successively by following order:

Polyamide 66＞polyamide 6 〉=polyamide 6 12＞polyamide 11 〉=polyamide 12

Incidentally, only consider final degree of crystallinity, then copolymer is more favourable than homopolymers.And normally, be better than homopolymers from copolymer in flexibility and consider that copolymer also is more favourable than homopolymers.

In containing hard fragment of polyamide homopolymer conduct and the situation of polyethers as the polyamide block copolymer (polyamide elastomer) of soft segment, final degree of crystallinity can be regulated by the ratio of hard fragment and soft segment.When being adjusted to, the final degree of crystallinity of polyamide block copolymer is no more than 40% (for example about 5～40%), preferably be no more than 35% (for example about 5～35%), during more preferably no more than 30% (for example about 10～30%), such copolymer is being that resin component is used in combination preventing that flexural deformation from being favourable when forming with thermoplastic polyurethane, and can provide with thermoplastic polyurethane be the flexibility that resin adapts.

Incidentally, term " final degree of crystallinity " is meant the thick plain film with 1mm, the degree of crystallinity that records by X-ray diffraction analysis, the formation of wherein said plain film be by the heated sample resin to the temperature higher 20 ℃ than its fusing point, with 3 ℃/minute speed resin is cooled to room temperature by the accurate thermal press then.The fusing point of resin is measured by Differential Scanning Calorimeter (DSC) according to JIS K 7122.

In the scope that such effect of the present invention is without prejudice, non-carbamate based thermoplastic resin component can contain other resin and various additive, for example filler and reinforcing agent (for example reinforcer), stabilizing agent (for example ultra-violet absorber, antioxidant and heat stabilizer), colouring agent, plasticizer, lubricant, fire retardant, antistatic additive and other etc.At non-carbamate based thermoplastic resin is that polyamide-based resin (comprises alicyclic polyamide, or have a polyamide-based resin of polyether segment) situation under, other resin can comprise that thermoplastic resin is (as polyester based resin, polycarbonate-based resin, polysulfones are resin, and polyimides is a resin, polyketone is a resin, polyolefin-based resins, phenylethylene resin series, (methyl) acrylic resin and halogen-containing vinyl resin) and other etc.

(thermoplastic polyurethane is a resin)

The thermoplastic polyurethane that can be connected with non-carbamate based thermoplastic resin is a resin, can and if need the reaction of chain extender to obtain by vulcabond, glycol.

Vulcabond can comprise aliphatic vulcabond, as hexamethylene diisocyanate (HMDI), or 2,2, the 4-trimethyl hexamethylene diisocyanate; Alicyclic diisocyanate, as 1,4-cyclohexane diisocyanate, dicyclohexyl methyl hydride 4,4 '-vulcabond, or IPDI (IPDI); Aromatic diisocyanates, as phenylene vulcabond, toluene di-isocyanate(TDI) (TDI), or diphenyl-methane 4,4 '-vulcabond (MDI); The araliphatic vulcabond, as XDI, and other etc.As vulcabond, can also use the compound that on its main chain or ring, is substituted with alkyl (as methyl).Vulcabond can be used alone or as a mixture.

The example of glycol can comprise that polyester-diol is [for example derived from aliphatic dicarboxylic acid component (C for example _4～12Aliphatic dicarboxylic acid is as adipic acid), aliphatic diol component (C for example _2～12Aliphatic diol is as ethylene glycol, propane diols, butanediol or neopentyl glycol) and/or lactone component (C for example _4～12Lactone is as 6-caprolactone) polyester-diol, polyethylene glycol adipate for example, poly-adipic acid 1,4-butanediol ester, poly-adipic acid 1,6-hexylene glycol ester and poly-epsilon-caprolactone], PTMEG [aliphatic polyether diol for example, for example poly-(oxidation C _2～4Alkylidene) glycol, as polyethylene glycol, poly-(oxidation trimethylene) glycol, polypropylene glycol, or polytetramethylene ether diol, and the block copolymer (for example polyoxygenated ethylidene-polyoxygenated propylidene block copolymer) of poly-(alkylidene oxide) glycol; The aromatic-polyether glycol, the adduct of aromatic diol and epoxyalkane for example is as bisphenol-A-alkylene oxide adduct (C for example _2～4The adduct of epoxyalkane such as oxirane or expoxy propane)]; Polyester ether glycol (by the polyester-diol that uses PTMEG to obtain) as a part of diol component; And other etc.In these glycol, what use under many situations is polyester-diol or PTMEG, as polytetramethylene ether diol (particularly polyester-diol).

As chain extender, can use glycol [for example short-chain diol, for example C _2～10Alkanediol is as ethylene glycol, propane diols, 1,4-butanediol or 1,6-hexylene glycol; Dihydroxy ethoxybenzene (BHEB)], [aliphatic diamine for example is as C to also have diamines in addition _2～10Alkylenediamine is as ethylenediamine or hexamethylene diamine; Alicyclic diamine is as IPD; Aromatic diamine is as phenylenediamine or dimethylphenylene diamine].Chain extender can be used alone or as a mixture.

Thermoplastic polyurethane is that resin can also comprise the thermoplastic polyurethane completely by using two pure and mild vulcabond of equivalent basically to obtain, also have incomplete in addition or contain thermoplastic polyurethane (PIC) isocyanate terminated base, that have free (or unreacted) isocyanates of small portion of residual, it is by using the vulcabond excessive a little with respect to glycol to obtain, and the thermoplastic polyurethane that contains terminal hydroxy group, it is by using the glycol excessive a little with respect to vulcabond to obtain.

At thermoplastic polyurethane is in the resin, particularly preferably is the TPUE by using glycol (glycol that for example has polyester unit or polyether units), vulcabond and glycol (for example short-chain diol) to obtain as chain extender.TPUE contains hard section (hard block) that the polyurethane that obtains by using two pure and mild vulcabond constitutes, and soft section (soft segment) being made of aliphatic polyether diol (for example polyoxygenated ethylidene glycol), aliphatic polyester diol or other etc.According to the difference of soft section kind, polyurethane elastomer can comprise the polyester urethane elastomer, the polyethers urethane elastomers, and other etc.Generally speaking, be resin as thermoplastic polyurethane, what preferably use is the polyester-polyurethane (particularly polyester urethane elastomer) that obtains with polyester-diol.These thermoplastic polyurethanes are that resin can be used alone or as a mixture.

Incidentally, in moulding composite article (IIa), be that resin has at least one polyether segment in order to the thermoplastic polyurethane that is connected with non-carbamate based thermoplastic resin (IIb) with polyether segment.

At the thermoplastic polyurethane that constitutes resin component is in the resin, and polyether segment is that the ratio of resin can for example not about 10～90 weight % with respect to whole thermoplastic polyurethane, preferred about 20～90 weight %, more preferably from about 30～90 weight %.

Thermoplastic polyurethane with polyether segment is a resin, can be for example by vulcabond and glycol with polyether units, and if the reaction of the words chain extender that needs and obtaining.

As the glycol with polyether units, [for example aliphatic polyether diol for example gathers (oxidation C can to use PTMEG _2～4Alkylidene) glycol, as polyethylene glycol, poly-(oxidation trimethylene) glycol, polypropylene glycol, or PTMG, and the block copolymer (for example polyoxygenated ethylidene-polyoxygenated propylidene block copolymer) of poly-(alkylidene oxide) glycol; The aromatic-polyether glycol, the adduct of aromatic diol and epoxyalkane for example is as bisphenol-A-alkylene oxide adduct (C for example _2～4The adduct of epoxyalkane such as oxirane or expoxy propane)]; Polyester ether glycol (by the polyester-diol that uses PTMEG to obtain) as a part of diol component; And other etc.These glycol can be used alone or as a mixture.In these glycol, aliphatic polyether diol preferably is as polyethylene glycol and PTMG.

Can mix the use polyester-diol with glycol with polyether units.Polyester-diol can comprise by C _4～12Aliphatic dicarboxylic acid component (as adipic acid), C _2～12Aliphatic diol component (as ethylene glycol, propane diols, butanediol or neopentyl glycol), C _4～12Lactone component (as 6-caprolactone) and the polyester-diol (for example aliphatic polyester diol) that obtains, polyethylene glycol adipate for example, poly-adipic acid 1, the 4-butanediol ester, poly-adipic acid 1,6-hexylene glycol ester, poly-epsilon-caprolactone, and other etc.

Thermoplastic polyurethane with polyether segment is that resin can also comprise the thermoplastic polyurethane completely by using two pure and mild vulcabond of equivalent in fact to obtain, also have incomplete in addition or contain thermoplastic polyurethane (PIC) isocyanate terminated base, that have free (or unreacted) isocyanates of small portion of residual, it is by using the vulcabond excessive a little with respect to glycol to obtain, and the thermoplastic polyurethane that contains terminal hydroxy group, it is by using the glycol excessive a little with respect to vulcabond to obtain.

At the thermoplastic polyurethane with polyether segment is in the resin, particularly preferably is by use to have the thermoplastic polyether urethane elastomers that glycol, vulcabond and the glycol (for example short-chain diol) of polyether units obtain as chain extender.The thermoplastic polyether urethane elastomers contains hard section (hard block) that the polyurethane that obtains by using two pure and mild vulcabond constitutes, and soft section (soft segment) being made of aliphatic polyether diol (for example polyoxygenated ethylidene glycol, PTMG).Thermoplastic polyurethane is that resin can contain at least one PTMG unit as polyether segment.

Thermoplastic polyurethane with polyether segment is that resin can be used alone or as a mixture.

As described in the non-carbamate based thermoplastic resin component, the thermoplastic polyurethane that constitutes resin component is the resin component that can contain amino and/or imino group (particularly amino-compound, as contain amino polyamide oligomer as well as).The thermoplastic polyurethane that has polyether segment with respect to 100 weight portions is a resin, component (the amino-compound particularly that contains amino and/or imino group, as contain amino polyamide oligomer as well as) ratio for example be about 0.01～10 weight portion, preferred about 0.1～8 weight portion, particularly about 0.5～7 weight portion.

In the scope that such effect of the present invention is without prejudice, thermoplastic polyurethane is that resin component can contain other resin (for example thermoplastic resin, particularly thermoplastic elastomer (TPE) are as polyamide-based elastomer, polyester based elastomers or polyolefin elastomer), stabilizing agent (for example heat stabilizer, ultra-violet absorber, antioxidant), plasticizer, lubricant, filler, colouring agent, fire retardant, antistatic additive and other etc.

In moulding composite article of the present invention, because non-carbamate based thermoplastic resin (Ib-1) contains the polyamide component with alicyclic ring, perhaps because non-carbamate based thermoplastic resin composition (Ib-2) contains amino group, therefore non-carbamate based thermoplastic resin (composition) is not using under the adhesive, is that resin is connected or bonds with thermoplastic polyurethane securely.And, in moulding composite article of the present invention, because polyamide-based resin and thermoplastic polyurethane are that resin all has polyether segment, and because the compatibility height of two kinds of interlaminar resins, therefore polyamide-based resin and thermoplastic polyurethane are that resin links together under adhesive-free securely.

In the moulding composite article, adhesion strength or bonding strength are not less than 30N/cm usually, being accompanied by the resin component that formed by non-carbamate based thermoplastic resin (for example animi resin parts) is separation on the resin component (for example barras parts) from thermoplastic polyurethane, occurs cohesional failure sometimes.The adhesion strength of such moulding composite article is generally 30N/cm to cohesional failure, preferably is not less than 40N/cm, particularly is not less than 50N/cm (being not less than 50N/cm to cohesional failure).

[preparation method of moulding composite article]

Moulding composite article of the present invention can be that resin makes by connecting non-carbamate based thermoplastic resin and thermoplastic polyurethane under heating.Normally by at least a resin of the present invention of heating, promptly non-carbamate based thermoplastic resin and thermoplastic polyurethane are at least a to fusion in the resin, and a kind of resin of molten condition contacted with other resin and guarantee to be connected.Such moulding composite article can be by in forming method being that resin is connected and makes with non-carbamate based thermoplastic resin and thermoplastic polyurethane, molding mode is to adopt common forming method, as thermoforming (for example hot-forming, injection press moulding), injection moulding (for example embedding injection moulding, double-colored (or two) injection moulding, core-back of the body injection moulding, sandwich injection moulding), extrusion molding (for example co-extrusion modling, T-die head laminated into type), or blow molding.

For example, at forming method as embedding in injection moulding or the injection press moulding, can be by heating and molten thermoplastic polyurethane series resin, and under the resin component that constitutes by non-carbamate based thermoplastic resin of contact at least a portion (following often abbreviate non-carbamate as be resin component), the molding thermoplastic polyurethane is a resin under molten condition, and two kinds of resins are linked together.Two kinds of resins can also following being joined together, promptly heat non-carbamate based thermoplastic resin to fusion, and be that the resin component (the following polyurethane series resin parts that often abbreviate as) that resin constitutes contacts with at least a portion by thermoplastic polyurethane the non-carbamate based thermoplastic resin under the molten condition.And, in forming method such as double injection moulding or co-extrusion modling, can be by differently heating and melting non-carbamate based thermoplastic resin and thermoplastic polyurethane are resin, and be resin moulded down, thereby guarantee the connection of two kinds of resins with the non-carbamate based thermoplastic resin of fusion and the thermoplastic polyurethane of fusion in that it is in contact with one another.The moulding composite article that wherein non-carbamate based thermoplastic resin component and polyurethane series resin parts firmly are connected, can be by at least a resin in fusion non-carbamate based thermoplastic resin and the polyurethane series resin, to make non-carbamate based thermoplastic resin and thermoplastic polyurethane be resin contact being connected, and cool off gains usually and obtain.And according to purpose and application, being enough to also non-carbamate based thermoplastic resin component is connected to thermoplastic polyurethane at least in part is resin component.

Incidentally, the resin (particularly matrix resin) that constitutes resin component can be not less than its fusing point and makes its fusion by being heated to.Substantially under the situation of noncrystalline resin, can be not less than its glass transition temperature (Tg) and make its fusion by being heated to.

According to the present invention, containing non-carbamate based thermoplastic resin and containing in the non-carbamate based thermoplastic resin composition of amino-compound, perhaps contain in the non-carbamate based thermoplastic resin of alicyclic polyamide component, because non-carbamate based thermoplastic resin contains amino group (compound or the resin itself of the self-contained amino of for example deriving contain amino), and amino group effect (chemical action) is a resin in thermoplastic polyurethane, even therefore in the moulding composite article that obtains by different kinds material, adhesion strength also can significantly improve, and this high bond strength can not be obtained by the physical action that brings by simple hot melt or thermal bonding.And, in containing the non-carbamate based thermoplastic resin of alicyclic polyamide component, because it is resin that the alicyclic ring of alicyclic polyamide component acts on thermoplastic polyurethane, even therefore in the moulding composite article that obtains by different kinds material, adhesion strength also can significantly improve, and this high bond strength can not be obtained by the physical action that brings by simple hot melt or thermal bonding.And then, all have in the polyamide-based resin of polyether segment and the mixture that thermoplastic polyurethane is resin at each, even in the moulding composite article that uses different materials, the high-affinity of two kinds of interlaminar resins also can improve the adhesion strength between resin component significantly.Therefore in this manual, " hot melt " not only comprises simple hot melt, and comprises the hot melt (thermally coupled) of chemical reaction in addition.

As mentioned above, at non-carbamate based thermoplastic resin and polyamide-based interlaminar resin, which resin is melted not limited especially.Can heat the barras (polyurethane series resin) that has usually than low melting point or glass transition temperature (Tg), and be connected on the animi resin parts that contain animi resin (non-carbamate based thermoplastic resin) with higher melt or Tg.And, also can heat the animi resin (non-carbamate based thermoplastic resin) that has higher melt or Tg usually, and be connected to and contain on the barras parts that have than the barras (polyurethane series resin) of low melting point or Tg.

In these methods, particularly the more common technology of former approach has advantage, because its feature ground and demonstrated effect of the present invention effectively.In the method for common use simple physical hot melt, when allowing the non-carbamate of molding formerly be resin component when polyurethane series resin with post moulding is connected, in most cases the molding temperature of polyurethane series resin becomes and is lower than the fusing point of the non-carbamate based thermoplastic resin of molding formerly, so hot melt is difficult to proceed.And even when the molding temperature of polyurethane series resin is higher than the fusing point of non-carbamate based thermoplastic resin, it is the surface of resin component that common heat also is not enough to the non-carbamate of hot melt.Therefore traditional technology does not comprise such mode usually, and promptly the non-carbamate of molding is a resin component before molded polyurethane is resin.Yet, according to the present invention, even under such situation, by amino group, alicyclic ring or be contained in the effect of the polyether segment in the non-carbamate based thermoplastic resin, can be that resin links together more easily also with non-carbamate based thermoplastic resin component and thermoplastic polyurethane.Therefore, the present invention can improve moulding composite article preparation method's selection freedom, and method step is rationalized.Containing non-carbamate based thermoplastic resin and containing in the non-carbamate based thermoplastic resin composition of amino compound, even the kind of polyurethane resin can not consider that polyethers system and polyester are the difference of polyurethane resin and freely selecting, so such resin combination has greatly reduced material cost.And when non-carbamate based thermoplastic resin contained alicyclic polyamide component, the present invention can also provide the height of polyurethane series resin kind freely to select, and can be that polyurethane and polyester are polyurethane without any using polyethers distinctively for example.

In the moulding composite article, although animi resin contains non-carbamate based thermoplastic resin and barras usually to contain thermoplastic polyurethane usually be resin in practical situation, it is that resin and barras also can contain non-carbamate based thermoplastic resin that animi resin also can contain thermoplastic polyurethane.And the hardness of non-carbamate based thermoplastic resin can be that the hardness of resin is identical with thermoplastic polyurethane.

More clearly, in hot-forming, can be by at least a resin in fusion animi resin (or composition) and the barras (or composition) in the metal die of compression moulding, two kinds of resins are in contact with one another adding to depress, and resin interconnected and make the moulding composite article.In hot-forming, animi resin and/or barras can be with granular form, powder type or other form be filled in the metal die, perhaps can join in the metal die with the form of the moulded products that forms by other forming method in advance.

In embedding injection moulding, can come any in moulding animi resin (or resin combination) or the barras (or resin combination) by using forming method (as injection moulding, extrusion molding, compression molding or film forming moulding), and the goods of moulding like this are embedded or put into metal die, then other resin injection is gone in space between moulded products and the metal die or the chamber to prepare the moulding composite article.In embedding injection moulding, the moulded products that preferably will be embedded in the metal die carries out preheating.

In double-colored (or two) injection moulding, can be by any one component in animi resin (or resin combination) or the barras (or resin combination) being injected in the metal die by two or more injection (mo(u)lding) machines, rotation by metal die or move the chamber that changes metal film, and other component is expelled in the moulded products and space or chamber between the metal die that so obtains, prepare the moulding composite article.

In core-back of the body injection moulding, can be by any one component in animi resin (or resin combination) or the barras (or resin combination) be injected in the metal die, the cavity of enlarged metal mould, and other component is expelled in the moulded products and space or chamber between the metal die that so obtains, prepare the moulding composite article.

In these forming methods, particularly consider from the angle of production in enormous quantities or other performance, suitable method for example is hot-forming, as injection press moulding and injection moulding (for example injection moulding, double injection moulding, core-back of the body injection moulding, sandwich injection moulding).

In hot melt, the hot melting temperature of animi resin and/or barras (or hot melting temperature) can be selected according to the kind of two kinds of resins (or resin combination), for example can be selected from about 100～300 ℃, and preferred about 120～290 ℃, more preferably from about 150～280 ℃.For example in hot-forming, melt temperature can be about 100～250 ℃, preferred about 120～230 ℃, and more preferably from about 150～220 ℃.And in injection moulding, the temperature of resin for example can be about 200～300 ℃ in the molding tube, preferred about 220～280 ℃, and more preferably from about 240～280 ℃.

The structure of moulding composite article and configuration are not limited especially to specifically a kind of, can be suitable for designing, the structure of decorate properties, sense of touch and other etc.For example, such structure can obtain by applying with the animi resin parts with laminated portion and whole barras parts, and preferably obtains (for example obtaining by apply the part animi resin parts that contact with human body (as hand) with the barras parts) with whole animi resin parts by applying with the barras parts with laminated portion usually.And concrete structure comprises for example two-dimensional structure (as plate like form of class and similar tabular form) and three-dimensional structure (as form, box or the shell mould of similar bar-shaped form, next life tubulose).

According to the present invention, can be without the production stage of complexity (for example producing the step of sags and crests, the step of application of adhesive) and with animi resin and barras directly and link together securely by hot melt at recombination region.Therefore the present invention can guarantee to obtain lightweight and powerful moulding composite article, and these goods are improved on for example design, decorate properties or sense of touch or feel performances such as (for example soft feel, flexibilities).

Industrial applicibility

Advantageously, it is that resin is connected or bonds with formation moulding composite article that resin of the present invention (or resin combination) can be used for directly with thermoplastic polyurethane, and resin wherein of the present invention (or resin combination) is direct to be that resin is connected or bonds with thermoplastic polyurethane.And the moulding composite article of gained can be used as various industrial components (or parts), for example automobile component (automotive interior part for example, as instrument board, central dial plate, center armrest case, door limit, important actor, auxiliary handle, steering wheel, perhaps air bag covering; Automobile outer part is as shirt rim or bumper; The automobile function assembly, as luggage carrier and gear boots, suspension boot, perhaps constant speed engages boots), household electrical appliance parts (cleaner pump for example, remote controller switch, the key-top of business automation equipment), the product (for example swim goggles, the capping of underwater camera) that is used for water, industrial parts (coating member; Consider and the various industrial parts of outfit packing for sealing property, water resistance, sound insulation value, vibrations insulating properties and other performance; The technically classified rubber roller), electronics and electrical equipment parts (covering of for example crooked rope electric wire, band, flexible pipe, pipe, noise reduction gear), moving articles, footwear (for example sport footwear, sole), and the parts (for example sunglasses and glasses) that need design or decorate properties.

In these, moulding composite article particularly suitable is made the component part of footwear and mechanical part such as roller (for example rubber rollers).The component part of footwear comprises footwear parts such as sole or vamp, and other etc.And the moulding composite article can be made into (or formation) sport footwear, footware (for example boots, rain boots, gardening footwear).In such shoemaking is used, because polyamide-based resin and flexible polyurethane hard or that glass fibre strengthens are being used in combination of resin, be difficult in the past, become simply now, for example can in a lot of layers, the material fit of different brackets be used thus.Therefore, the moulding composite article is gone a long way greatly and is improved the design or the function of footwear.

And in the application of roller (as rubber rollers), for example roller can comprise that wherein superficial layer at least contains the axle of non-carbamate based thermoplastic resin (composition), and the polyurethane series resin layer that forms around along the axle surface.Can obtain axle by form non-carbamate based thermoplastic resin bed on the surface of metal shaft, perhaps axle can contain non-carbamate based thermoplastic resin.In such roller is used, owing to for obtain cutting that the axle precision carries out finish with thermoplastic polyurethane be that the surface of resin is finished and can be carried out in an operation by same grinder, so the production process of roller can be simplified greatly and cost is exponentially and reduces.And because such chemistry that passes through connects the roller that obtains and have high bond strength, and seldom has space or cavity between axle and roller, so roller can bear under the high torque (HT) and uses.

Embodiment

Following embodiment is used to describe in further detail the present invention, should not be interpreted as limitation of the present invention by any way.

Embodiment 1

(i) preparation of alicyclic polyamide

In the autoclave of crossing with nitrogen replacement,, and in 4 hours, the water in the reaction system is discharged from reaction system with nitrogen at pressurization (1.7MPa) and 220 ℃ of salt (1000g) and 12 carbon alkane dicarboxylic acids that heat two (4-aminocyclohexyl) methane down.Subsequently, the temperature with system in 1 hour is increased to 275 ℃ gradually, and the water of remnants is discharged outside the system fully.Internal pressure with autoclave is reduced to atmospheric pressure afterwards.Obtain number-average molecular weight after the cooling and be about 23000 and the end amino group concentration be the transparent polyamide (polymer 1) of 43mmol/kg.The ratio (hereinafter referred to as " MR value ") that calculates the monomer residue that has alicyclic amino in the polymer 1 and other monomer residue for the former/latter=50/50.

The (ii) preparation of moulding composite article

The polymer 1 that obtains with above-mentioned (i) makes the flat board of wide 100mm, long 100mm, thick 2mm by injection moulding, and 1/5 surface of above-mentioned polyamide moulding goods (about 20mm is wide from the edge meter) covers with aluminium platinum.Subsequently, the goods that cover are placed in the flat metal mould that 100mm is wide, 100mm is long, 4mm is dark, and TPU are injected in the space of metal die.Under 60 ℃ of 205 ℃ of barrel zone temperatures and metal die temperature, carry out the injection moulding of polyurethane resin.Incidentally, used two kinds of polyurethane resins, promptly polyethers be polyurethane resin (produce by BASF, Erastollan, 1195ATR) and polyester be polyurethane resin (produce, Erastollan, ET 195) by BASF.By using the moulding composite article that obtains by each polyurethane resin, peel off test.

(iii) hot melt evaluation (peeling off)

The moulding composite article of gained is cut into the wide and 100mm length of 20mm, and the cover part is used as in peeling off test clamps the handle of reinstating of controlling.For each test pieces, under 20mm/ minute rate of extension, control handle and carry out extension test by 180 ° of directions stretchings.By extension test, recorded the peel strength between non-carbamate based thermoplastic resin component and carbamate based thermoplastic resin component interface in merging.Based on peel strength, estimated the hot molten characteristic (adhesion strength) between non-carbamate based thermoplastic resin component and carbamate based thermoplastic resin component.

Usually, with regard to adhesion strength, peel strength is lower than peeling off of 50N/cm and is considered to interface peel usually.Under such situation, bonding is confirmed as binding deficient in many application, because attachment can be peeled off with hand.Peel strength surpasses peeling off of 50N/cm and is included into the dissection scope that comprises cohesional failure.That is to say that attachment is difficult to peel off with hand, such bonding strength is enough to be applied to industrial purposes.Peel strength is the cohesional failure that peeling off of 80～100N/cm is included into whole moulded products, and such moulded products is applicable to the harsh flexural fatigue of the tolerance that comprises sport footwear.

Comparative Examples 1

Prepare polyamide in the mode identical with embodiment 1 by polymerization, different is to replace two (4-aminocyclohexyl) methane with hexamethylene diamine.The number-average molecular weight of gained polyamide 6 12 (polymer 2) is about 20000, and the end amino group concentration is 51mmol/kg.The MR value of polyamide 6 12 (polymer 2) is 0/100.And, prepare the moulding composite article and peel off test in the mode identical with embodiment 1, different is to replace polymer 1 with polymer 2.

Embodiment 2

Air by the autoclave of nitrogen replacement in, stir under the pressurization (1.8MPa) in 250 ℃ of heating omega-lauryl lactans (1000g), 12 carbon alkane dicarboxylic acids (15g) and a spot of phosphoric acid.Stir after 4 hours, add two (4-aminocyclohexyl) methane in the mixture of gained, reaction continues to carry out under 280 ℃ 0.5 hour.Begin to cool down reactant mixture then, obtain having the transparent polyamide 12 (polymer 3) of cyclohexyl amino.The number-average molecular weight of polyamide 12 (polymer 3) is about 15000, and the end amino group concentration is 60mmol/kg.Calculate the MR value and be 1.2/98.8.

And, prepare the moulding composite article and peel off test in the mode identical with embodiment 1, different is to replace polymer 1 with polymer 3.

Comparative Examples 2

Air by the autoclave of nitrogen replacement in, stir under the pressurization (1.8MPa) in 250 ℃ of heating omega-lauryl lactans (1000g), 12 carbon alkane dicarboxylic acids (15g) and a spot of phosphoric acid, and under agitation in 4 hours, the water in the reaction system is discharged from reaction system with nitrogen.Subsequently, the temperature of system is increased to 275 ℃ at leisure, and the water of remnants is discharged outside the system fully.Internal pressure with autoclave returns back to normal pressure afterwards.Obtain number-average molecular weight after the cooling and be about 15000 transparent polyamide 12 (polymer 4).Polyamide 12 (polymer 4) has the end amino of aliphatic chain amino, and the end amino group concentration is 7mmol/kg.And the MR value of polymer 4 is 0/100.

And, prepare the moulding composite article and peel off test in the mode identical with embodiment 1, different is to replace polymer 1 with polymer 4.

Embodiment 3

The transparent polyamide (polymer 1) (60 weight portion) that embodiment 1 is obtained mixes with the polyamide 12 (polymer 4) (40 weight portion) that Comparative Examples 2 obtains, and mixture is mediated with double screw extruder, obtains polyamide alloy (polymer 5).The end amino group concentration of polyamide alloy (polymer 5) is 29mmol/kg, and the MR value is 29/71.

Prepare the moulding composite article and peel off test in the mode identical with embodiment 1, different is to replace polymer 1 with polymer 5.

Embodiment 4

The polyamide that contains alicyclic amino 12 (polymer 3) (40 weight portion) that embodiment 2 is obtained mixes with Comparative Examples 2 polyamide 12 (polymer 4) (60 weight portion) that obtain, that do not have alicyclic amino, and mixture mediated with double screw extruder, obtain polyamide 12 mixtures (polymer 6).The end amino group concentration of polyamide 12 mixtures (polymer 6) is 28mmol/kg, and the MR value is 0.4/99.6.

Prepare the moulding composite article and peel off test in the mode identical with embodiment 1, different is to replace polymer 1 with polymer 6.

Embodiment 5

(Degussa produces with polyamide elastomer, VestamidE47S3) (80 weight portion) mixes with the polyamide 12 (polymer 3) (20 weight portion) that embodiment 2 obtains, and mixture mediated with double screw extruder, obtain blend polyamide elastomer (polymer 7).The end amino group concentration of the polyamide elastomer (polymer 7) that mixes is 15mmol/kg, and the MR value is 0.14/99.86.

Prepare the moulding composite article in the mode identical with embodiment 1, different is that polymer 7 is that (BASF produces polyurethane resin with polyethers, Erastollan, ET880) use together, perhaps polyester is polyurethane resin (Japan Polyurethane Industry Co.Ltd., produce Mirastollan E585) use with polymer as polyurethane resin, and peel off test.The results are shown in Table 1 for gained.

Embodiment 6

Carry out the test of peeling off between polyamide elastomer (Degussa produces, Vestamid E47S3) and polyurethane resin in the mode identical with embodiment 5, the results are shown in Table 1 for gained.The end amino group concentration of used polyamide elastomer is 4mmol/kg, and the MR value is 0/100.

Shown in the result in the table 1, no matter the kind of polyurethane how, the moulding composite article of embodiment all demonstrates high-peeling strength.On the contrary, Comparative Examples 1 and 2 moulding composite article demonstrate lower peel strength, and the sheet material of embodiment 6 is that polyurethane has lower peel strength to polyester.

Embodiment 7～13 and Comparative Examples 3

(1) the non-carbamate based thermoplastic resin of preparation

(i) to 100 weight parts of polyamide 12 (number-average molecular weights: 19000, amino group concentration: add 5 weight parts of polyamide, 12 oligomer (number-average molecular weight: 3000 8mmol/kg), amino group concentration 530mmol/kg), with biaxial extruder mixing gains, obtain non-carbamate based thermoplastic resin (A1) (amino group concentration: 20mmol/kg).

(amino group concentration: 40mmol/kg), different is to replace polyamide 12 oligomer with hexamethylene diamine (0.5 weight portion) (ii) to obtain non-carbamate based thermoplastic resin (A2) in the mode identical with above-mentioned (i).

(iii) obtain non-carbamate based thermoplastic resin (A3) (amino group concentration: 100mmol/kg) in the mode identical with above-mentioned (i), different is with amino modified polyethers (Sanamyl TAP-10, by Sanyo Chemical Industries, Ltd. produces) (0.5 weight portion) replacement polyamide 12 oligomer.

(iv) obtain non-carbamate based thermoplastic resin (A4) (amino group concentration: 35mmol/kg) in the mode identical with above-mentioned (i), different is with polyamide 6 (number-average molecular weight: 23000, amino group concentration: 17mmol/kg) (100 weight portion) replaces polyamide 12 oligomer.

(v) to polyester elastomer (Hytrel, by DU PONT-TORAY CO., LTD produces) (100 weight portion) middle polyamide 12 oligomer (number-average molecular weight: 3000 that adds, amino group concentration 530mmol/kg) (5 weight portion), with biaxial extruder mixing gains, obtain non-carbamate based thermoplastic resin (A5) (amino group concentration: 15mmol/kg).

(vi) with above-mentioned (v) identical mode obtains non-carbamate based thermoplastic resin (A6) (amino group concentration: 15mmol/kg), different is to replace polyester elastomer with Merlon (Iupilon is produced by MitsubishiEngineering-Plastics Corporation) (100 weight portion).

(vii) with above-mentioned (v) identical mode obtains non-carbamate based thermoplastic resin (A7) (amino group concentration: 15mmol/kg), different is to replace polyester elastomer with polyphenylene sulfide (Fortron is produced by Polyplastics Co.Ltd.) (100 weight portion).

(viii) as a comparison, only use the polyamide 12 (non-carbamate based thermoplastic resin (A8)) of amino group concentration as 5mmol/kg.

(2) preparation of moulding composite article and peel off test

With ester based thermoplastic polyurethane elastomer (ET195 is produced by BASF), prepare the plain film of wide 120mm, long 25mm, thick 2mm with injection (mo(u)lding) machine.Plain film is placed in the metal die of wide 120mm, long 25mm, thick 4mm to carry out injection moulding, and the non-carbamate based thermoplastic resin that under the condition that connects 60 ℃ of temperature 250 ℃ (barrel zone temperature), metal die temperature, carries out obtaining in above-mentioned (1) or the injection moulding of resin combination, to obtain the moulding composite article.

The moulding composite article of gained is cut into the sheet that 20mm is wide and 100mm is long.The part that covers with aluminium platinum is controlled handle as what pincers were reinstated.Under 20mm/ minute rate of extension, control handle and carry out extension test by 180 ° of directions stretchings.By extension test, recorded the peel strength between non-carbamate based thermoplastic resin component and carbamate based thermoplastic resin component interface in merging.Based on peel strength, estimated the hot molten characteristic between resin component.

The results are shown in Table 2.

Table 2

Non-carbamate is the amino group concentration peel strength

Thermoplastic resin ( Mmol/kg) ( N/cm)

Embodiment 7 Al 20 130

Embodiment 8 A2 40 110

Embodiment 9 A3 100 130

Embodiment 10 A4 35 110

Embodiment 11 A5 15 80

Embodiment 12 A6 15 70

Embodiment 13 A7 15 80

Comparative Examples 3 A8 5 30

Can clearly be seen that by table the moulding composite article of embodiment 7～13 connects with higher adhesion strength than the Comparative Examples 3 that does not contain any amino-compound.

Embodiment 14～21 and Comparative Examples 4～5

(1) preparation of polyamide

Prepare the polyamide elastomer or the polyamide that will use with following process.

(i) polyamide elastomer (A9)

Nitrogen flows down through 3 hours 12 carbon alkane lactams (500g) and 12 carbon alkane dicarboxylic acids (50g) is joined in the pressure vessel (about 2MPa).In the mixture of acquisition like this, add polytetramethylene ether diol (molecular weight is 1300, and two ends are hydroxyl) (500g), and under reduced pressure added thermal agitation 5 hours, obtain polyamide elastomer (A9).

(ii) polyamide elastomer (A10)

Prepare polyamide elastomer (A10) in the mode identical with above-mentioned (A9), different is to use 12 carbon alkane lactams (800g), 12 carbon alkane dicarboxylic acids (90g) and polytetramethylene ether diol (320g).

(iii) polyamide elastomer (A11)

Prepare polyamide elastomer (A11) in the mode identical with above-mentioned (A9), different is to use 12 carbon alkane lactams (300g), 12 carbon alkane dicarboxylic acids (30g) and polytetramethylene glycol (450g).

(iv) polyamide elastomer (A12)

Prepare polyamide elastomer (A12) in the mode identical with above-mentioned (A9), different is to use 12 carbon alkane lactams (500g) and 12 carbon alkane dicarboxylic acids (25g), and replace polytetramethylene ether diol with polypropylene glycol (molecular weight is 1000, and two ends are hydroxyl).

(v) polyamide elastomer (A13)

Prepare polyamide elastomer (A13) in the mode identical with above-mentioned (A12), different is to replace polypropylene glycol with polyethylene glycol (molecular weight is 1000, and two ends are hydroxyl).

(vi) polyamide (B1)

With in the autoclave of nitrogen replacement, in the presence of small amounts of phosphoric acid, 12 carbon alkane lactams (1000g) and 12 carbon alkane dicarboxylic acids (110g) are heated to 250～260 ℃, in 4 hours, from system, remove water and nitrogen in the system subsequently.Then with system cooling, the polyamide that obtains contrasting (B1).

(2) preparation of moulding composite article

With polyamide elastomer or the polyamide in above-mentioned (1), form moulding composite article (plain film that 100mm is wide, 100mm is long and 2mm is thick) by injection moulding, about 1/5 surface (about 20mm is wide from the edge meter) of above-mentioned moulded products covers with aluminium platinum.Subsequently, the resin component that covers is placed in the flat metal mould that 100mm is wide, 100mm is long, 4mm is dark, and thermoplastic polyurethane (TPU) is injected in the space of metal die, obtain the moulding composite article.Under 60 ℃ of 205 ℃ of barrel zone temperatures and metal die temperature, carry out the injection moulding of TPU.

Incidentally, use polyethers based thermoplastic polyurethane C1 (produce by BASF, Erastollan, ET890) or polyethers based thermoplastic polyurethane C2 (produced by BASF, Erastollan is 1195ATR) as above-mentioned TPU.

(3) hot melt evaluation (peeling off test)

The moulding composite article of gained in embodiment and the Comparative Examples is cut into the wide and 100mm length of 20mm, and the cover part is used as in peeling off test clamps the handle of reinstating of controlling.For each test pieces, under 20mm/ minute rate of extension, control handle and carry out extension test by 180 ° of directions stretchings.By extension test, recorded the peel strength between non-carbamate based thermoplastic resin component and carbamate based thermoplastic resin component interface in merging.Based on peel strength, estimated the hot molten characteristic (adhesion strength) between animi resin parts and barras parts.

The results are shown in Table 3.

Table 3

Polyamide elastomer polyurethane peel strength

(N/cm)

Embodiment 14 A9 C1 140

Embodiment 15 A10 C1 90

Embodiment 16 A11 C1 180

Embodiment 17 A12 C1 130

Embodiment 18 A13 C1 130

Embodiment 19 A9 C2 140

Embodiment 20 A10 C2 100

Embodiment 21 A13 C2 140

Comparative Examples 4 B1 C1 16

Comparative Examples 5 B1 C2 10

Can be clear that by table 3, use the Comparative Examples of polyamide-based resin (not containing polyether segment as non-carbamate based thermoplastic resin) more much lower than the peel strength of embodiment, wherein non-carbamate based thermoplastic resin and thermoplastic polyurethane are that resin all contains polyether segment among the embodiment.

Claims (19)

1. moulding composite article, wherein containing the resin component of non-carbamate based thermoplastic resin and containing thermoplastic polyurethane is that the resin component of resin directly interconnects, wherein non-carbamate based thermoplastic resin is non-carbamate based thermoplastic resin Ib, wherein non-carbamate based thermoplastic resin Ib contains and is selected from polyamide component with alicyclic ring and contains at least a in the amino compound, and the described amino group concentration that contains amino compound is 40～1000mmol/kg.

2. the moulding composite article of claim 1, wherein non-carbamate based thermoplastic resin Ib is the resin Ib-1 that contains the polyamide component with alicyclic ring, perhaps contains non-carbamate based thermoplastic resin and the resin combination Ib-2 that contains amino-compound.

3. the moulding composite article of claim 1, the amino group concentration of wherein non-carbamate based thermoplastic resin Ib is for being not less than 10mmol/kg.

4. the moulding composite article of claim 1, wherein in non-carbamate based thermoplastic resin Ib, the polyamide component with alicyclic ring is selected from least a in alicyclic polyamide-based resin and the alicyclic polyamide elastomer.

5. the moulding composite article of claim 1, wherein in non-carbamate based thermoplastic resin Ib, the polyamide component with alicyclic ring contains

At least a alicyclic polyamide component that is selected from alicyclic polyamide-based resin, alicyclic polyamide elastomer and alicyclic polyamide oligomer as well as; With

At least a aliphatic polyamide that is selected from is that resin and aromatic polyamides are the non-alicyclic polyamide component of resin.

6. the moulding composite article of claim 1, wherein in non-carbamate based thermoplastic resin Ib, the polyamide component with alicyclic ring can obtain as diamine components by using alicyclic diamine.

7. the moulding composite article of claim 1, wherein non-carbamate based thermoplastic resin Ib contains polyamide-based resin, in constituting all polyamide components of polyamide-based resin, the alicyclic monomer residue with respect to the mol ratio of other monomer residue for the former/latter=100/0～0.1/99.9.

8. the moulding composite article of claim 1, wherein non-carbamate based thermoplastic resin Ib is that Ib-2 contains the amino compound and the resin combination of non-carbamate based thermoplastic resin, and non-carbamate based thermoplastic resin contains, and to be selected from polyamide-based resin, polyester based resin, polycarbonate-based resin, polyphenylene sulfide be that resin, polysulfones are that resin, TPI are that resin, polyether-ketone are at least a in resin, olefin-based resin, phenylethylene resin series, (methyl) acrylic resin and the halogen-containing vinyl resin.

9. the moulding composite article of claim 1 wherein in non-carbamate based thermoplastic resin Ib, contains amino compound and have a plurality of primary amino radicals in molecule.

10. the moulding composite article of claim 1, wherein in non-carbamate based thermoplastic resin Ib, contain amino compound and be number-average molecular weight and be 500～10000 and amino group concentration be the polyamide oligomer as well as of 50～700mmol/kg.

11. the moulding composite article of claim 1, wherein non-carbamate based thermoplastic resin Ib is the resin combination Ib-2 that contains non-carbamate based thermoplastic resin and contain amino-compound, with respect to the non-carbamate based thermoplastic resin of 100 weight portions, the ratio that contains amino compound is 0.01～20 weight portion.

12. the moulding composite article of claim 1, wherein non-carbamate based thermoplastic resin Ib contains following resin combination:

Polyamide oligomer as well as; With

At least aly be selected from the non-carbamate based thermoplastic resin that polyamide-based resin, polyester based resin, polycarbonate-based resin and polyphenylene sulfide are resin.

13. the moulding composite article of claim 1, the resin component that wherein contains non-carbamate based thermoplastic resin Ib is that the resin component of resin directly is connected with containing at least a thermoplastic polyurethane, and described thermoplastic polyurethane is that resin is selected from polyester urethane elastomer and polyethers urethane elastomers.

14. the moulding composite article of claim 1 is the component parts of footwear or the component parts of roller.

15. one kind can be the direct-connected non-carbamate based thermoplastic resin of resin with thermoplastic polyurethane, it is non-carbamate based thermoplastic resin Ib, and

Non-carbamate based thermoplastic resin Ib contains and is selected from polyamide component with alicyclic ring and contains at least a in the amino-compound.

16. the resin of claim 15 for containing the resin Ib-1 of the polyamide component with alicyclic ring, perhaps contains non-carbamate based thermoplastic resin and the resin combination Ib-2 that contains amino-compound.

17. a method for preparing the moulding composite article of claim 1, this method comprise that heating is at least a and be selected from non-carbamate based thermoplastic resin and thermoplastic polyurethane is the resin of resin, and

Two kinds of resins are interconnected.

18. the method for claim 17, this method comprises

With at least a non-carbamate based thermoplastic resin and the thermoplastic polyurethane of being selected from is that the resin of resin is heated to fusion,

The resin of at least a molten condition is contacted with other resin, and

Two kinds of resins are interconnected.

19. the method for claim 17, wherein by being selected from the forming method of thermoforming, injection moulding, extrusion molding and blow molding, making non-carbamate based thermoplastic resin and thermoplastic polyurethane is that resin interconnects in forming process.