A transparent molding composition based on polyamide, impact modifier, and glass short fibers, and its use.

Abstract

The present invention provides (A) - 10 to 95% by weight of at least one semicrystalline aliphatic polyamide having an average number of carbon atoms to nitrogen atoms of at least 8; - 90-5% by weight of at least one amorphous polyamide Polyamide mixture containing 35-84%; (B) at least one impact modifier greater than 10-30%, especially 15-30%; (C) 6–20% short glass fibers; (D) 0-10% of at least one prepolymer; (E) 0-5%, in particular 0.1-5%, of at least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof Contains by weight (total 100%) The refractive index of each of components (A), (B), (C), and (D) is 1.500 to 1.540, The composition is free of PEBA and has a dry modulus at 23°C of greater than 1700 MPa. It relates to a transparent molding composition.

Description

Technical Field

[0001] The present invention relates to a transparent molding composition based on a mixture of a semi-crystalline aliphatic polyamide, an amorphous polyamide, an impact modifier, and short glass fibers, optionally a prepolymer, having an average number of carbon atoms per nitrogen atom of 8 or more, wherein the refractive indices of the polyamide, the impact modifier, the short glass fibers, and the mixture of the prepolymer are from 1.500 to 1.540, the composition has no PEBA, and has a high modulus of elasticity, particularly a modulus of elasticity exceeding 1700 MPa, and relates to the use of the composition for the production of articles obtained by injection, particularly for sports or electronics applications. <000,

[0002] The sports and electronics markets currently require molding compositions based on transparent polyamides, which, after molding, have a high modulus of elasticity, particularly at least 1700 MPa, good impact strength, a transmittance of at least 70% for a 2 mm wafer, particularly good fatigue resistance for the sports market and sufficient sebum resistance for the electronics market.

[0003] Patent EP3,309,199B1 describes a composition comprising an amorphous copolyamide, and optionally a semi-crystalline polyamide, and a glass filler. The composition has high transparency but low impact strength.

[0004] Patent FR3,018,280B1 describes a composition comprising a semi-crystalline polyamide, an amorphous polyamide, glass fibers, and optionally PEBA. These compositions exhibit low transmittance and slight haze. However, no information is given about the modulus of elasticity, impact properties, or fatigue resistance.

[0005] Application EP3,486,287A1 describes a composition comprising a semi-crystalline polyamide, an impact modifier, and glass fiber S.

[0006] These compositions have good fatigue strength but high haze, and no information about transmittance is given.

[0007] None of the above compositions satisfy the following three and / or four properties: - Transmittance exceeding 70% or haze below 50% - Elastic modulus exceeding 1700 MPa - Good impact strength and / or fatigue strength.

[0008] Therefore, the present invention is (A) 10-95% by weight of at least one semicrystalline aliphatic polyamide in which the average number of carbon atoms relative to nitrogen atoms is 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-84%; (B) At least one impact-resistant modifier in an amount of 10-30%, especially 15-30%; (C) Glass short fibers 6-20%; (D) At least one prepolymer in 0-10% of its original concentration; (E) At least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof, in an amount of 0-5%, particularly 0.1-5%. This includes by weight (total 100%), The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540. The above composition does not contain polyether block amide (PEBA) and relates to a transparent molded composition having a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0009] Therefore, the inventors unexpectedly discovered that a mixture of amorphous and semicrystalline polyamides within a specific range, an impact modifier within a specific range, optionally the addition of a specific range of glass short fibers to at least one prepolymer, the refractive index of each glass short fiber of the constituent fibers, amorphous and semicrystalline polyamides, an impact modifier, and a prepolymer makes it possible to obtain a composition having a high modulus of elasticity exceeding 1700 MPa, high transmittance, and / or slight haze, as well as good impact strength and / or good fatigue strength.

[0010] In the sense of the present invention, amorphous polyamide refers to a transparent amorphous polyamide having only a glass transition temperature (not a melting temperature (Tm)), or a polyamide with little crystallinity having a glass transition temperature and melting point such that the crystallization enthalpy during a cooling step at a rate of 20 K / min by differential scanning calorimetry (DSC) is less than 30 J / g, particularly less than 20 J / g, preferably less than 15 J / g, as measured according to standard ISO 11357-3:2013. The glass transition temperature (Tg) for these polyamides, as measured by DSC at a heating rate of 20 K / min according to standard ISO 11357-1:2009 and ISO 11357-2:2013, is greater than 75°C.

[0011] In the sense of the present invention, semicrystalline polyamide refers to a polyamide having a crystallization enthalpy exceeding 30 J / g, preferably exceeding 40 J / g, during a cooling step at a rate of 20 K / min by DSC as measured by ISO standard 11357-3:2013, and a dissolution temperature (Tm) by DSC as measured by ISO standard 11357-3:2013.

[0012] The nomenclature used to define polyamides is described in ISO standard 1874-1:2011 "Plastics - Polyamide (PA) Moulding And Extrusion Materials - Part 1: Designation" and is well known to those skilled in the art.

[0013] The term "polyamide" as used in this explanation includes both homopolyamides and copolyamides.

[0014] In one embodiment, the composition according to the present invention is a thermoformable composition.

[0015] Regarding excluded PEBA: Polyether block amides (PEBA) are copolymers comprising amide units (Ba1) and polyether units (Ba2), wherein the amide unit (Ba1) corresponds to an aliphatic repeating unit selected from units obtained from at least one amino acid, or from at least one lactam, or from units XY obtained by the following polycondensation: - At least one diamine, the diamine being a linear or branched aliphatic diamine, or an aromatic diamine or a mixture thereof; and - At least one dicarboxylic acid, the diacid is selected from aliphatic diacids or aromatic diacids. The polyether unit (Ba2) is derived in particular from at least one polyalkylene ether polyol, especially a polyalkylene ether diol.

[0016] Regarding component A: Semicrystalline polyamide Component (A) contains 10-95% semicrystalline aliphatic polyamide.

[0017] Advantageously, component (A) contains 15-90% by weight of semicrystalline aliphatic polyamide.

[0018] More advantageously, component (A) contains 20-85% by weight of semicrystalline aliphatic polyamide.

[0019] More advantageously, component (A) contains 25-80% by weight of semicrystalline aliphatic polyamide.

[0020] In particular, component (A) contains 30-75% by weight of semicrystalline aliphatic polyamide.

[0021] The at least one semicrystalline aliphatic polyamide is obtained from the polycondensation of at least one lactam, or the polycondensation of at least one amino acid, or the polycondensation of at least one diamine Xa and at least one dicarboxylic acid Ya.

[0022] The average number of carbon atoms per nitrogen atom in the semi-crystalline aliphatic polyamide is 8 or more.

[0023] In particular, the average number of carbon atoms per nitrogen atom in the semi-crystalline aliphatic polyamide is 8 to 14.

[0024] Advantageously, the average number of carbon atoms per nitrogen atom in the semi-crystalline aliphatic polyamide is 9 or more.

[0025] In particular, the average number of carbon atoms per nitrogen atom in the semi-crystalline aliphatic polyamide is 9 to 14.

[0026] More advantageously, the average number of carbon atoms per nitrogen atom in the semi-crystalline aliphatic polyamide is 10 or more.

[0027] In particular, the average number of carbon atoms per nitrogen atom in the semi-crystalline aliphatic polyamide is 10 to 14.

[0028] In the case of the PA-Xa·Ya homopolyamide, the number of carbon atoms per nitrogen atom is the average of the units Xa and the unit Ya.

[0029] In the case of the copolyamide, the number of carbon atoms per nitrogen atom is calculated according to the same principle. The molar ratios of the various amide units are used in the calculation.

[0030] In one embodiment, the semi-crystalline aliphatic polyamide is a mixture of two semi-crystalline aliphatic polyamides whose average number of carbon atoms per nitrogen atom is 8 to 14, particularly 9 to 14, particularly 10 to 14.

[0031] When the at least one semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one lactam, thus, it may contain a single lactam or several lactams.

[0032] Advantageously, the at least one semicrystalline aliphatic polyamide is obtained from the polycondensation of a single lactam, the lactam being selected from caprolactam, laurolactam, and undecanolactam, and preferably laurolactam.

[0033] If a lactam has an average number of carbon atoms relative to the nitrogen atom of a semicrystalline aliphatic polyamide of 8 or less, then it is obvious that it is a form of copolyamide with other amino acids, lactams, or PAXaYa, just as a copolyamide has an average number of carbon atoms relative to the nitrogen atom of 8 or more.

[0034] If the at least one semicrystalline aliphatic polyamide is obtained from the polycondensation of at least one amino acid, the at least one amino acid may be selected from C6-C18, preferably C10-C18, and more preferably C10-C12 amino acids.

[0035] C6-C12 amino acids include, in particular, 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid, and 11-aminoundecanoic acid, as well as their derivatives, especially N-heptyl-11-aminoundecanoic acid.

[0036] If an amino acid has an average number of carbon atoms relative to the nitrogen atom of a semicrystalline aliphatic polyamide of 8 or less, then it is immediately apparent that it is a form of copolyamide with other amino acids, lactams, or PAXaYa, such that a copolyamide has an average number of carbon atoms relative to the nitrogen atom of 8 or more.

[0037] If the at least one semicrystalline aliphatic polyamide is obtained from the polycondensation of at least one amino acid, it may contain a single amino acid or several amino acids.

[0038] Advantageously, the semicrystalline aliphatic polyamide is obtained from the polycondensation of a single amino acid, the amino acid being selected from 11-aminoundecanoic acid and 12-aminododecanoic acid, and preferably 11-aminoundecanoic acid.

[0039] The at least one semicrystalline aliphatic polyamide is obtained from the polycondensation of at least one diamine Xa and at least one diacid Ya, where the diamine is C4-C36, preferably C5-C18, preferably C5-C12, and more preferably C10-C12, the at least one diacid Ya is C4-C36, preferably C6-C18, preferably C6-C12, and more preferably C10-C12, the at least one diamine Xa is an aliphatic diamine, and the at least one diacid Ya is an aliphatic diacid.

[0040] The diamine may be linear or branched. Preferably, it is linear.

[0041] The at least one C4-C36 diamine Xa may be selected from, in particular, 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonameethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, and 1,18-octadecamethylenediamine, octadecenediamine, eicosanediamine, docosanediamine, and diamines obtained from fatty acids.

[0042] Advantageously, the at least one diamine Xa is C5-C18 and is selected from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonameethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, and 1,18-octadecamethylenediamine.

[0043] Advantageously, the at least one C5-C12 diamine Xa is selected in particular from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonameethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine.

[0044] Advantageously, the at least one C6-C12 diamine Xa is selected in particular from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonameethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine.

[0045] Advantageously, the diamine Xa used is a C10-C12 diamine, and is particularly selected from 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine.

[0046] The at least one dicarboxylic acid Ya is C4-C36 and may be selected from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, brassic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, octadecanediic acid, and diacides obtained from fatty acids.

[0047] The diacitor may be linear or branched. Preferably, it is linear.

[0048] Advantageously, the at least one dicarboxylic acid Ya is C6-C18 and is selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, brassic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, and octadecanediic acid.

[0049] Advantageously, the at least one dicarboxylic acid Ya is C6-C12 and is selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, and dodecanediic acid.

[0050] Advantageously, the at least one dicarboxylic acid Ya is C10-C12 and is selected from sebacic acid, undecanediic acid, and dodecanediic acid.

[0051] If diamine Xa has an average number of carbon atoms relative to the nitrogen atom of a semicrystalline aliphatic polyamide of 8 or less, then it is clear that it is related to a dicarboxylic acid, just as copolyamides have an average number of carbon atoms relative to the nitrogen atom of 8 or more, and vice versa.

[0052] Polyamide XaYa may also be a semicrystalline aliphatic polyamide with an average number of carbon atoms relative to nitrogen atoms of 8 or less, in which case it is in the form of a copolyamide, such that the copolyamide has an average number of carbon atoms relative to nitrogen atoms of 8 or more.

[0053] If the semicrystalline aliphatic polyamide is obtained from the polycondensation of at least one diamine Xa and at least one dicarboxylic acid Ya, it may contain a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.

[0054] In one embodiment, the semicrystalline aliphatic polyamide is obtained from the polycondensation of a single diamine Xa and a single dicarboxylic acid Ya.

[0055] Advantageously, the semicrystalline aliphatic polyamide is selected from PA10, PA11, PA12, PA1010, and PA1012, with PA11 and PA12 being particularly important.

[0056] Advantageously, semicrystalline polyamides are partially or entirely of bio-derived origin.

[0057] Amorphous polyamide Component (A) also contains 5-90% of at least one amorphous polyamide.

[0058] Advantageously, component (A) contains 10-85% amorphous polyamide.

[0059] More advantageously, component (A) contains 15-80% amorphous polyamide.

[0060] More advantageously, component (A) contains 20-75% amorphous polyamide.

[0061] In particular, component (A) contains 25-70% amorphous polyamide.

[0062] Amorphous polyamides are polyamides of formula XY or A / XY. - A is an aliphatic repeating unit selected from a unit obtained from the polycondensation of at least one amino acid, a unit obtained from the polycondensation of at least one lactam, and a unit obtained from the polycondensation of at least one aliphatic diamine and at least one aliphatic diacid. - X is at least one alicyclic diamine, - Y is at least one dicarboxylic acid, and the diacid is selected from linear or branched aliphatic diacids, alicyclic diacids, and aromatic diacids. The diamine and the diacid each contain 4 to 36 carbon atoms, preferably 6 to 18 carbon atoms.

[0063] Advantageously, amorphous polyamides are polyamides of formula A / XY. The amino acid, lactam, diamine, and dicarboxylic acid constituent unit A is as defined above for the defined semicrystalline aliphatic polyamides.

[0064] Amorphous polyamides may also be homopolyamides or copolyamides.

[0065] The molar ratio of diamine X to dicarboxylic acid Y is preferably stoichiometric.

[0066] Dicarboxylic acids contain 4 to 36 carbon atoms, and preferably 6 to 18 carbon atoms.

[0067] The alicyclic diamine may be selected from, for example, bis(3,5-dialkyl-4-aminocyclohexyl)-methane, bis(3,5-dialkyl-4-aminocyclohexyl)-ethane, bis(3,5-dialkyl-4-aminocyclohexyl)-propane, bis(3,5-dialkyl-4-aminocyclohexyl)-butane, bis-(3-methyl-4-aminocyclohexyl)-methane or 3'-dimethyl-4,4'-diamino-dicyclohexyl-methane (hereinafter referred to as B), commonly called "BMACM" or "MACM"), p-bis(aminocyclohexyl)-methane (hereinafter referred to as P), commonly called "PACM", isopropylidene di(cyclohexylamine), isophorone-diamine (hereinafter referred to as IPD), commonly called "PACP", and 2,6-bis(aminomethyl)norbornane, commonly called "BAMN".

[0068] A non-comprehensive list of these alicyclic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th edition (1992), pp. 386-405).

[0069] The dicarboxylic acid may be selected from linear or branched aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.

[0070] If dicarboxylic acid Y is aliphatic and linear, it is as defined above for diacid Ya.

[0071] If dicarboxylic acid Y is alicyclic, it may contain the following carbon skeletons: norbornylmethane, cyclohexane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl) or di(methylcyclohexyl)propane.

[0072] If dicarboxylic acid Y is aromatic, it may be selected from terephthalic acid (represented by T), isophthalic acid (represented by I), and naphthalene acid.

[0073] Advantageously, the dicarboxylic acid Y is aromatic and may be selected from terephthalic acid (represented by T) and isophthalic acid (represented by I).

[0074] Advantageously, amorphous polyamides are partially or entirely of bio-derived origin.

[0075] Advantageously, semicrystalline aliphatic polyamides and / or semicrystalline polyamides are partially or entirely of biodegradable origin.

[0076] Advantageously, amorphous polyamides are selected from 11 / B10, 12 / B10, 11 / P10, 12 / P10, 11 / BI / BT, 12 / BI / BT, 11 / PI / BT, 12 / PI / BT, 11 / PI / PT, 12 / PI / PT, 11 / BI, 12 / BI, 11 / PI, and 12 / PI, with 11 / B10 being particularly important.

[0077] Advantageously, the semicrystalline aliphatic polyamides are selected from PA10, PA11, PA12, PA1010, PA1012, particularly PA11 and PA12, and the amorphous polyamides are selected from 11 / B10, 12 / B10, 11 / P10, 12 / P10, 11 / BI / BT, 12 / BI / BT, 11 / PI / BT, 12 / PI / BT, 11 / PI / PT, 12 / PI / PT, 11 / BI, 12 / BI, 11 / PI, and 12 / PI, particularly 11 / B10.

[0078] Advantageously, the semicrystalline aliphatic polyamide is PA11, and the amorphous polyamide is selected from 11 / B10, 12 / B10, 11 / P10, 12 / P10, 11 / BI / BT, 12 / BI / BT, 11 / PI / BT, 12 / PI / BT, 11 / PI / PT, and 12 / PI / PT, in particular 11 / B10 and 12 / B1 / BT.

[0079] Regarding impact resistance modifier (B): PEBA is excluded from the definition of impact modifiers.

[0080] The impact resistance modifier is present in an amount of 10% to 30% by weight, particularly 15% to 30% by weight, relative to the total weight of the composition.

[0081] The impact modifier may be any impact modifier, as long as it is a polymer that has a lower modulus of elasticity than the resin and has good adhesion to the matrix, so that it dissipates cracking energy.

[0082] Impact modifiers are advantageously composed of polymers, particularly polyolefins, whose flexural modulus, as measured according to standard ISO 178, is less than 100 MPa and whose Tg (measured according to standard 11357-2 at the inflection point of a DSC thermogram) is less than 0°C.

[0083] The polyolefin in the impact resistance modifier may be functional or non-functional, or it may be a mixture of at least one functional polyolefin and / or at least one non-functional polyolefin. For simplicity, the polyolefin is denoted as (B1), and functional polyolefins (B1) and non-functional polyolefins (B2) are described below.

[0084] Some of the polyolefins listed below are not limited, but it is clear that, for example, homopolymers of polyethylene or polypropylene have a refractive index of less than 1.500. In this case, the polyolefin cannot be used alone and must be mixed with one or more other materials so that the refractive index of the mixture is between 1.500 and 1.540.

[0085] Non-functional polyolefins (B2) are conventionally homopolymers or copolymers of α-olefins or diolefins such as ethylene, propylene, 1-butene, 1-octene, and butadiene. Examples include the following: - Homopolymers and copolymers of polyethylene, particularly LDPE, HDPE, LLDPE (linear low-density polyethylene), VLDPE (very low-density polyethylene), and metallocene polyethylene. - Propylene homopolymer or copolymer - Ethylene / α-olefin copolymers such as ethylene / propylene, EPR (an abbreviation for ethylene-propylene-rubber), and ethylene / propylene / diene (EPDM). - Styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS) block copolymers - A copolymer of ethylene and at least one product selected from salts or esters of unsaturated carboxylic acids such as alkyl (meth)acrylates (e.g., methyl acrylate), or vinyl esters of saturated carboxylic acids such as vinyl acetate (EVA), in which the proportion of comonomer can reach 40% by weight.

[0086] Functional polyolefin (B1) may be a polymer of α-olefin having a reaction unit (functional value), such reaction unit being an acid, an anhydride, or epoxy group. Examples include the aforementioned polyolefin (B2) which is grafted, copolymerized, or tripolymerized by an unsaturated epoxide such as glycidyl (meth)acrylate, or by a carboxylic acid or the corresponding salt or ester such as (meth)acrylic acid (which can be completely or partially neutralized by a metal such as Zn), or by a carboxylic acid anhydride such as maleic anhydride.

[0087] The functional polyolefin (B1) may be selected from the following maleic anhydride or glycidyl methacrylate graft(co)polymers, with a grafting rate of, for example, 0.01 to 5% by weight: - For example, PE, PP, copolymers of ethylene and propylene, butene, hexene, or octene, containing 35-80% by weight of ethylene. - Ethylene / α-olefin copolymers such as ethylene / propylene, EPR (an abbreviation for ethylene-propylene-rubber), and ethylene / propylene / diene (EPDM). - Styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS) block copolymers - Ethylene and vinyl acetate copolymer (EVA) containing 40% by weight or less of vinyl acetate - Ethylene and alkyl (meth)acrylate copolymer containing 40% by weight or less of alkyl (meth)acrylate - Ethylene and vinyl acetate (EVA) and alkyl (meth)acrylate copolymer containing 40% by weight or less of the comonomer.

[0088] The functional polyolefin (B1) may also be selected from ethylene / propylene copolymers obtained by condensing maleic anhydride-grafted propylene with a monoamine polyamide (or polyamide oligomer) (products described in EP-A-0,342,066).

[0089] Functional polyolefin (B1) may also be a copolymer or ternary polymer of at least the following units: (1) ethylene, (2) vinyl esters of alkyl (meth)acrylates or saturated carboxylic acids, and (3) (meth)acrylic acids or epoxy such as anhydrides like maleic anhydride or glycidyl (meth)acrylate.

[0090] An example of the latter type of functionalized polyolefin is the following copolymer, which preferably contains at least 60% by weight of ethylene and, for example, 0.1 to 10% by weight of the copolymer: - Ethylene / alkyl (meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymer; - Ethylene / vinyl acetate / maleic anhydride or glycidyl methacrylate copolymer; - Ethylene / vinyl acetate or alkyl (meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymer.

[0091] In the previous copolymer, (meth)acrylic acid may be chlorided with Zn or Li.

[0092] In (B1) or (B2), the term "alkyl (meth)acrylate" means C1-C8 alkyl methacrylates and acrylates, which may be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethyl-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate, and ethyl methacrylate.

[0093] Furthermore, the previously cited polyolefin (B1) may also be crosslinked by any suitable method or agent (such as a diepoxy, diacid, or peroxide), and the term functional polyolefin also includes mixtures of the previously cited polyolefin with a difunctional reagent such as a diacid, dianhydride, or diepoxy that can react with them, or mixtures of at least two functional polyolefins that can react with each other.

[0094] The copolymers (B1) and (B2) described above may be copolymerized in a statistical or ordered manner and may have a linear or branched structure.

[0095] The molecular weight, index MFI, and density of these polyolefins can also vary widely and are known to those skilled in the art. The melt flow index, MFI, is the degree of fluidity in the molten state. It is measured according to standard ASTM 1238.

[0096] Advantageously, the functional polyolefin (B1) is selected from styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS) block copolymers grafted with maleic anhydride or glycidyl methacrylate, with a grafting rate of, for example, 0.01 to 5% by weight.

[0097] This could be, for example, Kraton® FG1901 (SEBS functional maleic anhydride), Globalprene® 9901 (SEBS functional maleic anhydride), or Taipol® (SEBS maleic anhydride).

[0098] However, while the polyamide MFIs, (B1) and (B2) may be selected within a wide range, it is recommended that the polyamide MFI be greater than (B) to promote the dispersion of (B).

[0099] The impact-resistant modifier may also have a core-shell structure.

[0100] The core-shell preferably has the form of spherical polymer particles. These particles are also called core-shell particles or core-shell polymers. A first layer forms the core, and a second or all subsequent layers form their respective shells.

[0101] The core-shell may be functionalized or non-functionalized. If the core-shell is functionalized, this allows for better compatibility with the polyamide matrix of the present invention. As an example, maleic anhydride type functionalization is preferred.

[0102] Regarding the size of the spherical polymer particles, it has a weight-average particle size of 20 nm to 500 nm. The weight-average particle size of the polymer is preferably 20 nm to 400 nm, more preferably 20 nm to 350 nm, and advantageously 20 nm to 300 nm.

[0103] The polymer particles have a multilayer structure comprising at least one layer (F) containing a polymer (F1) with a glass transition temperature of less than 0°C and another layer (G) containing a polymer (G1) with a glass transition temperature of more than 60°C.

[0104] Preferably, the polymer (G1) with a glass transition temperature higher than 60°C is the outer layer of polymer particles having a multilayer structure.

[0105] Polymer particles are obtained by a multi-step method, such as two or three or more steps.

[0106] Preferably, the polymer (F1), having a glass transition temperature of less than 0°C in layer (F), is produced in the first step of a multi-step method for forming the core of polymer particles having a multilayer structure. The polymer (F1) preferably has a glass transition temperature of less than -5°C, more preferably less than -15°C, and advantageously less than -25°C.

[0107] Preferably, polymers (G1) with a glass transition temperature higher than 60°C are produced in the final step of a multi-step method that forms the outer layer of polymer particles having a multilayer structure.

[0108] There may be one or more intermediate layers obtained by one or more intermediate processes.

[0109] The glass transition temperature (Tg) of a multilayer polymer may be evaluated by dynamic methods such as thermomechanical analysis.

[0110] Polymer (F1) and layer (F) contain 0% to less than 50% by weight of monomers containing aromatic groups. Polymer (G1) and layer (G) contain 0% to less than 50% by weight of monomers containing aromatic groups.

[0111] According to one embodiment, the polymer (G1) and layer (G) do not contain monomers containing aromatic groups.

[0112] For polymers (F1) having a glass transition temperature of less than 0°C, it contains at least 50% by weight of polymer units derived from isoprene or butadiene, and layer (F) is the innermost layer of polymer particles having a multilayer structure. In other words, layer (F) containing polymer (F1) is the core of the polymer particles.

[0113] As an example, the core polymer (F1) may consist of an isoprene homopolymer or butadiene homopolymer, an isoprene-butadiene copolymer, an isoprene copolymer having 98% by weight or less of vinyl monomer, and a butadiene copolymer having 98% by weight or less of vinyl monomer. The vinyl monomer may be styrene, alkylstyrene, acrylonitrile, alkyl (meth)acrylate, or butadiene, or isoprene, or a mixture thereof, provided that polymer (F1) contains less than 50% by weight of monomers containing aromatic groups.

[0114] The polymer (F1) may be crosslinked. Crosslinkable monomers useful for the present invention are not limited, but include aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, allyl carboxylates such as trimethacrylate, triacrylate, allyl acrylate and allyl methacrylate, and diallyl compounds such as diallyl phthalate, diallyl sebacate and triallyl triazine.

[0115] According to one embodiment, the core is a butadiene homopolymer.

[0116] According to other embodiments, the core is a butadiene-styrene copolymer.

[0117] The glass transition temperature Tg of a polymer (F1) containing at least 50% by weight of polymer units derived from isoprene or butadiene is more preferably -100°C to 10°C, even more preferably -80°C to 0°C, and advantageously -70°C to -20°C.

[0118] Examples of polymers (G1) include homopolymers and copolymers containing monomers and / or vinyl monomers that include double bonds. Preferably, polymer (G1) is a (meth)acrylic polymer.

[0119] Preferably, polymer (G1) contains at least 70% by weight of monomers selected from C1-C12 alkyl (meth)acrylates. More preferably, polymer (G1) contains at least 80% by weight of C1-C4 alkyl methacrylate monomers and / or C1-C8 alkyl acrylate monomers.

[0120] Most preferably, the acrylic acid or methacrylic acid monomer of polymer (G1) is selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof, provided that the glass transition temperature of polymer (G1) is at least 60°C.

[0121] The polymer (G1) may contain functional monomers selected from glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids, such as dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, and 2-aminoethyl acrylate or methacrylate, as well as mixtures thereof.

[0122] Advantageously, polymer (G1) contains at least 70% by weight of monomer units derived from methyl methacrylate.

[0123] Preferably, the glass transition temperature Tg of the polymer (G1) is 60°C to 150°C. More preferably, the glass transition temperature of the polymer (G1) is 80°C to 150°C, advantageously 90°C to 150°C, and even more advantageously 100°C to 150°C.

[0124] Preferably, polymer (G1) is grafted onto the polymer produced in the previous step.

[0125] According to one embodiment, the polymer (G1) is crosslinked.

[0126] The core-shell may be obtained by a method comprising several steps, including at least two steps. Such a method is described, for example, in the references US2009 / 0149600 or EP0,722,961.

[0127] Preferably, the polymer (F1) produced in step (F) having a glass transition temperature of less than 0°C is the first step of a multi-stage process.

[0128] The weight percentage ra of the polymer layer (F1) included in step (F) relative to the complete multilayer polymer is at least 60% by weight, preferably at least 70% by weight, and more preferably at least 75% by weight.

[0129] The weight ratio rb of the outer layer polymer (G1) in step (G) to the complete multilayer polymer is at least 5% by weight, preferably at least 6% by weight, and more preferably at least 7% by weight.

[0130] According to the present invention, the ratio rb of the outer layer (G) containing polymer (B1) to the complete multilayer polymer is 30% by weight or less.

[0131] Preferably, the ratio of polymer (G1) to the complete multilayer polymer is 5% to 30% by weight.

[0132] Advantageously, impact modifiers can be selected from SEBS, SBS, and core-shell structures.

[0133] Regarding glass short fibers (C): Glass short fibers are present in the composition at a concentration of 6-20% by weight, particularly 6-15% by weight.

[0134] The glass short fibers may have a circular or non-circular cross-section.

[0135] A fiber with a circular cross-section is defined as a fiber in which every point around it is at an equal distance from its center, and thus represents a perfect circle or an approximate circle.

[0136] Therefore, any glass fiber that is neither perfectly circular nor nearly perfectly circular is defined as a fiber with a non-circular cross-section.

[0137] Examples of non-circular fibers include, for example, elliptical, oval or cocoon-shaped, star-shaped, flake-shaped, flattened, cruciate, polygonal, and ring-shaped non-circular fibers.

[0138] The glass short fibers are preferably 2 to 13 mm in length, and preferably 3 to 8 mm, before the composition is used.

[0139] The glass fibers may be as follows: - It has a circular cross-section with a diameter of 4 to 25 μm, preferably 4 to 15 μm. - Or having a non-circular cross-section with an L / D ratio of 2 to 8, particularly 2 to 4 (where L represents the maximum cross-sectional dimension of the fiber and D represents the minimum cross-sectional dimension of the fiber). L and D may be measured by scanning electron microscopy (SEM).

[0140] Regarding prepolymer (D): At least one prepolymer is optionally present in an amount of 0 to 10% by weight relative to the total weight of the composition.

[0141] The term "prepolymer" refers to a polyamide oligomer whose number-average molecular weight is always lower than that of the polyamide used in the matrix. In particular, the prepolymer has a number-average molecular weight of 1,000 to 15,000 g / mol, especially 1,000 to 10,000 g / mol.

[0142] The prepolymer may be selected from aliphatic, linear or branched polyamide oligomers, alicyclic polyamide oligomers, semi-aromatic polyamide oligomers, aromatic polyamide oligomers, aliphatic, linear or branched, alicyclic, semi-aromatic, and aromatic polyamides, as defined above.

[0143] Therefore, the prepolymer or oligomer is derived from the following condensation; - At least one lactam, or - At least one amino acid, or - At least one dicarboxylic acid and at least one diamine, or A mixture of those.

[0144] Therefore, the prepolymer or oligomer cannot be equivalent to the condensation of a diamine with a lactam or amino acid.

[0145] The prepolymer may also be a copolyamide oligomer, or a mixture of polyamide and copolyamide oligomer.

[0146] For example, the prepolymer may have a monofunctional value of NH2, a monofunctional value of CO2H, or a difunctional value of CO2H or NH2.

[0147] Therefore, the prepolymer may be a monofunctional or difunctional acid or amine, that is, if it is monofunctional (in which case the other end is nonfunctional, especially CH3), it has a single terminal amine or acid function, or if it is difunctional, it has two terminal amine functions or two terminal acid functions.

[0148] Advantageously, the prepolymer has a monofunctional value, preferably NH2 or CO2H.

[0149] Furthermore, it may be non-functional at two ends, particularly diCH3.

[0150] Monofunctional NH2 prepolymers may be produced by reacting a dicarboxylic acid with an aryl monocarboxylic acid obtained by condensation of NH2 or a COOH-functional alkyl (linear or branched), preferably COOH, or a lactam, amino acid, or diamine.

[0151] The DiNH2 prepolymer may be produced by reacting a diamine, obtained after the condensation of a lactam, amino acid, or diamine, with a dicarboxylic acid.

[0152] Functional CO2H prepolymers may be produced by reacting a dicarboxylic acid with an aryl monocarboxylic acid obtained by condensation of NH2 or COOH-functional alkyl (linear or branched), preferably COOH, or lactam, amino acid, or diamine.

[0153] The DiCO2H prepolymer may be produced by reacting a dicarboxylic acid obtained after the condensation of a lactam, amino acid, or diamine with another dicarboxylic acid.

[0154] Non-functional diCH3 prepolymers may be produced by reacting the amine terminus of the prepolymer with an alkyl monocarboxylic acid and the acid terminus with an alkylamine.

[0155] Advantageously, in the compositions of the present invention, the prepolymer is selected from long-chain polyamides and is compatible with the matrix polyamide, and in particular, the matrix polyamide is selected from long-chain polyamides and is especially aliphatic, semi-aromatic, or alicyclic.

[0156] Advantageously, the prepolymer corresponds to a polyamide, particularly an aliphatic polyamide, and is selected from PA6, PA11, PA12, PA11 / 6, and PA6 / 12, or mixtures thereof.

[0157] Advantageously, a single prepolymer is used in the composition.

[0158] The prepolymer used in the composition of the present invention has a number average molecular weight of 1,000 to 15,000 g / mol, particularly 1,000 to 13,000 g / mol, particularly 1,000 to 10,000 g / mol, particularly 1,000 to 9,000 g / mol, particularly 1,000 to 8,000 g / mol, particularly 1,000 to 7,000 g / mol, particularly 1,000 to 6,000 g / mol, particularly 1,000 to 5,000 g / mol, particularly 2,000 to 5,000 g / mol, particularly 2,000 to 4,000 g / mol. It may also be particularly 2,000 to 3,000 g / mol.

[0159] Advantageously, the weight percentage of the prepolymer is 0.1–10%, particularly 1–10% by weight, preferably 1–7% by weight, more preferably 3–7% by weight, and even more preferably 5–7% by weight, relative to the total weight of the composition.

[0160] Advantageously, the prepolymer is selected from diCH3, diNH2, monoNH2, monoacid, diacid, and amino acid prepolymers.

[0161] In particular, the prepolymer is mono-NH2, or mono-acid or di-acid, especially mono-NH2.

[0162] The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540 at 560 nm.

[0163] The refractive index is measured at a wavelength of 560 nm at 23°C using an Abbe refractometer from Atago (model NAR_1T SOLID).

[0164] Regarding the refractive index of fibers, the latter is accessible in datasheets and / or literature.

[0165] Regarding additive (E): At least one additive is present in an amount of 0 to 5% by weight, particularly 0.1 to 5% by weight, relative to the total weight of the composition.

[0166] At least one additive is selected from stabilizers, colorants, plasticizers, processing aids, or mixtures thereof.

[0167] It should be noted that the composition after the addition of additives must maintain its transparency properties.

[0168] As an example, stabilizers may include UV stabilizers, organic stabilizers, or more generally, combinations of organic stabilizers such as phenolic antioxidants (e.g., Ciba-BASF type Irganox 245 or 1098 or 1010), phosphite antioxidants (e.g., Ciba-BASF Irgafos® 126 or Irgafos® 168), and other stabilizers such as HALS meaning hindered amine light stabilizers (e.g., Ciba-BASF Tinuvin 770), anti-UV (e.g., Ciba's Tinuvin 312), or phosphorus stabilizers. Amine antioxidants such as Crompton's Naugard 445, or polyfunctional stabilizers such as Clariant's Nylostab S-EED may also be used.

[0169] This stabilizer may also be an inorganic stabilizer, such as a copper-based stabilizer. Examples of such inorganic stabilizers include halides and copper acetate. Secondly, other metals such as silver may be considered, but these have been found to be less effective. These copper-based compounds are typically related to alkali metal halides, particularly potassium.

[0170] As an example, plasticizers are selected from benzenesulfonamide derivatives such as n-butylbenzenesulfonamide (BBSA); ethyltoluenesulfonamide or N-cyclohexyltoluenesulfonamide; hydroxybenzoic acid esters such as 2-ethylhexyl parahydroxybenzoate and 2-decylhexyl parahydroxybenzoate; esters or ethers of tetrahydrotetrahydrofurfuryl alcohol such as oligoethyleneoxytetrahydrotetrahydrofurfuryl alcohol; esters of citric acid, or esters of hydroxymalonic acid such as oligoethyleneoxymalonate.

[0171] The use of a mixture of plasticizers is not outside the scope of this invention.

[0172] Regarding the composition: The composition of the present invention exhibits a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0173] A distinction is made between different moduli of elasticity (e.g., tensile modulus, flexural modulus, etc.). If the inventors of this invention examine the flexural modulus, it is always lower than the tensile modulus.

[0174] These moduli can be influenced by temperature and the moisture level in the sample.

[0175] In one embodiment, the modulus of elasticity defined above corresponds to both the flexural modulus and the tensile modulus, where the flexural modulus is measured according to standard ISO 178:2010 and the tensile modulus (or modulus of elasticity E) is measured according to standard ISO 527-1 and 2:2012.

[0176] In other embodiments, the modulus of elasticity defined above corresponds to the modulus of flexure and is measured as described above.

[0177] In other embodiments, the elastic modulus defined above corresponds to the tensile modulus and is measured as described above.

[0178] In one embodiment, the composition of the present invention has bending and tensile moduli exceeding 1700 MPa when measured dry at 23°C.

[0179] Advantageously, the flexural or tensile modulus measured dry at 23°C exceeds 1800 MPa.

[0180] Advantageously, the tensile modulus measured dry at 23°C exceeds 1900 MPa, and is particularly high at 2000 MPa.

[0181] In one embodiment, the transparent molded composition of the present invention exhibits a transmittance of more than 70%, as measured according to ASTM D1003, in a plate with a width and length of 100 mm x 100 mm and a thickness of 2 mm, produced from the polyamide molded composition in an unpolished mold.

[0182] Advantageously, the transmittance exceeds 75%, and especially above 80%.

[0183] In other embodiments, the transparent molded composition has a haze of less than 50%, particularly less than 40%, as measured according to ASTM D1003 on a 100 mm wide x 100 mm long, 2 mm thick plate produced from the polyamide molded composition in an unpolished mold.

[0184] For a favorable outcome, haze should be 35% or less.

[0185] Advantageously, the transparent molded composition of the present invention has a transmittance of more than 70% and a haze of less than 50%, particularly less than 40%, as measured according to ASTM D1003 on a plate with a width and length of 100 mm x 100 mm and a thickness of 2 mm, produced from the polyamide molded composition in an unpolished mold.

[0186] Advantageously, the transmittance exceeds 75%, especially above 80%, and the haze is 35% or less.

[0187] In yet another embodiment, the transparent molded composition of the present invention has an impact resistance of 15 kJ / m² measured according to ISO 179-1:2010 / 1eA (Charpy impact) at a temperature of 23°C ± 2°C and a relative humidity of 50% ± 10% in a dry sample state, using a V-notched bar measuring 80 mm × 10 mm × 4 mm. 2 Exceeding 17 kJ / m³, especially 17 kJ / m³ 2 It exceeds.

[0188] The composition of the present invention, (A) 10-95% by weight of at least one semicrystalline aliphatic polyamide in which the average number of carbon atoms relative to nitrogen atoms is 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-84%; (B) At least one impact-resistant modifier in an amount of 10-30%, especially 15-30%; (C) Glass short fibers 6-20%; (D) At least one prepolymer in 0-10% of its original concentration; (E) At least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof, in an amount of 0-5%, particularly 0.1-5%. This includes by weight (total 100%), The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540. The aforementioned composition does not contain PEBA and has a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0189] Advantageously, transparent molded compositions are (A) 10-95% by weight of at least one semicrystalline aliphatic polyamide in which the average number of carbon atoms relative to nitrogen atoms is 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-84%; B) At least one impact-resistant modifier in an amount of 10-30%, especially 15-30%; (C) Glass short fibers 6-20%; (D) At least one prepolymer in 0-10% of its original concentration; (E) At least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof, in an amount of 0-5%, particularly 0.1-5%. Composed of (100% total) by weight, The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540. The aforementioned composition does not contain PEBA and has a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0190] In other embodiments, a transparent molding composition, (A) 10-95% by weight of at least one semicrystalline aliphatic polyamide in which the average number of carbon atoms relative to nitrogen atoms is 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-83%; (B) At least one impact modifier in an amount of 10-30%, especially 15-30%; (C) Glass short fibers 6-20%; (D) At least one prepolymer, 1-10%; (E) At least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof, in an amount of 0-5%, particularly 0.1-5%. This includes by weight (total 100%), The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540. The aforementioned composition does not contain PEBA and has a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0191] In other embodiments, a transparent molding composition, (A) 10-95% by weight of at least one semicrystalline aliphatic polyamide in which the average number of carbon atoms relative to nitrogen atoms is 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-83%; (B) At least one impact modifier in an amount of 10-30%, especially 15-30%; (C) Glass short fibers 6-20%; (D) At least one prepolymer, 1-10%; (E) At least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof, in an amount of 0-5%, particularly 0.1-5%. Composed of (100% total) by weight, The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540. The aforementioned composition does not contain PEBA and has a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0192] In yet another embodiment, a transparent molded composition, (A) 10-95% by weight of at least one semicrystalline aliphatic polyamide in which the average number of carbon atoms relative to nitrogen atoms is 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-83.9% of the above; (B) At least one impact modifier in an amount of 10-30%, especially 15-30%; (C) Glass short fibers 6-20%; (D) At least one prepolymer in 0-10% of its original concentration; (E) At least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof, 0.1–5% This includes by weight (total 100%), The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540. The aforementioned composition does not contain PEBA and has a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0193] To the advantage, that is, (A) 10-95% by weight of at least one semicrystalline aliphatic polyamide in which the average number of carbon atoms relative to nitrogen atoms is 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-83.9% of the above; (B) At least one impact modifier in an amount of 10-30%, especially 15-30%; (C) Glass short fibers 6-20%; (D) At least one prepolymer in 0-10% of its original concentration; (E) At least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof, 0.1–5% Composed of a total of 100%, The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540. The aforementioned composition does not contain PEBA and has a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0194] In yet another embodiment, a transparent molded composition, (A) - 10-95% by weight of at least one semicrystalline aliphatic polyamide, in which the average number of carbon atoms relative to nitrogen atoms is 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-82.9% of the above; (B) At least one impact modifier in an amount of 10-30%, especially 15-30%; (C) Glass short fibers 6-20%; (D) At least one prepolymer, 1-10%; (E) At least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof, 0.1–5% This includes by weight (total 100%), The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540. The aforementioned composition does not contain PEBA and has a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0195] Advantageously, transparent compositions are (A) - 10-95% by weight of at least one semicrystalline aliphatic polyamide, in which the average number of carbon atoms relative to nitrogen atoms is 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-82.9% of the above; (B) At least one impact modifier in an amount of 10-30%, especially 15-30%; (C) Glass short fibers 6-20%; (D) At least one prepolymer, 1-10%; (E) At least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof, 0.1–5% Composed of a total of 100%, The refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540. The aforementioned composition does not contain PEBA and has a dry modulus of elasticity exceeding 1700 MPa at 23°C.

[0196] In the first variant, the semicrystalline aliphatic polyamide is dominant in mixture (A), and in particular, it is present in the mixture at an amount of 51% to 80% by weight.

[0197] Therefore, the term "predominant" means that in mixture (A), semicrystalline aliphatic polyamides make up more than 50% of the mixture, while amorphous polyamides make up less than 50%.

[0198] Therefore, amorphous polyamides are present in the mixture, particularly at a concentration of 20-49%.

[0199] All of the embodiments of the composition described above are effective for this first variant.

[0200] Advantageously, in this first variant, the composition exhibits resistance to a notched Ross Flex fatigue test at 23°C, measured according to standard ASTM D1052, with the sample notched and unperforated at a 60° fold angle, for more than 50,000 cycles.

[0201] In other embodiments, the present invention relates to the use of the above-defined compositions for a first variant for the manufacture of articles obtained by injection molding, selected from sports articles, particularly sports boots, particularly ski boots or ski boot components, or anti-slip materials, such as hard shoes with anti-slip materials for soccer, rugby or football, hockey skates or hockey skate components, or running shoes, golf balls or golf ball components, or lacrosse sticks, hockey articles, such as helmets for protecting the head, shoulders, elbows, hands, knees, back or shins, and sports articles, such as helmets, gloves, shoulder pads, elbow pads, knee pads, or shin guards.

[0202] Advantageously, the composition of the first variant is used to manufacture the outer sole of a sports shoe, which allows the pattern and color of the midsole of the sports shoe to be seen through the outer sole due to its transparency.

[0203] In the second variant, amorphous polyamide is dominant in mixture (A), particularly in the mixture at a concentration of 55% to 85% by weight.

[0204] Therefore, the term "predominant" means that in mixture (A), amorphous polyamides make up more than 50% of the mixture, while semicrystalline aliphatic polyamides make up less than 50%.

[0205] Therefore, semicrystalline aliphatic polyamides are present in the mixture, particularly at a concentration of 15-45%.

[0206] All of the embodiments of the composition described above are also valid for this second variant.

[0207] In other embodiments, the present invention relates to the use of a composition defined for a second variant for the manufacture of articles for electronics, telecommunications, or data conversion, such as for autonomous vehicles or interconnection applications.

[0208] In another aspect, the present invention relates to a method for preparing the above-defined composition, comprising the steps of mixing components (A), (B), (C), (D), and (E) in an extruder at a temperature between 230 and 330°C to produce granules, and then injecting the granules on an injection press at a temperature between 230 and 330°C to produce a desired article.

[0209] Therefore, this preparation method applies to all of the above-defined compositions, whether they are compositions in general or compositions of the first and second variants.

[0210] Transparent molded articles such as fibers, cloths, films, sheets, rods, tubes, and injection-molded parts, comprising the above-described composition, which may be produced in the form of a dry mixture or after compounding on an extruder.

[0211] Therefore, the article relates to all of the compositions defined above, whether or not they are compositions of the composition in general or the first and second variants.

[0212] In other embodiments, the present invention relates to a composite molded article comprising a resin element (I) comprising the above-defined composition, and a resin element (II) comprising a composition comprising a semicrystalline thermoplastic polymer, preferably thermal polyurethane (TPU) or foamed or non-foamed polyether block amide (PEBA), wherein the resin element (I) is directly bonded or bonded to the resin element (II).

[0213] A method for manufacturing a composite molded article as defined above, comprising heating at least one resin (I) and one resin (II) to attach one resin to the other. [Examples]

[0214] Preparation and mechanical properties of the composition of the present invention: Compositions shown in Tables I and II were prepared by mixing molten polyamide granules with an impact modifier, glass short fibers, and optional prepolymers and additives. These mixtures were prepared by compounding in an 18 mm diameter twin-screw co-rotating extruder with a planar temperature profile (T°). The screw speed was 300 rpm and the flow rate was 8 kg / hour.

[0215] Glass short fibers were introduced using a side feeder.

[0216] Polyamides, prepolymers, impact modifiers, and additives were added during the compounding process in the main hopper.

[0217] Subsequently, the compositions were molded in the shape of dumbbells (see Table 3) or bars using an injection molding machine (Engel) at a feed setting temperature of 240°C and a nozzle setting temperature of 260°C, and a molding temperature of 60°C, in order to investigate the properties of the compositions according to the following criteria.

[0218] The tensile modulus was measured at 23°C using a Type 1A dumbbell according to ISO standard 527-1:2012.

[0219] The machine used is an Instron 5966 type. The crosshead speed is 1 mm / min for elastic modulus measurement. The test conditions are 23°C ± 2°C for dry samples.

[0220] The composition is a dry composition.

[0221] The impact strength of a V-notched bar measuring 80 mm × 10 mm × 4 mm was measured according to ISO 179-1:2010 / 1eA (Charpy impact) at a dry sample temperature of 23°C ± 2°C and relative humidity of 50% ± 10%, or at a temperature of -30°C ± 2°C and relative humidity of 50% ± 10%.

[0222] Elongation at break and tensile strength were measured at 23°C in dry samples according to the standard ISO 527-1:2012.

[0223] A notched Ross Flex fatigue test was performed at 23°C according to standard ASTM D1052 09 (2014) (with a difference of 60° in the fold angle). Parts with a thickness of 2 mm, a length of 150 mm, and a width of 20 mm were prepared from the composition of the present invention (EIn) or the comparative composition (ECn) and then conditioned at 70°C and 62% relative humidity for 7 days. The cycle rate was 100 / min.

[0224] A 100×100×2mm³ wafer was fabricated by injection molding for transmittance and haze measurements. The following parameters were used: - Non-polishing type - ENGEL VICTORY500, 160T hydraulic press - Injection temperature (supply / nozzle): 260℃ / 280℃ - Mold temperature: 60°C - Hold time: 20 seconds - Material holding pressure: 525 bar - Cooling time: 20 seconds [Table 1] TIFF0007888554000001.tif255168TIFF0007888554000002.tif255168TIFF0007888554000003.tif77170[Table 2] TIFF0007888554000004.tif255168TIFF0007888554000005.tif121170PA11: Rilsan(registered trademark) (Arkema) PA11 / B10 (weight ratio 10:90) Kraton (trademark) FG 1901: A linear triblock copolymer based on styrene and ethylene / butylene, functionalized with maleic anhydride, d=0.91 g / cm3, supplied by Kraton Polymers. Paraloid™ EXL2690: Methyl methacrylate-butadiene-styrene (MBS) core-shell copolymer Additives: Antioxidant mixture (0.1% by weight) + Second antioxidant (0.2% by weight)

[0225] Injectability and surface appearance were also measured.

[0226] Various results are shown in Tables 1 to 6. [Table 3] The data for TIFF0007888554000006.tif96170EC2 and EC3 are not from the applicant, but are shown in EP 3,309,199 B1 and EP 3,486,287 A1, respectively. [Table 4] TIFF0007888554000007.tif131170 A Type 1A dumbbell was obtained by injection molding using an Engel type injection molding machine: [Table 5] TIFF0007888554000008.tif51170[Table 6] TIFF0007888554000009.tif77170

Claims

1. (A) - 10 to 95% by weight of at least one semicrystalline aliphatic polyamide having an average number of carbon atoms relative to nitrogen atoms of 8 or more. - At least one amorphous polyamide 90-5% by weight A polyamide mixture containing 35-84%; (B) At least one impact-resistant modifier in an amount of 10-30%, particularly 15-30%; (C) Glass short fibers 6-20%; (D) 0-10% of at least one prepolymer; (E) 0-5%, particularly 0.1-5%, of at least one additive selected from stabilizers, dyes, plasticizers, processing aids, or mixtures thereof. It contains a total of 100% by weight, A transparent molded composition in which the refractive indices of each component (A), (B), (C), and (D) are 1.500 to 1.540, A transparent molded composition which does not contain PEBA and has a dry modulus of elasticity measured at 23°C that exceeds 1700 MPa.

2. The transparent molded composition according to claim 1, characterized in that a plate with a width and length of 100 mm * 100 mm and a thickness of 2 mm, produced from the polyamide molded composition in an unpolished mold, has a transmittance of more than 70% as measured according to ASTM D1003.

3. The transparent molded composition according to claim 1 or 2, characterized in that a plate with a width and length of 100 mm x 100 mm and a thickness of 2 mm, produced from the polyamide molded composition in an unpolished mold, has a haze of less than 50%, particularly less than 40%, as measured according to ASTM D1003.

4. For a V-notched bar measuring 80 mm x 10 mm x 4 mm, the impact resistance measured according to ISO 179-1:2010 / 1eA (Charpy impact) at a dry sample state, temperature 23°C ± 2°C, relative humidity 50% ± 10%, was 15 kJ / m². ２ A transparent molded composition according to any one of claims 1 to 3, characterized in that it exceeds [a certain value].

5. A transparent molded composition according to any one of claims 1 to 4, characterized in that the impact resistance modifier is selected from SEBS, SBS, and a core-shell structure.

6. The amorphous polyamide is a polyamide of formula XY or A / XY, where - A is an aliphatic repeating unit selected from a unit obtained from the polycondensation of at least one amino acid, a unit obtained from the polycondensation of at least one lactam, and a unit obtained from the polycondensation of at least one aliphatic diamine and at least one aliphatic diacid. - X is an alicyclic diamine, - Y is a dicarboxylic acid, The aforementioned diacid is selected from linear or branched aliphatic diacids, alicyclic diacids, and aromatic diacids. The transparent molding composition according to any one of claims 1 to 5, characterized in that the diamine and the diacid contain 4 to 36 carbon atoms, preferably 6 to 18 carbon atoms.

7. A transparent molded composition according to any one of claims 1 to 6, characterized in that the amorphous polyamide is selected from 11 / B10, 12 / B10, 11 / P10, 12 / P10, 11 / BI / BT, 12 / BI / BT, 11 / PI / BT, 12 / PI / BT, 11 / PI / PT, 12 / PI / PT, 11 / BI, 12 / BI, 11 / PI, and 12 / PI, and is particularly 11 / B10.

8. The transparent molding composition according to any one of claims 1 to 7, characterized in that the semicrystalline aliphatic polyamide is a mixture of two semicrystalline aliphatic polyamides having an average number of carbon atoms relative to nitrogen atoms of 8 to 14, particularly 9 to 14, and particularly 10 to 14.

9. The transparent molded composition according to any one of claims 1 to 8, characterized in that the semicrystalline aliphatic polyamide is selected from PA10, PA11, PA12, PA1010, and PA1012, and is particularly PA11 and PA12.

10. The composition according to any one of claims 1 to 9, characterized in that the semicrystalline aliphatic polyamide is PA11, and the amorphous polyamide is selected from 11 / B10, 12 / B10, 11 / P10, 12 / P10, 11 / BI / BT, 12 / BI / BT, 11 / PI / BT, 12 / PI / BT, 11 / PI / PT, and 12 / PI / PT, and particularly 11 / B10 and 12 / BI / BT.

11. The composition according to any one of claims 1 to 10, characterized in that the semicrystalline polyamide and / or amorphous polyamide are partially or completely of biological origin.

12. A transparent molding composition according to any one of claims 1 to 11, characterized in that a semicrystalline aliphatic polyamide is predominant in the mixture (A), and in particular, is contained in the mixture in an amount of 51% to 80% by weight.

13. The transparent molded composition according to claim 12, characterized in that it has a resistance of more than 50,000 to a notched Ross Flex fatigue test at 23°C, measured according to the standard ASTM D1052, at a bending angle of 60° in a notched and non-perforated state.

14. Use of the composition according to claim 12 or 13 for the manufacture of articles obtained by injection, selected from sports articles, particularly ski boots or ski boot parts, or anti-slip, for example, hard shoes with anti-slip for soccer, rugby or football, hockey footwear or hockey footwear parts, or running shoes, golf balls or golf ball parts, or lacrosse sticks, hockey articles, for example, helmets for protecting the head, shoulders, elbows, hands, knees, back or shins, and sports articles, for example, helmets, gloves, shoulder pads, elbow pads, knee pads, or shin guards.

15. The use of the transparent molding composition according to claim 14, characterized in that it is used to manufacture an outer sole of a sports shoe, which allows the pattern and color of the midsole of the sports shoe to be seen through the outer sole due to its transparency.

16. A transparent molding composition according to any one of claims 1 to 11, characterized in that amorphous polyamide is predominant in mixture (A), and in particular is contained in the mixture in an amount of 55% to 85% by weight.

17. Use of the transparent molding composition according to claim 16 for the manufacture of articles for electronics, telecommunications, or data conversion, for example, for autonomous vehicles or interconnection applications.

18. A method for preparing a composition according to any one of claims 1 to 13 and 16, comprising the step of mixing components (A), (B), (C), (D), and (E) in an extruder at a temperature between 230 and 330°C to produce granules, the granules then being injected on an injection press at a temperature between 230 and 330°C to produce a desired article.

19. A transparent molded product such as a fiber, cloth, film, sheet, rod, tube, or injection-molded part, comprising the composition according to any one of claims 1 to 13 and 16, which may be produced in the form of a dry mixture or after compounding on an extruder.

20. A composite molded article comprising a resin element (I) comprising the composition according to any one of claims 1 to 13 and 16, and a resin element (II) comprising the composition comprising a thermoplastic polymer, particularly thermal polyurethane (TPU) or foamed or non-foamed polyether block amide (PEBA), wherein the resin element (I) is directly bonded or bonded to the resin element (II).

21. A method for manufacturing a composite molded article according to claim 20, comprising heating at least one resin (I) and one resin (II) to attach one resin to the other.

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