Composite materials

Abstract

To provide a thermoplastic composite material having excellent adhesion strength.SOLUTION: A composite contains directly adjoining and firmly bonded sections (I) and (II) of the following type: (I) section, formed from a thermoplastic moulding material FM-1 containing at least one polyamide (A) and optionally fillers and reinforcing materials (C) and additives (D); and (II) section, formed from a thermoplastic moulding material FM-2 containing at least one olefinic and / or vinyl aromatic polymer (E) and optionally fillers and reinforcing agents (F), plasticisers (G) and additives (H); wherein the moulding material FM-1 or FM-2 contains 0.1 to 5.0 wt.% of polyethyleneimine (B) or a copolymer or derivative thereof. There is also provided a method for producing the composite.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composite material in which a polyamide-based profile and an olefin / vinyl aromatic polymer-based profile are firmly bonded to each other at the contact zone of the two profiles without an intermediate layer or adhesive, and to a method for making said composite material. [Background technology]

[0002] Thermoplastic polyamide materials have established themselves in many areas of structural component production, particularly in the automotive sector, but also in the electronics sector, for example in the housings of mobile devices, due in particular to their good mechanical properties, resistance to chemicals, good processability, low specific gravity, etc.

[0003] Flexible, highly flexible synthetic resins are used for switch covers, particularly in automotive remote control keys and other electrical and electronic equipment, where protection from moisture and water intrusion is required. These covers, made from highly flexible olefin / vinyl aromatic polymers, must adhere to rigid housing components, and the adhesive strength should be as strong as possible. Often, the composites are also required to be resistant to higher temperatures and the simultaneous presence of moisture and water. Typically, the adhesive strength between a rigid polyamide and a flexible olefin / vinyl aromatic polymer is improved by adding a certain amount of the olefin / vinyl aromatic polymer to the polyamide molding compound or by grafting the olefin / vinyl aromatic polymer with carboxylic acid or anhydride groups.

[0004] The problem with this bonding is that the adhesion between the olefin / vinyl aromatic polymer and the modified polyamide, or between the modified olefin / vinyl aromatic polymer and the polyamide, becomes poor after storage at high temperature and / or high humidity. The modified olefin / vinyl aromatic polymer adheres immediately after the composite is made, but rapidly loses its adhesive strength after storage at a temperature of 70°C and a relative humidity of 62%. When the polyamide is modified with an appropriate amount of a flexible component, the excellent mechanical properties, good processability, and other properties of the polyamide mentioned above are lost. This is where the present invention comes into play. Summary of the Invention

[0005] The object of the present invention is therefore to provide thermoplastic composite materials based on thermoplastic polyamides and thermoplastic olefin / vinyl aromatic polymers, which have mechanical properties suitable for the above-mentioned applications and at the same time have excellent adhesive strength, even after storage at high temperature and in the presence of moisture, in particular after storage at a temperature of 70° C. and a relative humidity of at least 50%. The object of the present application is achieved in accordance with the subject matter of the claims, in particular by a composite of at least one profile based on polyamide and at least one adjacent profile made of an olefin / vinyl aromatic polymer, and by the use of polyethyleneimines or copolymers or derivatives thereof to improve the adhesive strength between the different profiles.

[0006] The core of the present invention is the unexpected discovery that polyethyleneimines significantly improve adhesion between thermoplastic polyamide molding materials and thermoplastic molding materials based on olefin / vinyl aromatic polymers, specifically olefin / vinyl aromatic polymers, including polystyrene block copolymers such as SEBS and SEBS-g-MAH. Polyethyleneimines can be added to polyamide molding materials or olefin / vinyl aromatic polymer-based molding materials without detracting from the beneficial mechanical properties of the polyamide or olefin / vinyl aromatic polymer-based molding materials. Surprisingly, this high adhesive strength is maintained for a long time even under the influence of heat and humidity. Composites according to the present invention preferably achieve adhesive strengths (peel forces) of at least 50 N, specifically at least 70 N (either without storage or immediately after preparation). Furthermore, the adhesive strength of composites according to the present invention preferably decreases by less than 30%, particularly preferably by less than 20%, relative to the initial value before storage during 120 hours of storage at 70°C and 62% relative humidity. The adhesive strength is determined by a roller peel test at 23°C in which a 30 mm wide profile (II) of the composite molding used for the measurement is peeled from profile (I) by moving it on a roller at an angle of 90° and a pulling speed of 50 mm / min. The average peel force [N] across the measurement profile is taken as the adhesive strength.

[0007] It is a known basic principle from other fields that polyethyleneimines can be added to polyamide molding materials, but cannot be added to molding materials based on thermoplastic elastomers, specifically olefin / vinyl aromatic polymers, due to problems with adhesion strength.

[0008] With regard to the prior art, reference is made to the following documents: WO 2015 / 024912 and similarly WO 2015 / 024911 describe composite synthetic resin molded articles having a first synthetic resin component and a second synthetic resin component, and including a polyethyleneimine to improve adhesion between them. These prior art documents also relate to methods for making the composite synthetic resin molded articles, methods for improving adhesion between the first and second synthetic resin components of a composite synthetic resin molded article, and the use of polyethyleneimines to improve adhesion between the first and second synthetic resin components of a composite synthetic resin molded article. Both synthetic resin components are made of polyamide. In addition, one synthetic resin component contains a three-dimensional reinforcing fabric and therefore cannot be thermoplastically processed by injection molding or extrusion. A polyamide-based film without reinforcing fibers is used as a layer to enhance adhesion between the two synthetic resin components. Therefore, all of the described contact zones are formed by a polyamide-based molding material.

[0009] WO 2011 / 138300 describes a composite molding comprising at least one profile made of a polyamide molding compound and at least one profile made of a vulcanized elastomer, such as EPDM, EPM, ACM, fluororubber, NBR, H-NBR, or AEM, either alone or in combination. The polyamide molding compound comprises a mixture of 60 to 99 parts by weight of a polyamide and at least 40% by weight of the following monomers: a) 0.5 to 25% by weight, based on the graft copolymer, of a polyamine having at least four nitrogen atoms, and b) 1 to 40 parts by weight of a graft copolymer that can be prepared using polyamide-forming monomers selected from lactams and ω-aminocarboxylic acids and / or equimolar combinations of diamines and dicarboxylic acids, where the sum of the parts by weight of a) and b) is 100. The presence of the graft copolymer is said to provide improved adhesion between the profiles.

[0010] From the perspective of the present application, the thermoplastic polyamide molding materials or composite moldings proposed herein do not contain crosslinked or vulcanized elastomer components, which may contain, alone or in combination, e.g., EPDM, EPM, ACM, fluororubber, NBR, H-NBR, or AEM. Elastomers can be used in the form of rubber compounds containing, for example, vulcanizing agents, vulcanization activators, oils, and / or fillers. The thermoplastic polyamide molding materials proposed herein also preferably do not contain a graft copolymer that can be prepared using a) 0.5 to 25% by weight, based on the graft copolymer, of a polyamine having at least four nitrogen atoms, and b) 75 to 99.5% by weight, based on the graft copolymer, of a polyamide-forming monomer selected from lactams, ω-aminocarboxylic acids, and / or equimolar combinations of diamines and dicarboxylic acids, where the sum of the parts by weight of a) and b) is 100.

[0011] In view of the present application, it is preferred to use exclusively ungrafted polyethyleneimines as component (B), i.e. the molding material as a whole is free from grafted polyethyleneimines.

[0012] EP 1 541 336 A1 relates to a thermoplastic multilayer composite comprising at least one first layer based on a fluoropolymer and at least one additional second layer directly adjacent to the first layer, at least in part. In such a multilayer composite, adhesion between the two layers is achieved by forming the second layer with a polyamide / polyamine copolymer as the base material. Such a second layer can be particularly advantageously used as an adhesion-promoting layer for a third additional polyamide-based layer. In the form of a hollow body or hollow shape, a structure comprising at least three layers can be used as a fuel line in the automotive sector.

[0013] From the standpoint of the present application, it is preferred to use exclusively polyethyleneimines as component (B) that does not contain any amide-forming copolymer units, i.e., the molding material as a whole does not contain any polyethyleneimines that contain amide-forming copolymer units.

[0014] German Patent Application No. 19736345 A1 relates to a thermoplastic multicomponent injection-molding composition made of at least partially incompatible independent components, i.e., a polyamide molding composition and a modified block copolymer, which are firmly bonded to one another by injection molding or extrusion. The block copolymer is based on vinyl aromatic and olefinic monomers and is grafted with carboxyl groups or groups derived therefrom. The polyamide molding composition contains the modified block copolymer to improve adhesion. The adhesive strength is good immediately after injection molding, but decreases to unacceptable values ​​within one to two days when stored in a standard climate (70°C / 62% relative humidity).

[0015] Therefore, the present invention specifically relates to directly adjacent and firmly adhered (I) a profile formed from a thermoplastic molding material FM-1, which comprises at least one polyamide (A), and optionally fillers and / or reinforcing materials (C) and additives (D), (II) a profile formed from a thermoplastic molding material FM-2 containing at least one olefin and / or vinyl aromatic polymer (E), and optionally fillers and reinforcing materials (F), plasticizers (G), and additives (H); Including, The present invention relates to a composite material, wherein the molding material FM-1 or the molding material FM-2 contains 0.1 to 5.0% by weight of polyethyleneimine (B) or a copolymer or derivative thereof.

[0016] The molding material FM-1 or FM-2 contains polyethyleneimine (B) preferably in an amount of 0.5 to 4.0 weight percent, particularly preferably 0.8 to 3.0 weight percent, based on the total weight of the molding material FM-1 or FM-2, respectively.

[0017] Thus, a composite according to the present invention refers to a molding having at least one profile (I) and at least one profile (II) that are firmly bonded to each other at at least one point or at at least one contact surface without the use of an intermediate layer or adhesive to promote adhesion. That is, profile (I) and profile (II) are in direct contact at at least one point and bonded to each other through this contact. For example, if one or both profiles are planar, the contact surface can be limited to only one narrow side of the profile in question, can extend over the entire side of one profile, or can be characterized by a partial or complete overlap of the upper or lower surfaces of both profiles. For example, profile (II) can be bonded to profile (I) at one or all of its sides and also at a portion of its upper or lower surface.

[0018] The composite material according to the invention is preferably a hard-soft composite in which profile (I) has a higher Shore hardness of D or A than profile (II), each determined in the dry state according to ISO 7619-1 (2012-02). In this respect, it is particularly preferred if profile (I) has a Shore hardness of at least 70D, preferably at least 75D, particularly preferably at least 80D, and / or profile (II) has a Shore hardness of at most 60D, preferably at most 50D, particularly preferably at most 39D or 90A, each determined in the dry state according to ISO 7619-1 (2012-02).

[0019] Furthermore, it is preferred that the elastic modulus of profile (I) is greater than that of profile (II), each determined in the dry state according to ISO 527 (2012). It is preferred that profile (I) has an elastic modulus of at most 1000 MPa, preferably at most 4000 MPa, particularly preferably at most 8000 MPa, and / or profile (II) has an elastic modulus of at most 500 MPa, at most 300 MPa, particularly preferably at most 200 MPa.

[0020] The composite material according to the present invention preferably refers to a rigid-flexible composite in which rigid (hard) and flexible (soft) profiles are adjacent to each other and bonded to each other at at least one point or one contact surface. The rigid (hard) profile (I) and the flexible (soft) profile (II) preferably form separate parts of the molding and can be bonded to each other only at the contact transitions between the profiles, i.e., the contact points or surfaces described above, for example, by abutting and / or overlapping. In this way, the unique and very different material properties of the independent profiles (I) and (II) of the composite are fully utilized. This means that completely different molding materials must be used to produce the various profiles. Polyamide-based molding material FM-1 is used to produce rigid profile (I), while olefin / vinyl aromatic polymer-based molding material FM-2 is used to produce profile (II).

[0021] For purposes of this invention, the terms "olefin / vinyl aromatic polymer" and "olefin and / or vinyl aromatic polymer" are used interchangeably and include a general term including both homopolymeric and copolymeric polyolefins and copolymers made from vinyl aromatic and olefin monomers, as well as modifications thereof grafted with carboxylic acid or carboxylic acid anhydride groups.

[0022] In the context of the present invention, the term "polyamide" (abbreviated PA) is recognized as a generic term that includes homopolyamides and copolymeric polyamides. The selected spellings and abbreviations of polyamides and their monomers are consistent with those specified in ISO 16396-1 (2015(D)). In the following, the abbreviations used are used synonymously with the IUPAC names of the monomers, and specifically the following abbreviations exist for the monomers: MACM stands for bis(4-amino-3-methyl-cyclohexyl)methane, also known as (3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, CAS No. 6864-37-5); PACM stands for bis(4-amino-cyclohexyl)methane, also known as (4,4'-diaminodicyclohexylmethane, CAS No. 1761-71-3); TMDC stands for bis(4-amino-3,5-dimethyl-cyclohexyl)methane, also known as (3,3',5,5'-tetramethyl-4,4'-diamino-dicyclohexylmethane, CAS No. 65962-45-0); T stands for terephthalic acid (CAS No. 100-21-0); and I stands for isophthalic acid (CAS No. 121-95-5).

[0023] In comparison with semi-crystalline polyamides, amorphous polyamides have no or extremely low, almost undetectable heats of fusion. In differential scanning calorimetry (DSC) according to ISO 11357 (2013) at a heating rate of 20 K / min, amorphous polyamides preferably exhibit a heat of fusion of at most 5 J / g, particularly preferably at most 3 J / g, and very particularly preferably 0 to 1 J / g. Due to their amorphous nature, amorphous polyamides have no melting point.

[0024] For the purposes of the present invention, semi-crystalline polyamides are polyamides which, in differential scanning calorimetry (DSC) according to ISO 11357 (2013) at a heating rate of 20 K / min, preferably have a heat of fusion of more than 5 J / g, particularly preferably at least 25 J / g, very particularly preferably at least 30 J / g.

[0025] According to a first preferred embodiment, the composite according to the invention is characterized in that the thermoplastic molding material FM-1 comprises the following components: (A) 30 to 99.9 weight percent of at least one polyamide; (B) 0.1 to 5.0 weight percent of polyethyleneimine or a copolymer or derivative thereof; (C) 0 to 60 weight percent fillers and / or reinforcing materials; (D) 0 to 5.0 weight percent of an additive other than (A) to (C). Including, The total of (A) to (D) is 100 weight percent of thermoplastic polyamide molding material FM-1; and Thermoplastic molding compound FM-2 contains: (E) 45 to 100 weight percent of at least one olefin and / or vinyl aromatic polymer; (F) 0 to 15 weight percent fillers and / or reinforcing materials; (G) 0 to 35 weight percent of a plasticizer; (H) 0 to 5.0 weight percent of additives other than (E), (F), and (G). Including, The total of (E) to (H) is 100 weight percent of the thermoplastic molding material FM-2. The molding material FM-2 does not contain component (B).

[0026] According to a second preferred embodiment, the composite is characterized in that the thermoplastic molding material FM-1 comprises the following components: (A) 35 to 100 weight percent of at least one polyamide; (C) 0 to 60 weight percent fillers and / or reinforcing materials; (D) 0 to 5.0 weight percent of an additive other than (A) and (C). Including, the sum of (A), (C), and (D) is 100 weight percent of thermoplastic polyamide molding material FM-1; Thermoplastic molding compound FM-2 contains: (E) 40 to 99.9 weight percent of at least one olefin and / or vinyl aromatic polymer; (B) 0.1 to 5.0 weight percent of polyethyleneimine or a copolymer or derivative thereof; (F) 0 to 15 weight percent fillers and / or reinforcing materials; (G) 0 to 35 weight percent of a plasticizer; (H) 0 to 5.0 weight percent of additives other than (E), (F), (G), and (B). Including, The sum of (B) and (E) to (H) is 100 weight percent of the thermoplastic molding material FM-2. The molding material FM-1 does not contain component (B).

[0027] The at least one polyamide (A) in the molding material FM-1 is preferably present in a proportion of 31 to 79.5 weight percent, particularly preferably 40 to 74 weight percent, relative to the total weight of the molding material FM-1, when the molding material FM-1 contains component (B) (first preferred embodiment), or is preferably present in a proportion of 35 to 80 weight percent, particularly preferably 43 to 74.8 weight percent, relative to the total weight of the molding material FM-1, when the molding material FM-1 does not contain component (B) (second preferred embodiment).

[0028] When molding material FM-2 contains component (B) (second preferred embodiment), the at least one olefin and / or vinyl aromatic polymer (E) is present in an amount of preferably 51 to 94.4 weight percent, particularly preferably 62 to 89 weight percent, relative to the total weight of molding material FM-2; or when molding material FM-2 does not contain component (B) (first preferred embodiment), the at least one olefin and / or vinyl aromatic polymer (E) is present in an amount of preferably 55 to 94.9 weight percent, particularly preferably 65 to 89.8 weight percent, relative to the total weight of molding material FM-2.

[0029] It is also preferred that the molding material FM-2 comprises, as component (E), at least one vinyl aromatic polymer and optionally at least one polyolefin. It is particularly preferred that the molding material FM-2 comprises at least 50 weight percent, in particular at least 70 weight percent, of the vinyl aromatic polymer, each of which is based on the total amount of (E).

[0030] The at least one olefin and / or vinyl aromatic polymer (E) of the molding material FM-2 is preferably selected from the group consisting of styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butylene-styrene block copolymer (SBS), styrene-styrene-butylene-styrene block copolymer (SSBS), polyethylene (PE), polypropylene (PP), polybutadiene (PB), poly-4-methylpentene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-methylhexadiene copolymer, propylene-methylhexadiene copolymer, ethylene-octene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-hexene copolymer, ethylene-propylene-methylhexadiene copolymer, poly(ethylene-vinyl acetate) (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-hexene copolymer, ethylene-propylene-diene terpolymer, and mixtures of these polymer materials.

[0031] Furthermore, it is preferred that the at least one olefin and / or vinyl aromatic polymer (E) of the molding material FM-2 is grafted with carboxylic acid or carboxylic acid anhydride groups, particularly preferably with acrylic acid, methacrylic acid, or maleic anhydride, and / or that the degree of graft polymerization is preferably from 0.1 to 4.0% by weight, more preferably from 0.4 to 2.5% by weight, particularly preferably from 0.5 to 2.0% by weight, based on the graft polymer (E), in each case.

[0032] The polyamides of component (A) are semicrystalline acyclic aliphatic polyamides, semicrystalline semiaromatic polyamides, cycloaliphatic polyamides, amorphous semiaromatic polyamides, or mixtures of these polyamides, and are particularly preferably of the AABB type, i.e., composed of dicarboxylic acids and diamines, with additional, concomitant proportions of lactams and amino acids being possible as components.

[0033] For example, the following monomers are suitable as diamines of component (A): 1,4-butanediamine, 2-methyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 2-methyl-1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, m-xylylenediamine, and p-xylylenediamine, with 1,6-hexanediamine, 1,10-decanediamine, and 1,12-dodecanediamine being preferred.

[0034] For example, the following monomers can be used as dicarboxylic acids for component (A): adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, C36 dimer fatty acids, and / or cis- and / or trans-1,4-cyclohexanecarboxylic acid and / or cyclohexanecarboxylic acid, trans-cyclohexane-1,3-dicarboxylic acid (CHDA), terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids, in particular 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, and mixtures thereof. Adipic acid, sebacic acid, tetradecanedioic acid, hexadecanedioic acid, and dodecanedioic acid are preferred.

[0035] Furthermore, the polyamides (A) can also contain lactams or aminocarboxylic acids, especially α,ω-amino acids or lactams having 6 to 12 carbon atoms, such as m-aminobenzoic acid, p-aminobenzoic acid, caprolactam (CL), α,ω-aminocaproic acid, α,ω-aminoheptanoic acid, α,ω-aminooctanoic acid, α,ω-aminononanoic acid, α,ω-aminodecanoic acid, α,ω-aminoundecanoic acid (AUA), laurolactam (LL), and α,ω-aminododecanoic acid (ADA). Caprolactam, aminocaproic acid, α,ω-aminoundecanoic acid, laurolactam, and α,ω-aminododecanoic acid are particularly preferred. However, the proportion of these lactams or amino acids, based on the total weight of the polyamide (A), is preferably less than 50 weight percent, more preferably less than 20 weight percent, and particularly preferably less than 10 weight percent.

[0036] The semicrystalline acyclic aliphatic polyamides (A1) are preferably selected from the group consisting of 46, 56, 66, 66 / 6, 69, 610, 612, 614, 616, 618, 810, 1010, 1012, 1014, 1016, 1212, 11, 12, 6 / 12, 66 / 6 / 610, with particular preference given to 66, 610, 612, 614 and 616. Here and below, for example, the designation "46" is to be understood as polyamide 46 or simply PA46.

[0037] The semicrystalline, semiaromatic polyamides (A2) of component (A) are preferably selected from the group consisting of 6T / 6I, 6T / 66, 6T / 6I / 66, 6T / 610, 6T / 612, 6T / 614, 6T / 616, 9T, 9MT (M=2-methyloctane-1,8-diamine), 10T, 12T, 10T / 6T, 11 / 10T, 12 / 10T, 11 / 9T, 12 / 9T, 10T / 1010, 10T / 106, 10T / 612, the proportion of terephthalic acid relative to the total amount of dicarboxylic acids being preferably greater than 30 mol %, particularly preferably greater than 50 mol %.

[0038] The polyamides of component (A) are also preferably cycloaliphatic polyamides (A3): MACM12 / PACM12, MACM14 / PACM14, MACM16 / PACM16, MACM18 / PACM18, 6I / 6T / MACMI / MACMT / 12, 6I / 6T / 612 / MACMI / MACMT / MACM12, 6I / 6T / 614 / MACMI / MACMT / MACM14, 6I / 6T / 616 / MACMI / MACMT / MACM16, 6I / MACMI / MACMT, 6I / PACMI / PACMT, MACMI / MACMT / 12, 6I / 6T / MACMI, MACMI / MACM36, 12 / PACMI, 12 / MACMT, 6I / PACMT, 6 / IPDT, MACM10, MACM12, MACM14, MACM16, MACM18, MACMI / 12, PACM10, PACM12, MACM14, PACM16, PACM18, PACMI / 12, TMDC10, TMDC12, TMDC16, TMDC18, MACMT / MACMI / 12, PACMT / PACMI / 12, or mixtures thereof.

[0039] Amorphous semi-aromatic polyamides (A4) can also be used as component (A), preferably selected from the group consisting of MXDI, MXDI / 6I, MXD6 / MXDI, 5I, 5T / 5I, 6I, 6 / 6I, 6T / 6I, 10T / 10I, 3-6T (3-6=2,2,4- or 2,4,4-trimethylhexanediamine), or mixtures thereof, with the 5T / 5I, 6T / 6I, or 10T / 10I system having a proportion of 5T, 6T, or 10T units of less than 50 mol % and with a 5T:5I, 6T:6I, or 10T / 10I composition range of 20:80 to 45:55, in particular 25:75 to 40:60.

[0040] The diamines of the cycloaliphatic polyamides (A3) are preferably selected from the group consisting of bis(4-amino-3-methyl-cyclohexyl)methane (MACM) and bis(4-aminocyclohexyl)methane (PACM), bis-(4-amino-3-ethyl-cyclohexyl)methane (EACM), bis(4-amino-3,5-dimethyl-cyclohexyl)methane (TMDC), 2,6-norbornanediamine (2,6-bis(aminomethyl)norbornane), 1,3-diaminocyclohexane, 1,4-diaminocyclohexanediamine, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2,2-(4,4'-diaminodicyclohexyl)propane, meta-xylylenediamine, para-xylylenediamine, and mixtures thereof. The diamines are particularly preferably selected from the group consisting of bis(4-amino-3-methyl-cyclohexyl)methane (MACM) and bis(4-aminocyclohexyl)methane (PACM), and mixtures thereof.

[0041] The dicarboxylic acids of the cycloaliphatic polyamide component (A3) are preferably selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids (NDA), especially 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, 1,6-hexanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid, 1,18-octadecanedioic acid, and mixtures thereof. 1,6-hexanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid, terephthalic acid, isophthalic acid, and mixtures thereof are particularly preferred. Furthermore, caprolactam and laurolactam are preferred monomers for preparing the cycloaliphatic polyamides of component (A3).

[0042] The alicyclic polyamides (A3) and the amorphous semi-aromatic polyamides (A4) preferably have a glass transition temperature Tg of more than 90°C, more preferably more than 110°C, particularly preferably more than 120°C.

[0043] The polyamides (A1) and (A2) preferably have a melting point of at least 170°C, preferably in the range of 180 to 340°C, or preferably in the range of 180 to 230°C if aliphatic (ie component A1).

[0044] The polyamides of component (A), in particular the polyamides (A1), (A2), (A3) and (A4), also preferably have a relative viscosity, measured in m-cresol (0.5% by weight, 20°C), in the range of 1.4 to 3.0, preferably in the range of 1.45 to 2.70, particularly preferably in the range of 1.50 to 2.40.

[0045] In a further embodiment, the at least one polyamide (A) of the molding material FM-1 comprises the following components: 20 to 100 weight percent, preferably 40 to 80 weight percent, of at least one semi-crystalline acyclic aliphatic polyamide (A1) and / or at least one semi-aromatic semi-crystalline polyamide (A2), 0 to 80 weight percent, preferably 20 to 60 weight percent, of at least one alicyclic polyamide (A3) and / or amorphous semi-aromatic polyamide (A4) or consisting of the above components, It is especially preferred that the weight percent of components (A1) through (A4) sum to 100 weight percent component (A).

[0046] In another particularly preferred embodiment of the composite, the at least one polyamide (A) of the molding material FM-1 comprises the following components: (A1) 20 to 80 weight percent, preferably 25 to 75 weight percent, of at least one semicrystalline acyclic aliphatic polyamide selected from the group consisting of PA66, PA610, PA612, PA614, and PA616; (A4) 20 to 80 weight percent, preferably 25 to 75 weight percent, of at least one amorphous semi-aromatic polyamide selected from the group consisting of 5T / 5I, 6T / 6I, and 10T / 10I or consisting of the above components, The weight percent of components (A1) and (A4) add up to 100 weight percent of component (A).

[0047] The molding material FM-1 preferably does not comprise any olefin / vinyl aromatic polymer, either in grafted or ungrafted form, i.e. the molding material FM-1 preferably does not comprise component (E).

[0048] The molding material FM-2 contains at least one olefin and / or vinyl aromatic polymer as component (E). That is, component (E) can contain at least one olefin polymer, or at least one vinyl aromatic polymer, or a combination of at least one olefin polymer and at least one vinyl aromatic polymer. The olefin polymer refers to homopolymerized or copolymerized polyolefins, particularly preferably polymers or copolymers based on ethylene, propylene, and butylene, and copolymers thereof with other α-olefin monomers, specifically 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene. The vinyl aromatic polymer is preferably a copolymer of styrene with other monomers having at least one olefinic double bond, such as α-olefins such as ethylene, propylene, and butylene, or acrylic acid or acrylic acid esters, or butadiene. Particularly preferred are block copolymers having at least one block (block A) formed from a vinyl aromatic monomer and at least one block (block B) formed from an olefin monomer, such as styrene block copolymers. Furthermore, mixtures of styrene block copolymers with polyolefins are also preferred.

[0049] The olefin and / or vinyl aromatic polymers used as constituents of component (E) can be or contain natural rubber, polybutadiene, polyisoprene, polyisobutylene, copolymers or hydrogenated copolymers of butadiene and / or isoprene with styrene or styrene derivatives and other comonomers, and / or copolymers formed by graft polymerization or copolymerization with acid anhydrides, (meth)acrylic acid, and their esters. Polymer (E) can also be a graft rubber having a crosslinked elastomeric core composed of butadiene, isoprene, or alkyl acrylate and a graft shell made of polystyrene, nonpolar or polar olefin homopolymers and copolymers (e.g., ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-octene rubber, or ethylene-vinyl acetate rubber), or nonpolar or polar olefin homopolymers and copolymers (formed by graft polymerization or copolymerization with acid anhydrides, (meth)acrylic acid, and their esters). The polymer (E) can also be a copolymer functionalized with a carboxylic acid, such as poly(ethene-co-(meth)acrylic acid) or poly(ethene-co-1-olefin-co-(meth)acrylic acid), in which the 1-olefin is an alkene or unsaturated (meth)acrylic acid ester with more than four atoms, and can include copolymers in which the acidic groups are partially neutralized with metal ions.

[0050] The polymer (E) is preferably based on styrene monomers (styrene and styrene derivatives) and other vinyl aromatic monomers and is fabricated as a block copolymer of several alkenyl aromatic compounds with a conjugated diene, as a hydrogenated block copolymer of an alkenyl aromatic compound with several conjugated dienes, or as a combination of these polymer types. The block copolymer contains at least one block (block A) derived from an alkenyl aromatic compound and at least one block (block B) derived from a conjugated diene. In the hydrogenated block copolymer, the proportion of aliphatic unsaturated carbon-carbon double bonds has been reduced by hydrogenation. Linear bi-, tri-, tetra-, and multi-block copolymers are suitable as block copolymers. However, branched and star structures can also be used in accordance with the present invention. Branched block copolymers can be obtained by known methods, for example, by grafting polymeric "side branches" onto the polymer backbone.

[0051] In addition to or in combination with styrene, the alkenyl aromatic monomer may also be a vinyl aromatic monomer substituted on the aromatic ring and / or C=C double bond with a C1-20 hydrocarbon radical or a halogen atom. Examples of preferred alkenyl aromatic monomers include styrene, p-methylstyrene, α-methylstyrene, ethylstyrene, tert-butylstyrene, vinyltoluene, 1,2-diphenylethylene, 1,1-diphenylethylene, vinylxylenes, vinyltoluenes, vinylnaphthalenes, divinylbenzenes, bromostyrenes, chlorostyrenes, and combinations thereof. Preferred are styrene, p-methylstyrene, α-methylstyrene, and vinylnaphthalene.

[0052] Examples of diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, isoprene, chloroprene, and piperene. 1,3-Butadiene and isoprene are preferred, and 1,3-butadiene (hereinafter simply referred to as butadiene) is particularly preferred.

[0053] The preferred alkenyl aromatic monomers are styrene and the diene monomer butadiene. That is, styrene-butadiene block copolymers are preferred. Typically, these block copolymers are prepared by anionic polymerization, as known per se.

[0054] In addition to styrene and diene monomers, further comonomers can also be used. The proportion of the comonomer is preferably 0 to 50% by weight, particularly preferably 0 to 30% by weight, and in particular 0 to 15% by weight, based on the total amount of monomers used. Suitable comonomers include, for example, acrylates, especially C1-12 alkyl acrylates such as n-butyl acrylate or 2-ethylhexyl acrylate, and the corresponding methacrylates, especially C1-12 alkyl methacrylates such as methyl methacrylate (MMA). Further possible comonomers include (meth)acrylonitrile, glycidyl (meth)acrylate, vinyl methyl ether, diallyl and divinyl ethers of difunctional alcohols, divinylbenzene, and vinyl acetate.

[0055] In addition to conjugated dienes, hydrogenated block copolymers may also contain lower hydrocarbon moieties such as ethylene, propylene, 1-butene, dicyclopentadiene, or non-conjugated dienes. In hydrogenated block copolymers, the proportion of non-reducing aliphatic unsaturated bonds attributable to the B block is less than 50%, preferably less than 25%, and particularly preferably less than 10%. The proportion of aromatics in block A is preferably reduced to a maximum of 25%. Hydrogenated block copolymers such as styrene (ethylene-butylene) diblock copolymers and styrene (ethylene-butylene)-styrene triblock copolymers can be obtained by hydrogenating styrene-butadiene copolymers and styrene-butadiene-styrene copolymers.

[0056] The block copolymer preferably comprises from 20 to 90% by weight of block A, in particular from 25 to 60% by weight of block A. The diene can be incorporated in the B block in the 1,2 or 1,4 position.

[0057] The molecular weight of the block copolymer is 5,000 to 500,000 g / mol, preferably 20,000 to 300,000 g / mol, and particularly 40,000 to 200,000 g / mol.

[0058] Suitable hydrogenated block copolymers include commercially available products such as, for example, KRATON® (Kraton Polymers) G1650, G1651, G1652, and TUFTEC® (Asahi Chemical Industry Co., Ltd.) H1041, H1043, H1052, H1062, H1141, H1272.

[0059] Examples of non-hydrogenated block copolymers include polystyrene-polybutadiene, polystyrene-poly(ethylene-propylene), polystyrene-polyisoprene, poly(α-methylstyrene)-polybutadiene, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly(ethylene-propylene)-polystyrene (SEPS), polystyrene-polyisoprene-polystyrene, and poly(α-methylstyrene-polybutadiene-poly(α-methylstyrene), and combinations thereof.

[0060] Suitable commercially available non-hydrogenated block copolymers include various products under the trade names SOLPRENE® (Phillips), KRATON® (Shell), VECTOR® (Dexco), and SEPTON® (Kuraray Co., Ltd.).

[0061] According to a further preferred embodiment, the molding material according to the invention is characterized in that component (E) comprises a polyolefin homopolymer or an ethylene α-olefin copolymer, particularly preferably an EP and / or EPDM elastomer (ethylene-propylene rubber or ethylene-propylene-diene rubber). For example, this may be an elastomer based on an ethylene-C3-12 α-olefin copolymer having 20 to 96% by weight, preferably 25 to 85% by weight, of ethylene, in which the C3-12 α-olefin is selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and / or 1-dodecene. Component (E) is particularly preferably ethylene-propylene rubber, ethylene-butylene rubber, ethylene-octene rubber, and / or LLDPE and / or VLDPE.

[0062] Alternatively or additionally (e.g. in a mixture), (E) may comprise a terpolymer based on ethylene-C3-12-alpha olefin with a non-conjugated diene, preferably comprising 25 to 85% by weight of ethylene and up to 10% by weight of a non-conjugated diene, with the C3-12-alpha olefin being particularly preferably selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and / or 1-dodecene, and / or the non-conjugated diene being preferably selected from the group consisting of bicyclo(2,2,1)heptadiene, hexadiene-1.4, dicyclopentadiene, and / or especially 5-ethylidenenorbornene.

[0063] Component (E) is preferably composed of carboxylic acid or carboxylic acid anhydride groups, which are reacted through a thermal or radical reaction of the main chain polymer with an unsaturated dicarboxylic acid anhydride, unsaturated dicarboxylic acid, or unsaturated dicarboxylic acid monoalkyl ester, preferably with a reagent selected for this purpose from the following group: acrylic acid, maleic acid, maleic anhydride, maleic acid monobutyl ester, fumaric acid, aconitic acid, and / or itaconic anhydride.

[0064] Preferably, 0.1 to 4.0% by weight of an unsaturated anhydride or unsaturated dicarboxylic acid is grafted onto the polymer (E). In general, the degree of graft polymerization is preferably in the range of 0.4 to 2.5%, particularly preferably in the range of 0.5 to 2.0%.

[0065] A mixture of an ethylene-propylene copolymer and an ethylene-butylene copolymer, each having a maleic anhydride graft polymerization degree (MAH graft polymerization degree) in the range of 0.4 to 2.5% by weight, can also be used as a constituent of component (E).

[0066] Polyolefin elastomers can be statistical, alternating, or segmented copolymers with linear, branched, or core-shell structures, and preferably contain functional groups, thus including homopolymers or copolymers of olefins such as ethylene, propylene, butene-1, or copolymers of olefins and copolymerizable monomers such as vinyl acetate, (meth)acrylic acid esters, and methylhexadiene.

[0067] Examples of crystalline olefin polymers include low-, medium-, and high-density polyethylenes, polypropylene, polybutadiene, poly-4-methylpentene, ethylene-propylene block or statistical copolymers, ethylene-methylhexadiene copolymers, propylene-methylhexadiene copolymers, ethylene-propylene butene copolymers, ethylene-propylene-hexene copolymers, ethylene-propylene-methylhexadiene copolymers, poly(ethylene-vinyl acetate) (EVA), poly(ethylene-ethyl acrylate) (EEA), ethylene-octene copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-propylene-diene terpolymers, and combinations of these polymers.

[0068] Also preferred are ionomers, in which the polymer-bound carboxyl groups are bonded together in whole or in part by metal ions.

[0069] Particularly preferred are copolymers of butadiene and styrene functionalized by grafting with maleic anhydride, non-polar or polar olefin homopolymers and copolymers formed by grafting with maleic anhydride, and copolymers functionalized with carboxylic acids, such as poly(ethene-co-(meth)acrylic acid) or poly(ethene-co-1-olefin-co-(meth)acrylic acid), in which the acidic groups are partially neutralized with metal ions.

[0070] Polymer (E) is styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butylene-styrene block copolymer (SBS), styrene-styrene-butylene-styrene block copolymer (SSBS), ethylene / propylene copolymer, ethylene / propylene / diene copolymer (EPDM), polyethylene (PE), polypropylene (PP), polybutadiene (PB), poly-4-methylpentene, ethylene-propylene copolymer The polymer (E) is advantageously selected from the group consisting of ethylene-butene copolymers, ethylene-methylhexadiene copolymers, propylene-methylhexadiene copolymers, ethylene-octene copolymers, ethylene-propylene-butene copolymers, ethylene-propylene-hexene copolymers, ethylene-propylene-methylhexadiene copolymers, poly(ethylene-vinyl acetate) (EVA), ethylene-ethyl acrylate copolymers (EEA), ethylene-hexene copolymers, ethylene-propylene-diene terpolymers, and mixtures of these polymer materials. These polymers (E) are particularly preferably grafted with acrylic acid, methacrylic acid, or maleic anhydride, with a degree of graft polymerization of 0.1 to 4.0 percent by weight, based on the graft polymer (E).

[0071] Particularly preferred vinyl aromatic polymers for component (E) are styrene-ethylene / butylene-styrene copolymers (SEBS) and / or SEBS grafted with maleic anhydride (MAH) (SEBS-g-MAH). SEBS and SEBS-g-MAH each preferably contain 20 to 70% by weight of styrene. SEBS-g-MAH preferably has a melt volume flow rate (MVR) of at least 80 ml / 10 min, preferably 90 to 200 ml / 10 min, and particularly preferably 100 to 160 ml / 10 min, at 275°C under a 5 kg load. The amount of maleic anhydride in SEBS-g-MAH is preferably 0.1 to 4.0% by weight, more preferably 0.4 to 2.5% by weight, and particularly preferably 0.5 to 2.0% by weight.

[0072] Particularly preferred olefin polymers for component (E) are polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer (EP), ethylene-butylene copolymer (EB), and graft-modified olefin polymers with maleic anhydride (MAH) or acrylic acid (AA), such as PE-g-MAH, PE-g-AA, PP-g-MAH, PP-g-AA, EP-g-MAH, EP-g-AA, EB-g-MAH, and EB-g-AA, as well as mixtures thereof. The amount of acrylic acid or maleic anhydride in PE-g-MAH, PE-g-AA, PP-g-MAH, PP-g-AA, EP-g-MAH, EP-g-AA, EB-g-MAH, and EB-g-AA is preferably 0.1 to 4.0% by weight, more preferably 0.4 to 2.5% by weight, and particularly preferably 0.5 to 2.0% by weight.

[0073] Component (E) is also preferably composed of a mixture of the vinyl aromatic and olefin polymers mentioned above, particularly preferably a mixture of SEBS-g-MAH and PP, SEBS and PP-g-MAH, or SEBS-g-MAH and PP-g-MAH, in which the amount of maleic anhydride in the PP-g-MAH and / or SEBS-g-MAH is preferably 0.1 to 4.0% by weight, more preferably 0.4 to 2.5% by weight, and particularly preferably 0.5 to 2.0% by weight.

[0074] The possible systems given above for this component can also be used in mixtures.

[0075] According to the present invention, molding material FM-1 or FM-2 contains a specific proportion of polyethyleneimine as component (B). The proportion of component (B) in molding material FM-1 or FM-2 is preferably in the range of 0.5 to 4.0% by weight, more preferably in the range of 0.8 to 3.0% by weight. It is preferred that only molding material FM-1 contains a specific amount of polyethyleneimine as component (B), and molding material FM-2 does not contain component (B).

[0076] Polyethyleneimines as component (B) in the context of the present invention are understood to mean polymers in which NH or N groups are present in the main chain, each separated from the other by two methylene groups, as described, for example, in Encycl. Polym. Sci. Eng. 1, 680-739. For the purposes of the present invention, both homopolymers and copolymers and their derivatives are included. It is preferred to use branched polyethyleneimines.

[0077] The homopolymers are generally obtained by polymerizing ethyleneimine (aziridine) in aqueous or organic solution in the presence of an acid-releasing compound, acid, or Lewis acid. Such homopolymers are typically branched polymers containing primary, secondary, and tertiary amino groups in a ratio of about 30%:40%:30%. 13 The distribution of amino groups, as determined using C-NMR spectroscopy, is preferably in the range of 1:0.7:0.5 to 1:1.5:1, in particular 1:0.8:0.6 to 1:1.2:0.8, in terms of the ratio of primary to secondary to tertiary amino groups.

[0078] A compound having at least two amino functional groups is preferably used as the comonomer. Suitable comonomers are, for example, alkylenediamines having 2 to 10 carbon atoms in the alkylene group, with ethylenediamine and propylenediamine being preferred. Other suitable comonomers are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetriamine, dihexamethylenetriamine, aminopropylethylenediamine, and bisaminopropylethylenediamine.

[0079] Similarly, polyethyleneimines for purposes of the present invention include amidated polymers, which are typically obtained by reacting polyethyleneimines with carboxylic acids, their esters or anhydrides, carboxylic acid amides, or carboxylic acid halides.

[0080] Additionally, alkoxylated polyethyleneimines are suitable, which can be obtained, for example, by reacting polyethyleneimine with ethylene oxide and / or propylene oxide. Other suitable polyethyleneimines according to the present invention include polyethyleneimines containing hydroxyl groups and amphoteric polyethyleneimines (incorporation of anionic groups), as well as lipophilic polyethyleneimines, which are generally obtained by incorporating long-chain hydrocarbon groups into the polymer chain.

[0081] Polyethyleneimines typically have a weight average molecular weight (MW) Mw of 600 to 3,000,000, preferably 700 to 2,000,000. Preferred MW is 800 to 50,000, especially 1,100 to 25,000. The MW is determined by light scattering according to ASTM D4001.

[0082] The polyethyleneimine of component (B) can be a branched polyethyleneimine having a number average molar mass Mn in the range of 500 to 50,000 or 500 to 25,000 g / mol, preferably in the range of 1000 to 2500 or 600 to 2000 g / mol.

[0083] The polyethyleneimine of component (B) is preferably a branched polyethyleneimine having a primary to secondary amine ratio in the range of 1:2 to 2:1, preferably in the range of 1.2:1 to 1:1.2, and / or a primary to tertiary amine ratio in the range of 3:1 to 1:1, preferably in the range of 2:1 to 1.4:1, and / or a secondary to tertiary amine ratio in the range of 3:1 to 1:1, preferably in the range of 2:1 to 1.2:1.

[0084] The polyethyleneimine of component (B) is preferably a branched polyethyleneimine having a primary amino terminal group content in the range of 5,000 to 20,000 μeq / g (mmol / kg), preferably 7,000 to 12,000 μeq / g (mmol / kg).

[0085] The polyethyleneimine of component (B) is further preferably a branched polyethyleneimine having a water content of less than 4 weight percent, preferably less than 3 weight percent, particularly preferably less than 2 weight percent.

[0086] In addition, the proposed molding materials FM-1 and FM-2 may contain, in addition to the polyamide, olefin / vinyl aromatic polymer, and polyethyleneimine, additives in the form of fillers and / or reinforcing materials, i.e., component (C) or (F). Component (C) is preferably present in molding material FM-1 in a proportion ranging from 20 to 60 weight percent, preferably from 25 to 55 weight percent. Component (F) is preferably present in molding material FM-2 in a proportion ranging from 0 to 10 weight percent, and molding material FM-2 is preferably free of component (F). Furthermore, molding material FM-2 is preferably free of fibrous reinforcing material (F2).

[0087] Components (C) and (F) are Particularly preferred are inorganic pigments including soot, talc, mica, silicates, quartz, wollastonite, kaolin, silicic acid, magnesium carbonate, magnesium hydroxide, chalk, ground or precipitated calcium carbonate, lime, feldspar, barium sulfate, zinc oxide, zinc sulfide, lithopone, titanium dioxide (rutile, anatase), iron oxide, iron manganese oxide, metal oxides, especially spinels including copper-iron spinel, copper chromium oxide, zinc-iron oxide, cobalt-chromium oxide, cobalt-aluminum oxide, magnesium aluminum. particulate fillers (C1) or (F1) selected from the group consisting of aluminum oxide, copper-chromium-manganese mixed oxides, copper-manganese-iron mixed oxides, rutile pigments including titanium zinc rutile, nickel antimony titanate, chromium antimony titanate, hard or soft magnetic metals or alloys or ceramics, hollow spherical siliceous fillers, aluminum oxide, boron nitride, boron carbide, aluminum nitride, calcium fluoride, and other inorganic pigments, and mixtures thereof; and / or a fibrous reinforcement component (C2) or (F2) preferably selected from the group consisting of glass fibers, carbon fibers, graphite fibers, aramid fibers, nanotubes, or mixtures thereof, wherein the fibers of components (C2) and (F2) can have a circular or non-circular cross-sectional area; It is preferable that it consists of

[0088] The fillers (C1) and (C2), as well as (F1) and (F2), can also be surface-treated.

[0089] Components (C2) and (F2) are preferably glass fibers that are or consist essentially of the constituents silicon dioxide, calcium oxide, magnesium oxide, and aluminum oxide, with a weight ratio SiO2 / (CaO+MgO) of less than 2.7, preferably less than 2.5, in particular between 2.1 and 2.4. In particular, components (C2) or (F2) are E-glass fibers according to ASTM D578-00.

[0090] According to the present invention, the glass fibers (components C2 and F2) can also be high-strength glass fibers, preferably based on the ternary silicon dioxide-aluminum oxide-magnesium oxide system or the quaternary silicon dioxide-aluminum oxide-magnesium oxide-calcium oxide system, and containing 58-70 wt. % silicon dioxide (SiO), 15-30 wt. % aluminum oxide (AlO), 5-15 wt. % magnesium oxide (MgO), 0-10 wt. % calcium oxide (CaO), and 0-2 wt. % additional oxides, such as zirconium dioxide (ZrO), boron oxide (BO), titanium dioxide (TiO), or lithium oxide (LiO). The high-strength glass fibers preferably have a tensile strength of 4000 MPa or more, an elongation at break of at least 5%, and a tensile modulus of elasticity greater than 80 GPa. Specific examples of these high-strength glass fibers of component (C2) include S-glass fiber size 910 or 995 manufactured by Owens Corning, T-glass fiber manufactured by Nittobo, HiPertex manufactured by 3B, HS4-glass fiber manufactured by Sinoma Jinjing Fiberglass, R-glass fiber manufactured by Vetrotex, and S-1 and S-2-glass fibers manufactured by AGY.

[0091] The glass fibers of components (C2) and (F2) can be in the form of short fibers, preferably cut glass with a length ranging from 0.2 to 20 mm, or in the form of continuous fibers (rovings).

[0092] The glass fibers of components (C2) and (F2) according to the invention preferably have a circular or non-circular cross-section.

[0093] Glass fibers with a circular cross section, i.e., round glass fibers, typically have a diameter in the range of 5 to 20 μm, preferably in the range of 6 to 17 μm, and particularly preferably in the range of 6 to 13 μm. They are preferably used as short glass fibers (cut glass having a length of 0.2 to 20 mm, preferably 2 to 12 mm).

[0094] When components (C2) and (F2) are flat glass fibers, i.e., glass fibers with a noncircular cross-sectional area, flat glass fibers are preferably used in which the ratio of the main cross-sectional diameter to the secondary cross-sectional diameter perpendicular thereto is greater than 2, preferably 2 to 8, in particular 2 to 5. These so-called flat glass fibers have an oval, elliptical, elliptical with one or more constrictions (so-called cocoon fibers), polygonal, rectangular, or almost rectangular cross-sectional area. Another feature of the flat glass fibers used is that the length of the main cross-sectional diameter is preferably in the range of 6 to 40 μm, in particular in the range of 15 to 30 μm, and the length of the secondary cross-sectional diameter is in the range of 3 to 20 μm, in particular in the range of 4 to 10 μm. Flat glass fibers have the highest packing density. That is, the cross-sectional area of ​​the glass fiber occupies as precisely as possible at least 70%, preferably at least 80%, particularly preferably at least 85% of the apparent square surrounding the glass fiber cross-section.

[0095] Mixtures of glass fibers with circular or non-circular cross-sections can also be used to reinforce the molding materials according to the invention, preferably with a predominance of flat glass fibers, i.e., more than 50% by weight of the total mass of fibers.

[0096] The glass fibres according to the invention are preferably provided in sizes suitable for each thermoplastic, in particular polyamide, and contain adhesion promoters, for example based on amino or epoxy silane compounds.

[0097] According to a further preferred embodiment, E-glass or high-strength glass fibers used as rovings in components (C2) and (F2) preferably have a diameter of 8 to 20 μm, preferably 12 to 18 μm. The cross section of the glass fibers is circular, oval, elliptical, elliptical with one or more constrictions, polygonal, rectangular, or nearly rectangular. So-called flattened glass fibers, with a cross-sectional diameter ratio of 2 to 5, are particularly preferred. These continuous fibers, especially those in components (C2) and (F2), are incorporated into the polyamide molding compound according to the present invention by known processing methods for producing long-fiber-reinforced rod-shaped particles (fiber length and particle length are the same), specifically by extrusion, in which open-ended fiber strands (rovings) are completely impregnated with molten polymer, followed by cooling and chopping. The long-fiber-reinforced rod-shaped particles obtained in this manner, preferably with particle lengths of 3 to 25 mm, especially 4 to 12 mm, are further processed into moldings using conventional processing methods, such as injection molding or pressing. To strengthen the molding material according to the invention, the fibers with no ends (long glass fibers) can also be combined with cut fibers (short glass fibers).

[0098] Finally, the proposed molding material FM-1 can also contain additives such as component (D), and molding material FM-2 can also contain additives such as component (H). For molding material FM-1, component (D) is preferably present in a proportion ranging from 0.1 to 4.0 weight percent, preferably from 0.2 to 2.0 weight percent. For molding material FM-2, component (H) is preferably present in a proportion ranging from 0.1 to 4.0 weight percent, preferably from 0.2 to 2.0 weight percent.

[0099] The additives of components (D) and (H) can be selected from the group consisting of stabilizers, ageing inhibitors, antioxidants, antiozonants, light stabilizers, UV stabilizers, UV absorbers, UV screeners, inorganic heat stabilizers, especially those based on copper and alkali halides and / or lanthanide compounds, organic heat stabilizers, conductive additives, optical brighteners, processing aids, nucleating agents, crystallization accelerators, crystallization retarders, flow agents, lubricants, mold release agents, organic dyes, tagging agents, and mixtures thereof.

[0100] The molding material FM-2 can also contain 0 to 35 weight percent of a plasticizer as component (G). The molding material FM-2 preferably contains 5 to 35 weight percent, particularly preferably 10 to 33 weight percent, of the plasticizer. Preferably, paraffinic and / or naphthenic oils, preferably free of aromatic fractions, are used as component (G). The term "paraffinic" refers to acyclic saturated hydrocarbons, while the term "naphthenic" refers to cyclic saturated hydrocarbons. Therefore, plasticizers (G) based on aliphatic hydrocarbons, especially acyclic and / or cyclic aliphatic hydrocarbons, are preferred. Typically, mixtures of paraffinic and / or naphthenic hydrocarbons are present in liquid, oily, pasty, or solid form. Paraffinic oils are preferred, which are divided into liquid paraffins (paraffinum perliquidum), oily or pasty paraffins (paraffinum subliquidum), and solid paraffins (paraffinum solidum) depending on their viscosity and melting point. Liquid paraffin is particularly preferred.

[0101] In a preferred embodiment of the composite, the thermoplastic polyamide molding material FM-1 according to the invention comprises: (A) 40 to 74 weight percent of component (A), 20 to 100 weight percent, preferably 40 to 80 weight percent, of at least one semi-crystalline acyclic aliphatic polyamide (A1) and / or at least one semi-aromatic semi-crystalline polyamide (A2), 0 to 80 weight percent, preferably 20 to 60 weight percent, of at least one amorphous semi-aromatic polyamide (A4) and / or at least one cycloaliphatic polyamide (A3), Component (A), wherein the sum of the weight percentages of components (A1) to (A4) is 100 weight percent; (B) 0.8 to 3.0 weight percent polyethyleneimine; (C) 25 to 55 weight percent fillers and / or reinforcing materials; (D) 0.2 to 2.0 weight percent of an additive other than (A) to (C). It consists of The total of (A) to (D) is 100% by weight of the thermoplastic polyamide molding material, and the thermoplastic material FM-2 according to the present invention is (E) 55 to 94.9 weight percent of at least one vinyl aromatic polymer, particularly preferably at least one vinyl aromatic polymer selected from the group consisting of styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butylene-styrene block copolymer (SBS), styrene-styrene-butylene-styrene block copolymer (SSBS), grafted with acrylic acid, methacrylic acid, or maleic anhydride, and / or polyethylene, polypropylene, polybutadiene, poly-4-methylpentene, ethylene a vinyl aromatic polymer selected from the group consisting of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-methylhexadiene copolymer, propylene-methylhexadiene copolymer, ethylene-octene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-hexene copolymer, ethylene-propylene-methylhexadiene copolymer, poly(ethylene-vinyl acetate) (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-hexene copolymer, and ethylene-propylene-diene terpolymer, wherein the degree of graft polymerization is from 0.1 to 4.0 weight percent based on the graft polymer (E); (F) 0 to 10 weight percent fillers and / or reinforcing materials; (G) 5 to 35 wt. % of a plasticizer; (H) 0.1 to 4.0 weight percent of additives other than (E), (F), and (G). It consists of The total of (E) to (H) is 100 weight percent of the thermoplastic molding material FM-2.

[0102] The present invention also relates to the use of the thermoplastic molding materials FM-1 and FM-2 as described above for producing such composites. The composites according to the invention can be produced by injection molding or extrusion.

[0103] The method according to the invention for producing the composite material described above is preferably based on injection molding and comprises the following steps: (i) inserting a molding comprising at least one profile (I) formed from molding material FM-1 into an injection mold or injecting thermoplastic molding material FM-1 into an injection mold to form at least one profile (I), and (ii) the step of injecting the thermoplastic molding material FM-2 to form at least one profile (II) Including, Introducing the melt of molding material FM-1 and the melt of molding material FM-2 into an injection mold in parallel or sequentially without mixing or substantially without mixing; The process is such that the shapes (I) and (II) are in contact at least at one point.

[0104] In this case, it is preferable that the molding material FM-2 forms a flat profile (II) in the finished injection-molded product that is in contact with the profile (I) formed from the molding material FM-1, preferably on narrow sides and / or partial upper or lower surfaces, particularly preferably only on both sides.

[0105] In the context of the present description, the definition "without or substantially without mixing" means that the thermoplastic molding materials FM-1 and FM-2 for the composite enter the molding tool in an extrusion flow or in a co-flow manner.

[0106] In the process according to the invention, in step (i), the molded body comprising the profile (I) can be inserted into the injection mold as an independent preform made at least partially from the molding material FM-1. According to an alternative embodiment, this molded body is made in the injection mold in step (i).

[0107] The composite can be produced in a single injection molding process, i.e., steps (i) and (ii) can be carried out in parallel. This approach is advantageous due to its effectiveness and simplicity. However, in view of the present invention, it is also possible, and in many cases advantageous, to inject the thermoplastic molding material FM-1 into the injection mold in a first step, followed by the injection of the second thermoplastic molding material FM-2 in a second step (step ii).

[0108] The single step procedure can advantageously utilize single step standard sandwich injection processing or single step monosandwich processing known to those skilled in the art.

[0109] However, in view of the present invention, a multi-channel sandwich injection molding process can also be utilized in which two melts, molding materials FM-1 and FM-2, are injected into the injection mold from two different hot runner systems.

[0110] In the monosandwich process, the thermoplastic molding material FM-2 for the soft layer is injected from a simple extruder into the main cylinder containing the worm, e.g., a pusher screw extruder, before the thermoplastic molding material FM-1 arranged for the hard layer. The materials arranged vertically in the main cylinder in terms of orientation and rheology are injected into the mold in a single injection molding process, where the composite according to the invention is formed.

[0111] A molded article using the profile (I) can be produced separately from the molding material FM-1, or can be produced as is, in other words, in the same injection mold.

[0112] The insert process, in which a molded body using the shape material (I) or shape material (II) that has been separately prepared in advance is inserted into a molding die, is particularly suitable for producing small batches or large-sized carriers.

[0113] When producing composite parts using the profile (I) by injection molding, it is advantageous to use a core-back molding process. In this method, a tool is used in which one or more slides are drawn into the preform, i.e., after injection molding of the profile (I) based on the molding material FM-1, to create a cavity for the composite part from the molding material FM-2. This tool is also called a "multislide tool." Alternatively, the carrier can be produced using a turning tool.

[0114] In the composite according to the invention, excellent adhesion between the profile (I) and the profile (II) is achieved.

[0115] The present invention also relates to the use of polyethyleneimine or a copolymer or derivative thereof in a composite comprising a profile (I) formed from a molding material containing a polyamide and a profile (II) formed from a molding material containing an olefin / vinyl aromatic polymer, to improve the adhesive strength between the profiles (I) and (II). Again, the polyethyleneimine is preferably present in the molding material in an amount of 0.5 to 4.0 weight percent, preferably 0.8 to 3.0 weight percent, based on the total weight of the polyamide molding material. In the case of polyethyleneimine, branched polyethyleneimine is preferred, with a primary to secondary amine ratio of 1:2 to 2:1, preferably 1.2:1 to 1:1.2, and / or a primary to tertiary amine ratio of 3:1 to 1:1, preferably 2:1 to 1.4:1, and / or a secondary to tertiary amine ratio of 3:1 to 1:1, preferably 2:1 to 1.2:1.

[0116] More preferably, the polyethyleneimine is a branched polyethyleneimine having a number average molar mass Mn in the range from 500 to 50,000 or from 500 to 25,000 g / mol, preferably in the range from 600 to 2000 or from 1000 to 2500 g / mol.

[0117] The polyethyleneimine can preferably have the other properties already mentioned above for the thermoplastic polyamide molding compounds.

[0118] Preferred applications of the composite material include car ignition keys, function keys for car ignition keys, all kinds of remote controls e.g. for televisions, cranes and overhead cranes, handles for various pliers and power hand tools, housing seals for sealing against moisture and water, housings with flexible membranes or sealing lips, electrical switches with flexible membrane covers, electrical plugs with waterproof sealing lips, etc. Further embodiments are specified in the dependent claims. [Brief explanation of the drawings]

[0119] [Figure 1] 1 shows a composite specimen and holder used for roller peel testing to measure peel force, provided for illustrative purposes only and not to be construed as limiting.

[0120] JPEG0007792748000001.jpg68170 DETAILED DESCRIPTION OF THE INVENTION

[0121] Preparation of polyamide molding material FM-1 Polyamide granules and additives were metered into the feed zone, and glass fibers were added to the molten polymer via a side feeder 3 housing unit before the nozzle. The components in Table 1 were mixed in the proportions in Table 2 in a Werner and Pfleiderer twin-screw extruder using a 25 mm screw diameter corresponding to the given process parameters (see Table 3). The compounds outlined in Table 2 were extruded as strands through a 3 mm diameter nozzle, quenched with water, and granulated. The granules were dried at 100°C under a vacuum of 30 mbar for 24 hours.

[0122] Table 1: Materials used in the examples and comparative examples JPEG0007792748000002.jpg119121

[0123] Table 2: Adhesion strength to molding material FM-1 (B1, B2, and VB1 to VB5) and molding material FM-2 (I) to (III) JPEG0007792748000003.jpg122118

[0124] Table 3: Process parameters for compounding JPEG0007792748000004.jpg61170

[0125] To determine the mechanical properties, the compounds were injected into test specimens using an Arburg Allrounder 320-210-750 injection molding machine at specified cylinder temperatures of 240 to 280°C in zones 1 to 4 and a mold temperature of 100°C.

[0126] Preparation of molding material FM-2 Ingredient (I): Kraton G1651 (SEBS) 42.7% by weight Polybond 3200 (PP-g-MAH)24.0% by weight Plasticizer (Paraffinum Perliquidum) 33.0% by weight Irganox HP2921 0.3% by weight Component (II): Kraton FG1901 GT (SEBS-g-MAH) 99.7% by weight Irganox HP2921 0.3% by weight Component (III): Kraton G1651 (SEBS) 42.7% by weight Polybond 3200 (PP-g-MAH)23.0% by weight Plasticizer (Paraffinum Perliquidum) 33.0% by weight Lupasol G20 1.0% by weight Irganox HP2921 0.3% by weight

[0127] The SEBS, PP, and additives were metered into the feed zone, and the plasticizer was added to the molten polymer using a metering pump through the cylinder bore at the heating zone 3 level. These components were mixed in the specified ratios in a Werner and Pfleiderer twin-screw extruder with a 25 mm screw diameter at an average zone temperature of 200 to 230°C, a screw speed of 250 rpm, and a throughput of 8 kg / h. The molten polymer was extruded as a strand through a 3 mm diameter nozzle, quenched with water, and then granulated. The granules were dried at 80°C under a 30 mbar vacuum for 24 hours. The Shore hardness of test specimens made from this granulated material was 80A for molding material FM-2(I), 70A for molding material FM-2(II), and 78A for molding material FM-2(III). Preparation of composite test specimens

[0128] An Arburg Allrounder 520A injection molding machine equipped with a three-zone 30 mm standard screw was used to produce composite test specimens, so-called 2K peel plates made from a frame and a tab. For this purpose, in the first step (i), a frame plate (profile (I)) was injection-molded from molding material FM-1 (i.e., polyamide molding materials B1, B2, and VB1 to VB5). 25 seconds after the start of injection of the frame plate, the slide that occupied the cavity for profile (II) during step (i) was withdrawn from the tool. In the second step (ii), molding material FM-2 was injected into this now-vacant cavity, thus forming the flexible tab (profile (II)). The injection molding parameters used are summarized in the table below. Composite test specimen 1 can be seen in Figure 1. The frame has a side length of 120 mm, a width of 90 mm, and a thickness of 3 mm, while the tab 4 has a side length of 150 mm, a width of 30 mm, and a thickness of 1 mm. The overlapping area of ​​the frame 2 with the tab 4 is 50 × 30 mm. 2 The frame 2 includes an opening 3 having a side length c of 55 mm and a width d of 50 mm, and is arranged in the frame 2 so that the side of the tab 4 away from the sprue is positioned above the frame opening 3.

[0129] JPEG0007792748000005.jpg58170

[0130] Measurement method Unless otherwise specified, the test specimens were used dry. For this purpose, they were stored in a dry environment, i.e., on silica gel, at room temperature for at least 48 hours after injection molding.

[0131] The following measurement methods were used for this application: Melting point (Tm) and enthalpy of fusion (ΔHm): The melting point and enthalpy of fusion of the particulate material were determined according to ISO 11357-3 (2013). The DSC (differential scanning calorimetry) method was carried out at a heating rate of 20 K / min.

[0132] Glass transition temperature, Tg: The particulate glass transition temperature T was measured using differential scanning calorimetry (DSC) according to ISO 11357-2 (2013). g This was performed for each of two heating runs at a heating rate of 20 K / min. After the first heating run, the sample was quenched in dry ice. The glass transition temperature (T g ) was determined during the second heating. The "half-maximum" method identified the midpoint of the glass transition region as the glass transition temperature.

[0133] Relative viscosity, η rel : The relative viscosity was determined at 20°C according to ISO 307 (2007). For this purpose, 0.5 g of polymer particles were weighed into 100 ml of m-cresol (unless otherwise specified) and the relative viscosity (RV) was calculated according to Chapter 11 of the standard, according to RV = t / t0.

[0134] Tensile modulus: The tensile modulus was determined according to ISO 527 (2012) at 23 °C, a pulling speed of 1 mm / min, with an ISO tensile rod (type A1, dimensions 170 × 20 / 10 × 4) according to standard: ISO / CD 3167 (2003).

[0135] Breaking stress and elongation: The breaking stress and elongation at break were determined according to ISO 527 (2012) at 23 °C, a tensile speed of 5 mm / min, on ISO tensile rods type A1 (dimensions 170 × 20 / 10 × 4 mm) prepared according to ISO standard / CD 3167 (2003).

[0136] Charpy impact strength: ISO179 / 2 * eU (1997, * The Charpy impact strength was determined at 23 °C on ISO test rods type B1 (dimensions 80 × 10 × 4 mm) prepared according to ISO / CD 3167 (2003) according to JIS B 2 = instrumentation.

[0137] Notched Charpy impact strength: ISO179 / 2 * eA (1997, *The notched Charpy impact strength was determined at 23 °C on ISO test rods type B1 (dimensions 80 × 10 × 4 mfm) prepared according to ISO / CD 3167 (2003) according to 2 = instrumentation. Shore hardness

[0138] Shore hardness was determined using a Karl Franknach hardness tester according to ISO 7619-1 (2012-02) according to measurement methods A and D. The arithmetic mean value was obtained from five measurements. The dimensions of the test specimens used were 60 x 60 x 4 mm, and the specimens were stored at 23°C in a dry place until immediately before testing, but for at least 48 hours after preparation. Measurements were also performed at 23°C, with readings taken after 15 seconds.

[0139] Adhesion strength: Composite specimens (2K peel plates) for determining adhesion strength according to Figure 1 were stored at 70 °C and 62% relative humidity for different times. The specimens were stored overnight (12 h) in an air-conditioned environment at 23 °C / 50% relative humidity until the peel test. Storage time 0 h means that the prepared composite specimens were stored in a dry environment, i.e., on silica gel, at room temperature (23 °C) for 48 h after injection molding. The terms used below in relation to the composite specimens and holder for the roller peel test refer to Figure 1.

[0140] The adhesion strength was determined by a roller peel test at 23 °C. The 30 mm-wide tab 4 (section II) of the composite specimen 1 used for the test was peeled from the frame 2 (section I) at a pulling speed of 50 mm / min using a tensile tester while moving at a 90° angle on a deflection roller 7. Table 2 shows the average peel force [N] determined from five independent measurements of the test section. The tab part away from the sprue was attached to the upper specimen holder of the tensile tester, and the specimen holder 6 was attached to the lower specimen holder. The deflection roller 7 used had a diameter of 20 mm. The composite specimen frame 2 was free to move in a plane perpendicular to the tensile axis Z and was stabilized by an anchor roller 8. During the peel test, the frame 2 was moved intermittently across the entire measurement area of ​​the holder so that the failure zone (the zone between the still-adhered and already-detached parts) was always in the plane of the tensile axis Z.

[0141] Discussion of the results: Composites of profiles (I) made from polyamide molding compound B1 and profiles (II) made from molding compound FM-2(I) according to the invention have good adhesion strength and maintain this good adhesion at approximately the same level even after 5 days of storage at 70 °C and 62% relative humidity. By comparison, in contrast to B1, the adhesion strength of VB4, which does not contain component (B), to FM-2(I) is already 10% lower after preparation and insufficient after storage. The same situation emerges when comparing components B2 / FM-2(I) and VB5 / FM-2(I): excellent adhesion can be measured to B2 after preparation and after storage, while the adhesion of VB5 is insufficient after storage. Looking at the adhesion strength to molding compound FM-2(II), it becomes clear that molding compound B1 according to the invention has excellent adhesion strength both before and after storage, while the adhesion strength of VB4 is already 2.5 times lower than that of B1 after preparation and is insufficient after storage. The modification of polyamide molding compounds with MAH-grafted polyolefins according to the prior art does not result in sufficient adhesion in the composite, as shown by the comparative examples VB1 and VB3: when component (B) is simultaneously contained in both molding compounds or profiles (I) and (II) of the composite, no or only very weak adhesion strength is observed.

Claims

1. Directly adjacent and firmly attached, (I) a profile formed from a thermoplastic molding material FM-1 containing at least one polyamide (A), and optionally fillers and reinforcing materials (C) and additives (D); (II) a profile formed from a thermoplastic molding material FM-2 containing at least one olefin and / or vinyl aromatic polymer (E), and optionally a filler and reinforcing material (F), a plasticizer (G), and an additive (H); Including, the molding material FM-1 or the molding material FM-2 contains 0.1 to 5.0% by weight of polyethyleneimine (B), and the at least one olefin and / or vinyl aromatic polymer (E) of the molding material FM-2 is grafted with a carboxylic acid or carboxylic acid anhydride group; Composite material.

2. The thermoplastic molding material FM-1 comprises the following components: (A) 30 to 99.9 weight percent of at least one polyamide; (B) 0.1 to 5.0 weight percent polyethyleneimine; (C) 0 to 60 weight percent fillers and / or reinforcing materials; (D) 0 to 5.0 weight percent of an additive other than (A) to (C). Including, The sum of (A) to (D) is 100% by weight of the thermoplastic molding material FM-1; The thermoplastic molding material FM-2 comprises the following components: (E) 45 to 100 weight percent of at least one olefin and / or vinyl aromatic polymer; (F) 0 to 15 weight percent fillers and / or reinforcing materials; (G) 0 to 35 wt. % of a plasticizer; (H) 0 to 5.0 wt. % of additives other than (E), (F), and (G). Including, The total of (E) to (H) is 100% by weight of the thermoplastic molding material FM-2. The composite material of claim 1 , characterized in that

3. the at least one polyamide (A) is present in an amount of 31 to 79.5 percent by weight based on the total weight of the molding material FM-1; and / or The at least one olefin and / or vinyl aromatic polymer (E) is present in an amount of 55 to 94.9 weight percent based on the total weight of the molding material FM-2.

3. The composite material according to claim 1, wherein

4. The thermoplastic molding material FM-1 comprises the following components: (A) 35 to 100 weight percent of at least one polyamide; (C) 0 to 60 weight percent fillers and / or reinforcing materials; (D) 0 to 5.0% by weight of additives other than (A) and (C). Including, the sum of (A), (C), and (D) is 100 weight percent of the thermoplastic polyamide molding material FM-1; The thermoplastic molding material FM-2 comprises the following components: (E) 40 to 99.9 weight percent of at least one olefin and / or vinyl aromatic polymer; (B) 0.1 to 5.0 weight percent polyethyleneimine; (F) 0 to 15 weight percent fillers and / or reinforcing materials; (G) 0 to 35 wt. % of a plasticizer; (H) 0 to 5.0 weight percent of additives other than (E), (F), (G), and (B). Including, The sum of (B) and (E) to (H) is 100% by weight of the thermoplastic molding material FM-2. The composite material of claim 1 , characterized in that

5. the at least one polyamide (A) is present in an amount of 35 to 80 percent by weight based on the total weight of the molding material FM-1; and / or The at least one olefin and / or vinyl aromatic polymer (E) is present in an amount of 51 to 94.4 weight percent based on the total weight of the molding material FM-2. The composite material of claim 4, characterized in that

6. 6. The composite material according to claim 1, wherein the polyethyleneimine (B) is present in an amount of 0.5 to 4.0 percent by weight, based on the total weight of the molding material FM-1 or FM-2.

7. The at least one polyamide (A) of the molding material FM-1 is semicrystalline acyclic aliphatic polyamides (A1) from the group consisting of 46, 56, 66, 66 / 6, 69, 610, 612, 614, 616, 618, 810, 1010, 1012, 1014, 1016, 1212, 11, 12, 6 / 12, 66 / 6 / 610, and / or semi-crystalline, semi-aromatic polyamides (A2) from the group consisting of 6T / 6I, 6T / 66, 6T / 6I / 66, 6T / 610, 6T / 612, 6T / 614, 6T / 616, 9T, 9MT, 10T, 12T, 10T / 6T, 11 / 10T, 12 / 10T, 11 / 9T, 12 / 9T, 10T / 1010, 10T / 612, and / or MACM12 / PACM12, MACM14 / PACM14, MACM16 / PACM16, MACM18 / PACM18, 6I / 6T / MACMI / MACMT / 12, 6I / MACMI / MACMT, 6I / PACMI / PACMT, 6 I / 6T / MACMI, 6I / 6T / 612 / MACMI / MACMT / MACM12, MACMI / MACMT / 12, 6 / IPDT, 6I / 6T / 614 / MACMI / MACMT / MACM14, 6I / 6T / 616 / MACMI / MA alicyclic polyamides (A3) from the group consisting of CMT / MACM16, MACMI / MACM36, 12 / PACMI, 12 / MACMT, 6I / PACMT, MACM10, MACM12, MACM14, MACM16, MACM18, MACMI / 12, PACM10, PACM12, MACM14, PACM16, PACM18, PACMI / 12, TMDC10, TMDC12, TMDC16, TMDC18, MACMT / MACMI / 12, PACMT / PACMI / 12, and / or Amorphous semi-aromatic polyamides (A4) from the group consisting of 5I, 6I, 6 / 6I, MXDI, MXDI / 6I, MXD6 / MXDI, 5T / 5I, 6T / 6I, 10T / 10I, 3-6T (3-6=2,2,4- or 2,4,4-trimethylhexanediamine), or mixtures thereof, in which the 5T / 5I, 6T / 6I, or 10T / 10I system has a proportion of 5T, 6T, or 10T units of less than 50 mol % and the composition range of 5T:5I, 6T:6I, or 10T / 10I, expressed in mol %, is from 20:80 to 45:

55.

7. The composite material according to claim 1, wherein the composite material is selected from the group consisting of:

8. The at least one polyamide (A) of the molding material FM-1 comprises the following components: 20 to 100 percent by weight of at least one semi-crystalline acyclic aliphatic polyamide (A1) and / or at least one semi-aromatic semi-crystalline polyamide (A2), 0 to 80 percent by weight of at least one alicyclic polyamide (A3) and / or amorphous semi-aromatic polyamide (A4); And, the sum of the weight percentages of components (A1) through (A4) equals 100 weight percent of component (A); or 20 to 80 weight percent of at least one semicrystalline acyclic aliphatic polyamide (A1) selected from the group consisting of PA66, PA610, PA612, PA614, and PA616, 20 to 80 weight percent of at least one amorphous semi-aromatic polyamide (A4) selected from the group consisting of 5T / 5I, 6T / 6I, and 10T / 10I. And, Components (A1) and (A4) whose total weight percentages equal 100 weight percent of component (A). A composite material according to any one of claims 1 to 7, characterized in that it comprises or consists of said components.

9. 9. The composite according to claim 1, wherein the molding material FM-2 comprises, as component (E), at least one vinyl aromatic polymer and optionally at least one polyolefin.

10. 10. The composite of claim 9, wherein the molding material FM-2 comprises at least 50 percent by weight of vinyl aromatic polymer, based on the total weight of component (E).

11. The at least one olefin and / or vinyl aromatic polymer (E) of the molding material FM-2 is selected from the group consisting of styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butylene-styrene block copolymer (SBS), styrene-styrene-butylene-styrene block copolymer (SSBS), polyethylene (PE), polypropylene (PP), polybutadiene (PB), poly-4-methylpentene, ethylene-propylene copolymer, and ethylene-butene copolymer.

11. The composite of claim 1, wherein the polymer is selected from the group consisting of ethylene-methylhexadiene copolymer, propylene-methylhexadiene copolymer, ethylene-octene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-hexene copolymer, ethylene-propylene-methylhexadiene copolymer, poly(ethylene-vinyl acetate) (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-hexene copolymer, ethylene-propylene-diene terpolymer, and mixtures of these polymeric materials.

12. at least one of the olefin and / or vinyl aromatic polymers (E) is grafted with acrylic acid, methacrylic acid, or maleic anhydride; and / or The degree of graft polymerization is 0.1 to 4.0 weight percent based on the graft polymer (E). The composite material according to any one of claims 1 to 11, characterized in that

13. the polyethyleneimine of component (B) is a branched polyethyleneimine having a ratio of primary to secondary amines in the range of 1:2 to 2:1, and / or a ratio of primary to tertiary amines in the range of 3:1 to 1:1, and / or a ratio of secondary to tertiary amines in the range of 3:1 to 1:1; and / or the polyethyleneimine of component (B) is a branched polyethyleneimine having a number average molar mass Mn in the range of 500 to 50,000 g / mol; and / or the polyethyleneimine of component (B) is a branched polyethyleneimine having a primary amino group content in the range of 5,000 to 20,000 μeq / g; and / or The polyethyleneimine of component (B) is a branched polyethyleneimine having a water content of less than 4 weight percent. The composite material according to any one of claims 1 to 12, characterized in that

14. the polyethyleneimine of component (B) is a branched polyethyleneimine having a number average molar mass Mn in the range of 1000 to 2500 g / mol; 14. The composite of claim 13,

15. the polyethyleneimine of component (B) is a branched polyethyleneimine having a primary amino group content in the range of 7,000 to 12,000 μeq / g; 14. The composite material according to claim 13, characterized in that:

16. the molding material FM-1 contains the filler and the reinforcing material of component (C) in a proportion ranging from 20 to 60 weight percent; and / or the molding material FM-2 contains the filler and the reinforcing material of component (F) in a proportion ranging from 0 to 10 weight percent; and / or Components (C) and (F) the composition comprises particulate fillers (C1) and (F1) selected from the group consisting of soot, talc, mica, silicates, quartz, wollastonite, kaolin, silicic acid, magnesium carbonate, magnesium hydroxide, chalk, ground or precipitated calcium carbonate, lime, feldspar, inorganic pigments including barium sulfate, zinc oxide, zinc sulfide, lithopone, titanium dioxide (rutile, anatase), iron oxide, iron manganese oxide, metal oxides, in particular spinels including copper iron spinel, copper chromium oxide, zinc-iron oxide, cobalt-chromium oxide, cobalt-aluminum oxide, magnesium aluminum oxide, copper-chromium-manganese mixed oxides, copper-manganese-iron mixed oxides, rutile pigments including titanium zinc rutile, nickel antimony titanate, chromium antimony titanate, hard or soft magnetic metals or alloys or ceramics, hollow spherical silicic acid fillers, aluminum oxide, boron nitride, boron carbide, aluminum nitride, calcium fluoride, and mixtures thereof; and / or The fiber reinforcements (C2) and (F2) are selected from the group consisting of glass fibers, carbon fibers, graphite fibers, aramid fibers, nanotubes, or mixtures thereof, and components (C2) and (F2) can have a circular or non-circular cross-sectional area. The composite material according to any one of claims 1 to 15, characterized in that

17. The additive of component (D) is present in the molding material FM-1 in a proportion ranging from 0.1 to 4.0 weight percent; and / or The additive of component (H) is present in the molding material FM-2 in a proportion ranging from 0.1 to 4.0 weight percent; and / or the additives of components (D) and (H) are selected from the group consisting of stabilizers, ageing inhibitors, antioxidants, antiozonants, light stabilizers, UV stabilizers, UV absorbers, UV blockers, inorganic heat stabilizers, in particular those based on copper halides and alkali halides, organic heat stabilizers, conductive additives, optical brighteners, processing aids, nucleating agents, crystallization accelerators, crystallization retarders, flow agents, lubricants, mold release agents, organic pigments and dyes, marking agents, and mixtures thereof; The composite material according to any one of claims 1 to 16, characterized in that

18. the plasticizer of component (G) is present in the molding material FM-2 in an amount ranging from 5 to 35 weight percent; and / or the plasticizer of component (G) is selected from the group consisting of paraffinic and naphthenic oils; The composite material according to any one of claims 1 to 17, characterized in that

19. The profile (I) formed from the thermoplastic molding material FM-1 has a Shore hardness of at least 70D in the dry state, determined according to ISO 7619-1 (2012-02); and / or The profile (II) formed from the thermoplastic molding material FM-2 has a Shore hardness of at most 60D, determined in the dry state according to ISO 7619-1 (2012-02). The composite material according to any one of claims 1 to 18, characterized in that

20. Next steps: (i) a step of inserting a molded body comprising at least one profile (I) formed from molding material FM-1 into an injection mold for molding at least one profile (I), or injecting said thermoplastic molding material FM-1 into an injection mold; and (ii) Injection of the thermoplastic molding material FM-2 to form at least one profile (II). Including, The melt of the molding material FM-1 and the melt of the molding material FM-2 are introduced into an injection mold in parallel or sequentially without being mixed or substantially mixed; The shapes (I) and (II) are in contact with each other at at least one point. A method for producing a composite material according to any one of claims 1 to 19, characterized in that the composite material is produced by an injection moulding process.

21. A composite material comprising a profile (I) formed from a molding material FM-1 containing a polyamide, and a profile (II) formed from a molding material FM-2 containing an olefin and / or vinyl aromatic polymer, wherein at least one of the olefin and / or vinyl aromatic polymers of the molding material FM-2 is grafted with a carboxylic acid or carboxylic anhydride group, and wherein the composite material comprises polyethyleneimine for improving the adhesive strength between the profile (I) and the profile (II).

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