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    • 专利摘要:
    The present invention relates to the use of circular section glass fibers in a mixture comprising at least one MXDZ polyamide, obtained from the polycondensation of meta-xylylenediamine (MXD), with a C6 aliphatic (Z) dicarboxylic acid. at C18, in particular at C6 to C12, and at least one aliphatic polyamide A obtained from the polycondensation of a unit selected from: - a C 6 to C 12 lactam, - a C 6 to C 12 amino acid, and - a unit XY obtained from the polycondensation of a C4 to C18, especially C4 to C12, aliphatic diamine (X) and a C6 to C18 aliphatic (Y) dicarboxylic acid, in particular C6 to C12, to glass fibers circular section and optionally at least one impact modifier and / or at least one additive, said circular section glass fibers and said mixture constituting a composition, said circular section glass fibers being present from 30 to 75% by weight, particular of 4 0 to 65% by weight and relative to the total weight of the composition, to improve the mechanical properties of said composition, in particular elongation at break, after its implementation, in particular by injection or compression molding.
    公开号:FR3057575A1
    申请号:FR1752407
    申请日:2017-03-23
    公开日:2018-04-20
    发明作者:Benoit Brule；Antoine BREUIL；Hao Wang；Xiong Yao
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    © Publication no .: 3,057,575 (to be used only for reproduction orders)
    ©) National registration number: 17 52407 ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY
    COURBEVOIE
    ©) IntCI 8 : C 08 K 5/529 (2017.01), C 08 L 77/02, 77/06, C 07 J 5/00
    A1 PATENT APPLICATION
    ©) Date of filing: 23.03.17. (71) Applicant (s): ARKEMA FRANCE Public limited company (30) Priority: 19.10.16 FR 1660126. - FR. (72) Inventor (s): BRULE BENOIT, BREUIL ANTOINE, WANG HAO and YAO XIONG. (43) Date of public availability of the request: 20.04.18 Bulletin 18/16. ©) List of documents cited in the report preliminary research: Refer to end of present booklet (© References to other national documents ©) Holder (s): ARKEMA FRANCE Société anonyme. related: ©) Extension request (s): ©) Agent (s): ARKEMA FRANCE Société anonyme.
    FR 3 057 575 - A1 (041 USE OF GLASS FIBERS WITH A CIRCULAR SECTION IN A MIXTURE COMPRISING A SEMI-AROMATIC POLYAMIDE AND AN ALIPHATIC POLYAMIDE FOR IMPROVING THE MECHANICAL PROPERTIES OF SAID MIXTURE.
    The present invention relates to the use of working fibers, in particular by injection or molding by glass compress with circular section in a mixture comprising ion. at least one polyamide MXDZ, obtained from the polycondensation of meta-xylylene diamine (MXD), with an aliphatic dicarboxylic acid (Z) at C 6 to C 18 , in particular at C 6 to C 12 , and at least one aliphatic polyamide A obtained from the polycondensation of a motif chosen from:
    - a C 6 to C · ^ lactam,
    a C 6 to C 12 amino acid, and
    - an XY motif obtained from the polycondensation of an aliphatic diamine (X) at C 4 to C 18 , in particular at C 4 to C 12 and an aliphatic dicarboxylic acid (Y) at C 6 to C 18 , in particular in C 6 to C 12 , glass fibers with circular section and optionally at least one impact modifier and / or at least one additive, said glass fibers with circular section and said mixture constituting a composition, said glass fibers with circular section being present from 30 to 75% by weight, in particular from 40 to 65% by weight and relative to the total weight of the composition, to improve the mechanical properties of said composition, in particular the elongation at break, after its setting
    Use of circular section glass fibers in a mixture comprising a semi-aromatic polyamide and an aliphatic polyamide to improve the mechanical properties of said mixture
    The present invention relates to the use of glass fibers of circular cross section in a mixture comprising at least one polyamide MXDZ and at least one aliphatic polyamide, in particular semi-crystalline, for improving the mechanical properties of said composition, in particular the elongation at rupture, after its implementation, in particular by injection or compression molding.
    It also relates to the composition obtained with the semi-aromatic polyamide and the mixture of aliphatic polyamide comprising glass fibers with circular section and its use to constitute a monolayer structure or at least one layer of a multilayer structure, in particular in the electrical field. and / or electronics (E / E).
    Many applications in the E / E field require very rigid materials (phone shell, computer part, etc.). Rigidity is all the more important as the market trend is towards a reduction in the weight of electronic equipment and therefore towards a reduction in the thicknesses of the parts.
    However, the production of thin pieces brings other problems: ability to be injected, in particular sufficiently fluid materials to completely fill the mold and above all said pieces whose thickness is reduced must have mechanical properties, in particular the elongation at break, sufficient after its implementation, in particular by injection or compression molding to withstand the stresses during the life of the product.
    In these applications, rigid polyamides (PA) (module> 12GPa) find a great place. But as soon as the fiber content is greater than 30%, the use of fibers with a non-circular or flat cross-section (FF) is the solution chosen to satisfy all of the specifications, in particular the aspects of warping and mechanical properties.
    Thus, application EP2789591 indicates that glass fibers with non-circular cross-section make it possible to improve the mechanical properties, the dimensional precision and the warping of resins reinforced with said glass fibers of non-circular section. This is due, according to this request, as regards the improvement of the mechanical properties, to the fact that the glass fibers of non-circular section have a contact surface greater than that of the fibers of circular section.
    Application US 2011/0105655 describes compositions having a low distortion during molding and consisting of 25 to 72% by weight of a polyamide, from 20 to 65% by weight of glass fibers with a flat section of L / D ratio of 2 to 8, and from 8 to 25% of a flame retardant (L representing the large dimension of the cross section of the fiber and D the small dimension of the cross section of said fiber). The polyamide used is a mixture of 55-90% by weight of an aliphatic polyamide and 10 to 45% by weight of another polyamide chosen from MACM10-18, MACMI, MACMT, MXDI, MXDT, MXDX / MXDI, PACM10 -18, 6I, 6T, 6I / 6T and 6T / 66 compared to the total sum of the polyamides.
    The elongation at break values presented in the examples of this application are comprised from 1.3 to 1.5% for mixtures of ΡΑΧΥ (PA66) and PA6 or PA6I / 6T (MXDZ is not exemplified) comprising glass fibers, whatever the shape of the fibers, of flat or circular section. In addition, the use of flat section glass fibers always leads to a higher elongation at break than that obtained with circular section glass fibers.
    Patent JP5523520 describes polyamide granules having electrical properties and resistance to deformation.
    The granules consist of 5-40 parts by weight of a flame retardant, 5-200 parts by weight of a flat section glass fiber with an L / D ratio of at least 2.3 and 0- 40 parts by weight of a polyamide which can be a mixture of aliphatic polyamide with a semi-aromatic polyamide such as MXD10.
    However, these different compositions of the prior art and in particular with flat section glass fibers lead to compositions having mechanical properties which may be insufficient for an E / E application.
    In addition, the use of flat section glass fibers compared to circular section glass fibers generates a significant additional cost. In addition, there are far fewer suppliers of flat section fiberglass than suppliers of circular section fiberglass. These two aspects are essential in the industrial production of glass fiber reinforced resins.
    It is therefore necessary to be able to have compositions using glass fibers with circular section, thus making it possible to limit the cost of said composition and to ensure a perennial supply of glass fibers with circular section and to have compositions having improved mechanical properties, in particular the elongation at break, after its implementation, in particular by injection or compression molding, compared to flat section glass fibers. These various problems have been resolved with the use of circular section glass fibers with a specific blend based on aliphatic polyamide and MXDZ.
    The inventors have in fact unexpectedly found that the addition of glass fibers of circular cross-section in a mixture comprising at least one polyamide MXDZ, and at least one aliphatic polyamide, in particular semi-crystalline, makes it possible to improve the mechanical properties of said composition, in particular the elongation at break, after its implementation, in particular by injection or compression molding with respect to the same composition comprising glass fibers with flat section instead of glass fibers with circular section.
    Another advantage of the invention is that said compositions exhibit limited warpage during implementation, in particular by injection or compression molding of the composition, that is to say warpage of less than 2 mm, in particular less than 1 mm as determined on 100 * 100 * 1 mm plates 3 .
    Warping can be completely eliminated but as a rule it is less than 2mm, in particular less than 1mm.
    The present invention relates to the use of glass fibers of circular section in a mixture comprising at least one polyamide MXDZ, obtained from the polycondensation of meta-xylylene diamine (MXD), with an aliphatic dicarboxylic acid (Z) in Ü6 to Cw, in particular in Ü6 to C12, and at least one aliphatic polyamide A obtained from the polycondensation of a unit chosen from:
    - a lactam in Ü6 to C12,
    - an amino acid at Ü6 to C12, and
    an XY motif obtained from the polycondensation of an aliphatic diamine (X) at C4 to Cw, in particular at C4 to C12, and an aliphatic dicarboxylic acid (Y) at Ü6 to Cw, in particular at C6 to C12, glass fibers with circular section and optionally at least one impact modifier and / or at least one additive, said glass fibers with circular section and said mixture constituting a composition, said glass fibers with circular section being present from 30 to 75% by weight, in particular from 40 to 65% by weight and relative to the total weight of the composition, in order to improve the mechanical properties of said composition, in particular the elongation at break, after its implementation, in particular by injection or compression molding.
    Meta-xylylene diamine (MXD, CAS number 1477-55-0) can be used alone or in admixture with para-xylylene diamine (PXD, CAS number 539-48-0). But in the latter case, and throughout the description, the MXD must be in the majority compared to the PXD.
    Advantageously, the MXD is used alone.
    The aliphatic dicarboxylic acid (Z) at C6 to Cw can be chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid , tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.
    The aliphatic dicarboxylic acid (Z) is not a mixture of C6 to C-aliphatic dicarboxylic acids defined above and the MXDZ therefore corresponds to a homopolyamide. Nevertheless, MXDZ can correspond to a mixture of MXDZ. Advantageously, the ipβ to C12 aliphatic dicarboxylic acid (Z) can be chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.
    The expression "aliphatic polyamide" means a homopolyamide excluding a copolyamide. It is understood that it may be a mixture of aliphatic polyamides. Aliphatic polyamide A is therefore a homopolyamide.
    The nomenclature used to define polyamides is described in standard ISO 1874-1: 2011 Plastics - Polyamide materials (PA) for molding and extrusion Part 1: Designation, in particular on page 3 (tables 1 and 2) and is well known in the art. skilled in the art.
    When the aliphatic polyamide A is obtained from the polycondensation of a lactam, said lactam can be chosen from pyrrolidinone, 2-piperidinone, caprolactam, enantholactam, caprolactam, pelargolactam, decanolactam, undecanolactam, and lauryllactame, in particular lauryllactame. When the aliphatic polyamide A is obtained from the polycondensation of an amino acid, it can be chosen from 9-aminononanoic acid, 10 aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid and its derivatives, in particular N-heptyl-11aminoundecanoic acid, in particular 11-aminoundecanoic acid.
    When the aliphatic polyamide A is obtained from the polycondensation of an XY motif, the diamine (X) at C4 to Cw used in the polyamide XY is a linear or branched diamine, and can in particular be chosen from 1.4 -butanediamine, 1,5pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine 1,7heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1, 8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undécanediamine, 2butyl-2-ethyl-1,5-pentanediamine, 1,12 -dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine. Advantageously, the diamine (X) used is in C4 to C12, in particular chosen from
    1,4-butanediamine, 1,5-pentamethyldiamine, 2-methyl-1,5-pentanediamine, 1,6hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9nonanediamine, 2-methyl -1,8-octane-diamine, 2,2,4trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10décanediamine, 1,11-undécanediamine, 2-butyl-2-ethyl-1,5-pentanediamine , 1,12dodecanediamine.
    Advantageously, the diamine (X) used is C6 to Cw, in particular chosen from 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octane-diamine, 2,2,4trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10decanediamine.
    When the aliphatic polyamide A is obtained from the polycondensation of a unit XY, the aliphatic dicarboxylic acid (Y) at C6 to Cw, in particular at C6 to C12, used in the polyamide XY, is as defined above above.
    By fiberglass within the meaning of the invention is meant any glass fiber, in particular as described by Frederick T. Wallenberger, James C. Watson and Hong Li, PPG industries Inc. (ASM Handbook, Vol 21: composites (# 06781G), 2001 ASM International), provided that the said fiber is of circular section.
    Advantageously, said glass fibers have a diameter comprised from 4 μm to less than 25 μm, preferably from 4 to 15 microns and a L / D ratio (L representing the large dimension of the cross section of the fiber and D the small dimension of the cross section of said fiber) less than 2, in particular less than 1.5. Advantageously, the L / D ratio is equal to approximately 1.
    The expression "impact modifier" means a polyolefin-based polymer having a flexural modulus of less than 100 MPa measured at 23 ° C. according to the standard
    ISO 178: 2010 and of Tg below 0 ° C (measured according to standard 11357-2 at the point of inflection of the DSC thermogram), in particular a polyolefin, coupled or not with a Peba (polyether block amide) having a flexural modulus <200 MPa. It would not go beyond the scope of the invention to use a Peba alone as a shock modifier in the composition.
    The polyolefin of the impact modifier can be functionalized or nonfunctionalized or be a mixture of at least one functionalized and / or at least one nonfunctionalized.
    In particular, part or all of the polyolefins carry a function chosen from the carboxylic acid, carboxylic anhydride and epoxide functions, and is in particular chosen from an ethylene-propylene copolymer of elastomeric character (EPR), an ethylene-propylene copolymer -diene with an elastomeric nature (EPDM) and an ethylene / (meth) alkyl acrylate copolymer, an ethylene-higher alkene copolymer, in particular an ethylene-octene copolymer, an ethylene-alkyl acrylate-maleic anhydride terpolymer.
    Advantageously, the impact modifier is chosen from F493®, a Pebax®, in particular Pebax® 40R53 SP 01, a Lotader®, in particular Lotader® 5500 or Lotader® 7500, Exxelor VA1803®, or a mixture of these, in this case they are in a ratio ranging from 0.1 / 99.9 to 99.9 / 0.1, preferably 1/2 to 2/1 when they are a mixture of two.
    By way of example, the impact modifier is chosen from the following mixtures: F493® / Lotader®, in particular F493® / Lotader® 5500 or F493® / Lotader® 7500.
    The impact modifier can also be a “core-shell” type modifier, also known as a “core-shell type copolymer”.
    The “core-shell” type modifier is in the form of fine particles having an elastomer core and at least one thermoplastic shell, the particle size is generally less than a μm and advantageously between 150 and 500 nm.
    The "core-shell" modifier has an acrylic or butadiene base, unlike the impact modifier, which has a polyolefin base.
    Advantageously, the proportion of impact modifier is between 0 and 10% by weight relative to the total weight of the composition.
    The use of glass fibers of circular cross section in the mixture comprising at least one MXDZ and at least one aliphatic polyamide constitutes a composition.
    Advantageously, said composition is devoid of flame retardant.
    Advantageously, said composition is devoid of PA66.
    Advantageously, said composition is devoid of flame retardant and of PA66.
    The additives optionally used in the composition obtained with the use of glass fibers in a mixture of MXDZ and aliphatic polyamide A are the conventional additives used in polyamides and well known to those skilled in the art. The expression "improving the mechanical properties of said composition, in particular the elongation at break" means supporting sufficient deformation during application.
    Advantageously, the weight ratio MXDZ / A in the said composition is from 0.11 to 0.83, in particular from 0.11 to 0.66.
    Consequently, in this embodiment, the semi-aromatic polyamide MXDZ is always in a proportion lower than the aliphatic polyamide A or the mixture of aliphatic polyamides A.
    Advantageously, the aliphatic polyamide A is a semi-crystalline polyamide or a mixture of semi-crystalline polyamides.
    Advantageously, the aliphatic polyamide A is a semi-crystalline polyamide. The expression “semi-crystalline polyamide” within the meaning of the invention designates polyamides which have a melting temperature (Tf) and an enthalpy of fusion ΔΗ> 10 J / g, in particular> 12 J / g as well as a glass transition temperature (Tg) as determined by DSC according to standard ISO 11357-1: 2009 and ISO 11357-2 and 3: 2013, at a heating rate of 20K / min.
    Advantageously, the elongation at break of said composition after its implementation, in particular by injection or compression molding, is increased up to 30% compared to the same composition comprising glass fibers of flat section instead of glass fibers with circular section.
    In particular, said increase in said elongation at break is between 10 and 30% (please confirm or correct)
    Advantageously, said composition constituted by the use of said circular section glass fibers with said mixture comprises:
    - from 5 to 30% by weight, in particular from 5 to 20% by weight of MXDZ,
    from 20 to 60% by weight, in particular from 25 to 50% by weight of said at least one polyamide A,
    - from 30 to 75% by weight, in particular from 40 to 65% by weight of glass fibers with circular section,
    - from 0 to 10% of at least one impact modifier,
    - from 0 to 2% of at least one additive,
    The sum of the proportions of each constituent of the composition being equal to 100%.
    Advantageously, said composition constituted above is one of the following (the 5 percentages are given by weight):
    COMPOSITION NO. MXDZ Polyamidealiphatic A Glass fibers 1 5-30% 20-60% 30-75% 2 5-30% 20-60% 40-65% 3 5-30% 25-50% 30-75% 4 5-30% 25-50% 40-65% 5 5-20% 20-60% 30-75% 6 5-20% 20-60% 40-65% 7 5-20% 25-50% 30-75% 8 5-20% 25-50% 40-65%
    The sum of the constituents of each composition 1 to 8 is equal to 100%.
    Each of compositions 1 to 8 above can further comprise at least one impact modifier up to 10% by weight, the sum of the constituents being equal to 100%. Each of the compositions 1 to 8 above can also comprise at least one additive up to 2% by weight, the sum of the constituents being equal to 100%.
    Each of the compositions 1 to 8 above can also comprise at least one impact modifier up to 10% by weight and at least one additive up to 2% by weight, the sum of the constituents being equal to 100%.
    Advantageously, the MXDZ used in one of the compositions defined above comprises MXD10.
    MXD10 is therefore mixed with at least one other MXDZ, Z being a C6 to Cw dicarboxylic acid as defined above, in particular in a proportion greater than 50% by weight relative to the total sum of the MXDZ polyamides.
    Advantageously, the MXDZ used in one of the compositions defined above consists of MXD10 and MXD6.
    Advantageously, the MXDZ used in one of the compositions defined above consists of MXD10.
    Advantageously, the aliphatic polyamide A comprises an aliphatic polyamide obtained from the polycondensation of a unit XY in which the dicarboxylic acid (Y) is sebacic acid.
    Advantageously, said aliphatic polyamide A obtained from the polycondensation of a unit XY in which the dicarboxylic acid (Y) is sebacic acid is in proportion greater than 50% by weight relative to the total weight of the aliphatic polyamides A. Advantageously, said aliphatic polyamide A obtained from the polycondensation of an XY unit corresponds to a single polyamide whose dicarboxylic acid (Y) is sebacic acid.
    Advantageously, the aliphatic polyamide A comprises an aliphatic polyamide obtained from the polycondensation of an XY unit whose diamine (X) is C6 to Cio.The aliphatic polyamide A is therefore a mixture of at least two polyamides XY whose diamine ( X) is C6 to Cw, the diamines being different from each other, in particular.
    Advantageously, said aliphatic polyamide A obtained from the polycondensation of an XY unit, the diamine (X) of which is C6 to Cw is in proportion greater than 50% by weight relative to the total weight of the polyamides XY.
    Advantageously, said aliphatic polyamide A obtained from the polycondensation of an XY motif consists of a polyamide XY whose diamine (X) is C6 to Cw.
    In particular, the diamine (X) is chosen from hexamethylene diamine and decanediamine.
    Advantageously, said at least MXDZ consists of 0% to 49% by weight of MXD6 and 51 to 100% by weight of MXD10 and said aliphatic polyamide A obtained from the polycondensation of an XY motif consists of 0 to 49% by weight of PA610 and from 51 to 100% by weight of PA1010.
    Advantageously, MXDZ consists of MXD10 and said aliphatic polyamide A obtained from the polycondensation of an XY motif consists of 0 to 49% by weight of PA610 and 51 to 100% by weight of PA1010.
    Advantageously, MXDZ consists of MXD10 and said aliphatic polyamide A obtained from the polycondensation of an XY motif consists of PA1010. Advantageously, said at least MXDZ consists of 0% to 49% by weight of MXD6 and 51 to 100% by weight of MXD10 and said aliphatic polyamide A obtained from the polycondensation of an XY motif consists of 0 to 49% by weight of PA1010 and from 51 to 100% by weight of PA610.
    Advantageously, MXDZ consists of MXD10 and said aliphatic polyamide A obtained from the polycondensation of an XY motif consists of 0 to 49% by weight of PA1010 and 51 to 100% by weight of PA610.
    Advantageously, MXDZ consists of MXD10 and said aliphatic polyamide A obtained from the polycondensation of an XY motif consists of PA610.
    Advantageously, said aliphatic polyamide A is obtained from the polycondensation of a lactam or an amino acid, in particular lauryllactam or aminoundecanoic acid.
    Advantageously, MXDZ consists of MXD10 and said aliphatic polyamide A is obtained from the polycondensation of lauryllactam.
    Advantageously, MXDZ consists of MXD10 and said aliphatic polyamide A is obtained from the polycondensation of 11-aminoundecanoic acid.
    In an advantageous embodiment, said at least one additive of said composition constituted by the use of said glass fibers of circular section with said mixture is chosen from fillers, dyes, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, lubricants, flame retardants, natural waxes and their mixtures. In an advantageous embodiment, said composition constituted by the use of said circular section glass fibers with said mixture comprises:
    - from 5 to 30% by weight, in particular from 5 to 20% by weight, of a polyamide MXD10, obtained from the polycondensation of meta-xylylene diamine (MXD) or a mixture of meta-xylylene diamine and para-xylylene diamine, with sebacic acid,
    - from 20 to 60% by weight, in particular from 25 to 50% of PA1010 obtained from the polycondensation of decanediamine and sebacic acid,
    - from 30 to 75% by weight, in particular from 40 to 65% by weight of glass fibers with circular section,
    - from 0 to 10% by weight of at least one impact modifier,
    - from 0 to 2% of at least one additive.
    In an advantageous embodiment, said composition constituted by the use of said circular section glass fibers with said mixture comprises:
    - from 5 to 30% by weight, in particular from 5 to 20% by weight, of a polyamide MXD10, obtained from the polycondensation of meta-xylylene diamine (MXD) or a mixture of meta-xylylene diamine and para-xylylene diamine, with sebacic acid,
    - from 20 to 60% by weight, in particular from 25 to 50% of PA610 obtained from the polycondensation of hexamethylene diamine and sebacic acid,
    - from 30 to 75% by weight, in particular from 40 to 65% by weight of glass fibers with circular section,
    - from 0 to 10% by weight of at least one impact modifier,
    - from 0 to 2% of at least one additive.
    Advantageously, the MXDZ of compositions 1 to 8 defined above is MXD10 and the PAXY is PA1010.
    Advantageously, the MXDZ of compositions 1 to 8 defined above is MXD10 and the PAXY is PA610.
    Advantageously, the MXDZ of compositions 1 to 8 defined above is MXD10 and the aliphatic polyamide A is PA1012.
    Advantageously, the MXDZ of compositions 1 to 8 above defined is MXD10 and the aliphatic polyamide A is PA12.
    Advantageously, the MXDZ of compositions 1 to 8 defined above is MXD10 and the aliphatic polyamide A is PA11.
    The composition defined above can be used to constitute a monolayer structure or at least one layer of a multilayer structure.
    In particular, said structure is presented under the shape of an injected part.
    The composition defined above can also be used to constitute an object. Said object can be shaped by a method comprising a step of injection molding of said composition.
    Said object can be used in the electrical and / or electronic field.
    DESCRIPTION OF THE FIGURES
    Figure 1 (A and B) shows the warping obtained with 2 plates (100 * 100 * 1 mm 3 ) injected by:
    A: composition 11 or I2 of the invention,
    B: composition C1 or C4, and measured as described in example 2.
    A: injected plate 11 or I2 whose warping is limited and less than 1 mm,
    B: C1 or C4 injected plate whose warping is very significant and greater than 5 mm.
    EXAMPLES
    Example 1: Mechanical properties Summary
    PA610, PA1010 and MXD10 were prepared separately and respectively by polycondensation of hexamethylene diamine and sebacic acid, decanediamine and sebacic acid and meta-xylylene diamine and sebacic acid according to well known techniques. the skilled person.
    Compounding
    The compositions were prepared by melt blending the polymer granules. This mixing was carried out by compounding on an MC26 type twin screw extruder with a flat T profile at 270 ° C. The screw speed is 250rpm. The introduction of glass fibers of circular section or flat section is carried out by side feeding.
    Injection
    Plates of 100 * 100 * 1 mm 3 were prepared by injection of the different compositions:
    - Injection temperature (supply / nozzle): 250/270 ° C and 270/300 ° C
    - Mold temperature: 65 ° C and 90 ° C and 100 ° C
    - Hold time: 10 seconds
    - Cooling time: 20 and 30 seconds
    The following compositions were prepared (Table 1):
    Composition MXDZ(% inweight) PAXY(% inweight) Glass fibercircular section(% in weight)NittoboCSX3J451S0 Glass fiberflat section(% in weight)NittoboCSG3PA820S C1 - PA610 50% 50% - C2 - PA61050% - 50% C3 MXD1015% PA61035% - 50% 11 MXD1015% PA61035% 50% -
    C4 - PA101045% 55% - C5 - PA101045% - 55% I2 MXD1015% PA101030% 55% -
    C: Comparative composition I: Composition of the invention
    TABLE 1
    The elongation at break of compositions C2, C3 and 11 was determined according to ISO standard 527.
    The mechanical machine is an INSTRON 5966. The speed of the crosshead is 1mm / min. The test conditions are 23 ° C, 50% RH. The ISO 527 1A geometry samples having been previously conditioned for 2 weeks at 23 ° C, 50% RH. The deformation is measured by a contact extensometer.
    The results are presented in table 2 (test on five samples):
    Composition Elongation at break % standard deviation C2 2.7 0.08 C3 2.6 0.07 11 3.6 0.09
    TABLE 2
    Table 2 shows that the composition of the invention has a percentage of elongation at break increased by 30% compared to the same composition with glass fibers of flat section instead of glass fibers of circular section or a composition consisting of PA610 and flat section glass fibers.
    Example 2: Evaluation of the warping of polyamide compositions based on PA610 or PA1010, MXD10 and glass fibers with circular section or with flat section.
    Warping was assessed using the method described below:
    The injected plates are placed on a table. The operator presses on 3 angles of the plate to raise the fourth. The difference between the surface of the table and the sample is then measured, see the arrow in FIG. 1. On the left sample in FIG. 1 (A), the warping is limited, that is to say say less than 1mm.
    The results are presented in the following table 3:
    Composition Warping C1 Very important> 5mm * C2 <1mm 11 <1mm C4 Very important> 5mm C5 <1mm I2 <1mm
    * Warping is very important whatever the injection conditions (different T, different T of mold, cooling temperature, ...)
    C: Comparative composition
    I: Composition of the invention
    TABLE 3
    Table 3 shows that the introduction of circular section glass fibers into an aliphatic polyamide XY devoid of MXDZ induces a significant warping which is practically eliminated by the introduction of MXDZ, even for a proportion as large as 50% by weight of fiber fibers. glass with circular section.
    权利要求:
    Claims (9)
    [1" id="c-fr-0001]
    Claims
    1. Use of glass fibers with circular section in a mixture comprising at least one polyamide MXDZ, obtained from the polycondensation of meta-xylylene diamine (MXD), with an aliphatic dicarboxylic acid (Z) in Ü6 to Cw, in in particular in Ü6 to C12, and at least one aliphatic polyamide A obtained from the polycondensation of a unit chosen from:
    - a lactam in Ü6 to C12,
    - an amino acid at Ü6 to C12, and
    an XY motif obtained from the polycondensation of an aliphatic diamine (X) at C4 to Cw, in particular at C4 to C12 and an aliphatic dicarboxylic acid (Y) at Ce to Cw, in particular at C6 to C12, glass fibers with circular section and optionally at least one impact modifier and / or at least additive, said glass fibers with circular section and said mixture constituting a composition, said glass fibers with circular section being present from 30 to 75% by weight , in particular from 40 to 65% by weight and relative to the total weight of the composition, to improve the mechanical properties of said composition, in particular the elongation at break, after its implementation, in particular by injection or molding by compression.
    [2" id="c-fr-0002]
    2. Use according to claim 1, characterized in that the weight ratio MXDZ / A being from 0.11 to 0.83.
    [3" id="c-fr-0003]
    3. Use according to claim 1 or 2, characterized in that the elongation at break of said composition is increased up to 30% compared to the same composition comprising flat section glass fibers instead of glass fibers with circular section.
    [4" id="c-fr-0004]
    4. Use according to one of claims 1 to 3, characterized in that said composition comprises:
    - from 5 to 30% by weight, in particular from 5 to 20% by weight of MXDZ,
    from 20 to 60% by weight, in particular from 25 to 50% by weight of said at least one polyamide A,
    - from 30 to 75% by weight, in particular from 40 to 65% by weight of glass fibers with circular section,
    - from 0 to 10% of at least one impact modifier,
    - from 0 to 2% of at least one additive, the sum of the proportions of each constituent of the composition being equal to 100%.
    [5" id="c-fr-0005]
    5. Use according to one of claims 1 to 4, characterized in that MXDZ corresponds to MXD10.
    [6" id="c-fr-0006]
    6. Use according to one of claims 1 to 5, characterized in that the aliphatic polyamide A is obtained from the polycondensation of a unit XY, and Y corresponds to sebacic acid.
    [7" id="c-fr-0007]
    7. Use according to one of claims 1 to 6, characterized in that the aliphatic polyamide A is obtained from the polycondensation of a unit XY, and X corresponds to a diamine in Ü6 to Cw.
    [8" id="c-fr-0008]
    8. Use according to one of claims 1 to 7, characterized in that the aliphatic polyamide A is obtained from the polycondensation of a unit XY, and X is chosen from hexamethylene diamine and decanediamine.
    [9" id="c-fr-0009]
    9. Use according to one of claims 1 to 8, characterized in that said at least one additive is chosen from fillers, dyes, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners , antioxidants, lubricants, flame retardants, natural waxes and their mixtures.
    had 01
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    同族专利:
    公开号 | 公开日
    US20190241739A1|2019-08-08|
    CA3040610A1|2018-04-26|
    JP2019533054A|2019-11-14|
    CN109844026A|2019-06-04|
    FR3057573A1|2018-04-20|
    WO2018073537A1|2018-04-26|
    EP3529313A1|2019-08-28|
    KR20190069498A|2019-06-19|
    FR3057575B1|2020-10-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4822846A|1986-12-01|1989-04-18|Mitsubishi Gas Chemical Company, Inc.|Molding polyamide resin composition|
    EP1972659A1|2006-01-13|2008-09-24|Mitsubishi Engineering-Plastics Corporation|Polyamide resin composition for portable electronic device and molded article for portable electronic device|
    US20110105655A1|2007-11-16|2011-05-05|Ems-Patent Ag|Filled polyamide molding materials|
    EP2792714A1|2011-12-16|2014-10-22|Mitsubishi Gas Chemical Company, Inc.|Molded article|
    US20160130439A1|2014-11-11|2016-05-12|Ems-Patent Ag|Polyamide moulding compound, moulded article produced herefrom and also purposes of use|WO2020258266A1|2019-06-28|2020-12-30|Arkema France|Use of a reinforced thermoplastic composition|JPS5523520B2|1975-02-12|1980-06-23|
    WO2010139369A1|2009-06-05|2010-12-09|Ems-Patent Ag|Flame-protected, partially aromatic polyamide molding compounds|
    WO2012093722A1|2011-01-07|2012-07-12|旭化成ケミカルズ株式会社|Copolymer polyamide|
    US9242892B2|2011-12-06|2016-01-26|Nitto Boseki Co., Ltd.|Glass fibers having non-circular cross sections, and fiber-reinforced resin compact using same|FR3094010B1|2019-03-21|2021-10-08|Arkema France|Copolyamide compositions comprising reinforcing fibers and exhibiting high modulus stability and their uses|
    FR3094011B1|2019-03-21|2021-10-01|Arkema France|COMPOSITIONS OF COPOLYAMIDES INCLUDING REINFORCING FIBERS OF HIGH MODULE STABILITY AND THEIR USES|
    FR3101080A1|2019-09-19|2021-03-26|Arkema France|Polyamide compositions comprising reinforcing fibers and exhibiting high modulus stability and uses thereof|
    WO2021053292A1|2019-09-19|2021-03-25|Arkema France|Polyamide compositions comprising reinforcing fibers and having high modulus stability, and uses thereof|
    法律状态:
    2017-09-18| PLFP| Fee payment|Year of fee payment: 2 |
    2018-04-20| PLSC| Publication of the preliminary search report|Effective date: 20180420 |
    2018-09-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-09-13| PLFP| Fee payment|Year of fee payment: 4 |
    2020-09-14| PLFP| Fee payment|Year of fee payment: 5 |
    2022-02-09| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1660126A|FR3057573A1|2016-10-19|2016-10-19|USE OF GLASS FIBERS WITH A CIRCULAR SECTION IN A MIXTURE COMPRISING A SEMI-AROMATIC POLYAMIDE AND AN ALIPHATIC POLYAMIDE FOR IMPROVING THE MECHANICAL PROPERTIES OF SAID MIXTURE|
    FR1660126|2016-10-19|KR1020197013967A| KR20190069498A|2016-10-19|2017-10-18|Use of glass fibers having a circular cross section in a mixture comprising a semi-aromatic polyamide and an aliphatic polyamide for improving the mechanical properties of the mixture|
    US16/342,368| US20190241739A1|2016-10-19|2017-10-18|--use of circular section glass fibers in a mixture comprising a semi-aromatic polyamide and an aliphatic polyamide to improve the mechanical properties of said mixture|
    PCT/FR2017/052867| WO2018073537A1|2016-10-19|2017-10-18|Use of glass fibres having a circular cross-section in a mixture comprising a semi-aromatic polyamide and an aliphatic polyamide for improving the mechanical properties of the mixture|
    JP2019520728A| JP2019533054A|2016-10-19|2017-10-18|Use of circular cross-section glass fibers to improve the mechanical properties of said mixtures in mixtures containing semi-aromatic polyamides and aliphatic polyamides|
    EP17797676.8A| EP3529313A1|2016-10-19|2017-10-18|Use of glass fibres having a circular cross-section in a mixture comprising a semi-aromatic polyamide and an aliphatic polyamide for improving the mechanical properties of the mixture|
    CN201780064424.6A| CN109844026A|2016-10-19|2017-10-18|The glass fibre of circular cross-section improves the purposes of the engineering properties of the mixture in the mixture comprising partially aromatic polyamide and aliphatic polyamide|
    CA3040610A| CA3040610A1|2016-10-19|2017-10-18|Use of glass fibres having a circular cross-section in a mixture comprising a semi-aromatic polyamide and an aliphatic polyamide for improving the mechanical properties of the mixture|
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