• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to the use of at least one MXDZ polyamide, obtained from the polycondensation of meta-xylylenediamine (MXD), with a C6 to C18, in particular C6 to C12, aliphatic (Z) dicarboxylic acid. in a mixture comprising 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 - an XY unit obtained from the polycondensation of a C4 to C18 aliphatic (X), in particular C4 to C12 aliphatic diamine and a C6 to C18 aliphatic (Y) dicarboxylic acid, in particular C6 to C12, circular section glass fibers and optionally to at least one impact modifier and / or at least one additive, said at least one MXDZ polyamide and said mixture constituting a composition, and the weight ratio MXDZ / A being from 0.11 to 0.83, in particular from 0.11 to 0.83. at 0.66, to limit the warping of said composition when it is placed in n work, especially by injection or compression molding.
    公开号:FR3057574A1
    申请号:FR1752406
    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 number: 3,057,574 (to be used only for reproduction orders) (© National registration number: 17 52406 ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY
    COURBEVOIE © IntCI 8 : C 08 K 5/529 (2017.01), C 08 L 77/06, 77/02, C 08 J 5/06
    A1 PATENT APPLICATION
    ©) Date of filing: 23.03.17. (71) Applicant (s): ARKEMA FRANCE Public limited company © Priority: 19.10.16 FR 1660125. - FR. @ 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 Public limited company.
    FR 3 057 574 - A1 (o4) USE OF A SEMI-AROMATIC POLYAMIDE IN A MIXTURE OF ALIPHATIC POLYAMIDE COMPRISING GLASS FIBERS WITH A CIRCULAR SECTION TO LIMIT WETTING.
    The present invention relates to the use of at least one polyamide MXDZ, obtained from the polycondensation of meta-xylylene diamine (MXD), with a C 6 to C 18 aliphatic dicarboxylic acid (Z), in particular in C 6 to
    Cj 2 5 in a mixture comprising at least one aliphatic polyamide A obtained from the polycondensation of a unit chosen from:
    - a C 6 to C ^ 2 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 at least one MXDZ polyamide and said mixture constituting a composition, and the MXDZ / A weight ratio being included from 0.11 to 0.83, in particular from 0.11 to 0.66, in order to limit the warping of said composition during its use, in particular by injection or compression molding.
    Use of a semi-aromatic polyamide in a mixture of aliphatic polyamide comprising glass fibers of circular section to limit warping
    The present invention relates to the use of a semi-aromatic polyamide, in particular a MXDZ polyamide in a mixture of aliphatic polyamide, in particular semi-crystalline, comprising glass fibers of circular section, to limit the warping of the composition obtained. 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 parts brings other problems: ability to be injected, in particular materials sufficiently fluid to completely fill the mold and above all respect for the stability of the parts (absence of warping: major problem with these rigid materials obtained by adding glass fibers).
    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, and in particular to no longer have of warping fine injected parts.
    Thus, application EP2789591, in paragraph [0003], indicates that glass fibers with a 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. As regards the improvement in dimensional accuracy and warping, this is due, still according to application EP2789591, to the fact that glass fibers of non-circular section orient less in the direction of flow than the fibers of glass with circular section and therefore tend to be more oriented in two dimensions than the glass fibers of circular section in the injected part.
    Likewise, 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 ratio L / D from 2 to 8, and from 8 to 25% by weight of a flame-retardant agent (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 from 10 to 45% by weight of another polyamide which may be MXD6 relative to the total sum of the polyamides.
    Also, application US 2010/279111 describes compositions also having a low distortion during molding made up of 30 to 80% by weight of a polyamide and 20 to 70% of long glass fibers with flat section of L / D ratio from 2 to 8. The polyamide used is either a mixture of 55 to 85% by weight of an aliphatic polyamide and from 15 to 45% by weight of a polyamide which may be MXD6 relative to the total sum of the polyamides, or a mixture of 55 to 85% by weight of an aliphatic polyamide and 15 to 45% by weight of a copolyamide comprising one or more polyamides, for example MXDI or MXD6 and at least one other polyamide chosen from PA 66, 610, 6 and 12, relative to the total sum of the polyamides.
    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, 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 while limiting the drawback of these, namely in particular warping during the use of the compositions.
    These various problems have been solved by a specific alloy of MXDZ with a mixture of aliphatic polyamide and glass fibers of circular section.
    The term "alloy" here means a mixture.
    The inventors have in fact unexpectedly found that the addition of a polyamide MXDZ in a mixture of aliphatic polyamide, in particular semi-crystalline comprising glass fibers of circular section makes it possible to limit the warping of the composition during the setting. used in particular by injection or compression molding of the composition, warping which occurs when the mixture and the glass fiber are used without the polyamide MXDZ.
    Another advantage of the compositions of MXDZ in a mixture of aliphatic polyamide and glass fibers with circular section is to have mechanical properties, in particular of elongation at break greater, in particular by 30%, compared to a composition with flat section glass fibers.
    The present invention therefore relates to the use of at least one polyamide MXDZ, obtained from the polycondensation of meta-xylylene diamine (MXD), with an aliphatic dicarboxylic acid (Z) at Ü6 to Cw, in particular at Ü6 to C12, in a mixture comprising 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 cross section and optionally at least one impact modifier and / or at least one additive, said at least one polyamide MXDZ and said mixture constituting a composition, and the weight ratio MXDZ / A being from 0.11 to 0.83, in particular from 0.11 to 0.66, to limit the warping of said composition during its implementation, in particular by injection or compression molding.
    The expression "limit warping" means that warping is less than
    2mm, in particular less than 1 mm as determined on plates of 100 * 100 * 1 mm 3 .
    Warping can be completely eliminated but as a rule it is less than 2mm, in particular less than 1mm.
    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 in all the description, the MXD must be in 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 aliphatic dicarboxylic acid (Z) at Οβ to C12 can be chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.
    The term "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, caprylolactam, 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, 1,5pentamethyldiamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine la
    1.7- heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8octane-diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4trimethylhexamethylenediamine, 1,10- decanediamine, 1,11-undecanediamine, 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 in Ü6 to C10, 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 (also called polyamide XY), the aliphatic dicarboxylic acid (Y) at C6 to Cw, in particular at C6 to C12, used 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 μm 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 SP01, a Lotader®, in particular Lotader® 5500 or Lotader® 7500, Exxelor VA1803®, or a mixture of those here, 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 in 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 at least one MXDZ in the mixture comprising an aliphatic polyamide and glass fibers 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 MXDZ in a mixture of aliphatic polyamide A and glass fibers are the conventional additives used in polyamides and well known to those skilled in the art.
    The weight ratio MXDZ / A in said composition is from 0.11 to 0.83, in particular from 0.11 to 0.66.
    Consequently, the semi-aromatic polyamide MXDZ is always in a lower proportion 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.
    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 proportion of said at least one MXDZ polyamide used with said blend is from 5 to 30% by weight, in particular from 5 to 20% relative to the sum of the constituents of said composition.
    Advantageously, said composition constituted by the use of said at least one MXDZ polyamide with said mixture comprises:
    - from 5 to 30% by weight, in particular from 5 to 20, of MXDZ
    from 20 to 60% by weight, in particular from 25 to 50% of said at least one aliphatic 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% by weight of at least one impact modifier,
    - from 0 to 2% by weight 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 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 compositions 1 to 8 above can further comprise an 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 with said mixture defined above to constitute 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 with said mixture defined above to constitute one of the compositions defined above consists of MXD10 and MXD6. Advantageously, the MXDZ used with said mixture defined above to constitute 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 a unit XY whose diamine (X) is in Ü6 to
    Cw3057574
    Aliphatic polyamide A is therefore a mixture of at least two polyamides XY whose diamine (X) is C6 to Cio, the diamines being different from one another, in particular.
    Advantageously, said aliphatic polyamide A obtained from the polycondensation of an XY unit whose diamine (X) is C6 to Cio 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 unit consists of a polyamide XY whose diamine (X) is C6 to Cio.
    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 11-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 at least one MXDZ polyamide with said mixture is chosen from fillers, dyes, stabilizers, plasticizers, surfactants, agents nucleating agents, pigments, brighteners, antioxidants, lubricants, flame retardants, natural waxes and their mixtures.
    In an advantageous embodiment, said at least one additive of said composition constituted by the use of said at least one MXDZ polyamide with said mixture is chosen from fillers, dyes, stabilizers, plasticizers, surfactants, agents nucleating agents, pigments, brighteners, antioxidants, lubricants, natural waxes and their mixtures.
    In an advantageous embodiment, said composition constituted by the use of said at least one MXDZ polyamide 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% by weight of at least one additive.
    In an advantageous embodiment, said composition constituted by the use of said at least one MXDZ polyamide 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 metaxylylene 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% by weight of at least one additive.
    Advantageously, the MXDZ of compositions 1 to 8 above defined is MXD10 and the aliphatic polyamide A is PA1010.
    Advantageously, the MXDZ of compositions 1 to 8 defined above is MXD10 and the aliphatic polyamide A 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 defined above 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.
    According to another aspect, the present invention relates to a composition for processing, in particular by injection or compression molding, comprising:
    - from 5 to 30% by weight, in particular from 5 to 20% by weight, of at least one polyamide MXDZ, obtained from the polycondensation of meta-xylylene diamine (MXD) or a mixture of meta-xylylene diamine and para-xylylene diamine, with a diacid (Z) at Ü6 to Cw, in particular at C6 to C12,
    - from 20 to 60% by weight, in particular from 25 to 50% by weight of at least one aliphatic polyamide A obtained from the polycondensation of a unit chosen from a C6 to C12 lactam, a C6 to amino acid C12 and a unit XY 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 C6 to Cw, in particular at C6 to C12,
    - 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% by weight of at least one additive.
    The sum of the proportions of each constituent of the composition being equal to 100%.
    All the technical characteristics and embodiment detailed above for the use of at least one MXDZ in a mixture comprising at least one aliphatic polyamide A to constitute a composition are valid for the composition as such.
    Advantageously, said at least one MXDZ polyamide of said composition defined above comprises MXD10.
    Advantageously, said polyamide MXDZ of said composition defined above consists of MXD10.
    Advantageously, said dicarboxylic acid (Y) of said aliphatic polyamide A obtained from the polycondensation of an XY unit corresponds to sebacic acid. Advantageously, said diamine (X) of said aliphatic polyamide A obtained from the polycondensation of an XY motif corresponds to a C6 to C10 diamine, in particular (X) is chosen from hexamethylene diamine and decanediamine.
    Advantageously, said aliphatic polyamide A obtained from the polycondensation of a unit chosen from a C6 to C12 lactam is lauryllactam.
    Advantageously, said aliphatic polyamide A obtained from the polycondensation of a unit chosen from a C6 to C12 amino acid is aminoaminecanoic acid. Advantageously, said additive of said composition defined above is chosen from fillers, dyes, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, lubricants, flame retardants, natural waxes and their mixtures.
    Advantageously, said additive of said composition defined above is chosen from fillers, dyes, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, lubricants, natural waxes and their mixtures.
    According to another aspect, the present invention relates to the use of a composition defined above to constitute a monolayer structure or at least one layer of a multilayer structure.
    Advantageously, said structure is in the form of an injected part. According to another aspect, the present invention relates to an object obtained from a composition defined above.
    According to another aspect, the present invention relates to a method for shaping an object as defined above, characterized in that it comprises a compression molding step.
    According to another aspect, the present invention relates to the use of an object, as defined above, in the electrical and / or electronic field.
    DESCRIPTION OF THE FIGURES
    Figure 1 (A and B) shows the warping obtained with 2 injected plates (100 x 100 x 1mm 3 ) by:
    A composition 11 or I2 of the invention,
    B composition C1 or C4, and measured as described in Example 1.
    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: Evaluation of the warping of polyamide compositions based on PA610 or PA1010, MXD10 and glass fibers with circular section or with flat section.
    Synthesis
    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 the well known techniques of l skilled in the art.
    Compounding
    The compositions were prepared by melting 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 with 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 and the warpage was evaluated according to 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 1:
    Composition MXDZ(% inweight) PAXY(% inweight) Glass fibersectioncircular (%in weight)NittoboCSX3J451S0 Glass fiberflat section(% in weight)NittoboCSG3PA820S Warping C1 - PA61050% 50% - Very important> 5mm * C2 - PA61050% - 50% <1mm 11 MXD10(15%) PA61035% 50% - <1mm C4 - PA101045% 55% - Very important> 5mm * C5 - PA101045% - 55% <1mm I2 MXD1015% PA101030% 55% - <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 1
    Table 1 shows that the introduction of glass fibers of circular cross section into an aliphatic polyamide XY induces a significant warping which is practically eliminated by the introduction of MXDZ, even for a proportion as large as 50% or 55% by weight of fibers. glass with circular section.
    The same performances are therefore achieved in terms of warping with the compositions of the invention compared to compositions with flat fibers.
    Example 2: Mechanical properties
    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 were pre-conditioned for 2 weeks at 23 ° C, 50% RH. The deformation is measured by a contact extensometer.
    Composition C3 corresponds to PA610 (35% by weight), flat section glass fibers (Nittobo CSG3PA820S, 50% by weight) and MXD10 (15% by weight).
    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.
    权利要求:
    Claims (23)
    [1" id="c-fr-0001]
    Claims
    1. Use of at least one MXDZ polyamide, obtained from the polycondensation of meta-xylylene diamine (MXD), with an aliphatic dicarboxylic acid (Z) at C6 to Cw, in particular at C6 to C12, in a mixture comprising at least one aliphatic polyamide A obtained from the polycondensation of a unit chosen from:
    - a lactam in C6 to C12,
    a C6 to C12 amino acid, 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 C6 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 at least one MXDZ polyamide and said mixture constituting a composition, and the MXDZ / A weight ratio being from 0.11 to 0 , 83, in particular from 0.11 to 0.66, to limit the warping of said composition during its use, in particular by injection or compression molding.
    [2" id="c-fr-0002]
    2. Use according to claim 1, characterized in that the proportion of said at least one MXDZ polyamide is from 5 to 30% by weight, in particular from 5 to 20% relative to the sum of the constituents of said composition.
    [3" id="c-fr-0003]
    3. Use according to claim 1 or 2, characterized in that said composition comprises:
    - from 5 to 30% by weight, in particular from 5 to 20% by weight, of said at least one
    MXDZ,
    from 20 to 60% by weight, in particular from 25 to 50% of said at least one aliphatic 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% by weight of at least one impact modifier,
    - from 0 to 2% by weight of at least one additive.
    The sum of the proportions of each constituent of the composition being equal to
    100%.
    [4" id="c-fr-0004]
    4. Use according to one of claims 1 to 3, characterized in that said at least one MXDZ comprises MXD10.
    [5" id="c-fr-0005]
    5. Use according to one of claims 1 to 4, characterized in that said MXDZ consists of 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 5, characterized in that the aliphatic polyamide A is obtained from the polycondensation of a lactam or an amino acid, in particular lauryllactam or aminoundecanoic acid.
    [10" id="c-fr-0010]
    10. Use according to one of claims 1 to 9, 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.
    [11" id="c-fr-0011]
    11. Composition for use, in particular by injection or compression molding, comprising:
    - from 5 to 30% by weight, in particular from 5 to 20% by weight, of at least one MXDZ polyamide, obtained from the polycondensation of meta-xylylene diamine (MXD) with a C6 diacid (Z) in Cw, in particular in C6 to C12,
    - from 20 to 60% by weight, in particular from 25 to 50% by weight of at least one aliphatic polyamide A obtained from the polycondensation of a unit chosen from a lactam at Ü6 to C12, an amino acid at Ü6 to C12 and a unit XY 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 C6 to Cw, in particular at C6 to C12,
    - 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% by weight of at least one additive.
    The sum of the proportions of each constituent of the composition being equal to 100%.
    [12" id="c-fr-0012]
    12. Composition according to claim 11, characterized in that the at least one MXDZ polyamide comprises MXD10.
    [13" id="c-fr-0013]
    13. Composition according to claim 11 or 12, characterized in that the at least one MXDZ polyamide consists of MXD10.
    [14" id="c-fr-0014]
    14. Composition according to one of claims 11 to 13, characterized in that the aliphatic polyamide A is obtained from the polycondensation of a unit XY, and Y corresponds to sebacic acid.
    [15" id="c-fr-0015]
    15. Composition according to one of claims 11 to 14, characterized in that the aliphatic polyamide A is obtained from the polycondensation of a unit XY, and X corresponds to a diamine from C6 to Cw.
    [16" id="c-fr-0016]
    16. Composition according to one of claims 11 to 15, 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.
    [17" id="c-fr-0017]
    17. Composition according to one of claims 11 to 13, characterized in that the aliphatic polyamide A is obtained from the polycondensation of a lactam or an amino acid, in particular lauryllactam or aminoundecanoic acid.
    [18" id="c-fr-0018]
    18. Composition according to one of claims 11 to 17, 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.
    [19" id="c-fr-0019]
    19. Use of a composition according to one of claims 11 to 18 to constitute a monolayer structure or at least one layer of a multilayer structure.
    [20" id="c-fr-0020]
    20. Use according to claim 19, characterized in that the structure is in the form of an injected part.
    [21" id="c-fr-0021]
    21. Object obtained from a composition according to one of claims 11 to 18.
    [22" id="c-fr-0022]
    22. A method of shaping an object according to claim 21, characterized in that it comprises a compression molding step.
    [23" id="c-fr-0023]
    23. Use of an object according to claim 21, in the electrical and / or electronic field.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3057574A1|2018-04-20|USE OF A SEMI-AROMATIC POLYAMIDE IN AN ALIPHATIC POLYAMIDE MIXTURE COMPRISING CIRCULAR SECTION GLASS FIBERS FOR LIMITING WEIGHT
    FR3057575A1|2018-04-20|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
    EP2125953A1|2009-12-02|Composite material based on polyamide and on poly|, manufacturing process and use thereof
    EP2201067B1|2017-05-31|Thermoplastic polymer composition containing polyamide
    WO2019058077A1|2019-03-28|Use of a copolyamide composition as a matrix of filler material with glass fibres having a circular cross section for limiting warping
    EP2350194B1|2018-07-04|Thermoplastic polymer composition containing polyamide
    FR2921662A1|2009-04-03|POLYAMIDE OF HIGH FLUIDITY
    CN108603026B|2020-11-03|Polyamide resin composition
    CN111448257A|2020-07-24|Polyamide resin composition
    WO2020193482A1|2020-10-01|Use of copolyamides for manufacturing compositions that remain rigid under the effect of temperature
    EP0716126B1|2000-02-09|Translucent flexible polyamide composition and articles obtained therefrom
    EP3712197A1|2020-09-23|Use of copolyamides for manufacturing compositions with stable rigidity under the effect of humidity
    WO2020188204A1|2020-09-24|Copolyamide compositions comprising reinforcing fibers with high modulus stability and uses thereof
    EP3941968A1|2022-01-26|Copolyamide compositions comprising reinforcing fibers and having high modulus stability and uses thereof
    WO2020079371A1|2020-04-23|Transparent polymeric composition
    EP3390494A1|2018-10-24|Barrier structure made from mxdt/xt copolyamide with a high tg
    同族专利:
    公开号 | 公开日
    FR3057574B1|2020-08-28|
    US20190241738A1|2019-08-08|
    CA3040609A1|2018-04-26|
    EP3529312A1|2019-08-28|
    CN109844025A|2019-06-04|
    KR20190069497A|2019-06-19|
    FR3057572A1|2018-04-20|
    WO2018073536A1|2018-04-26|
    JP2019531394A|2019-10-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP2792714A1|2011-12-16|2014-10-22|Mitsubishi Gas Chemical Company, Inc.|Molded article|
    WO2014195226A1|2013-06-05|2014-12-11|Solvay Specialty Polymers Usa, Llc|Filled polymer compositions for mobile electronic devices|
    US20160278489A1|2013-10-02|2016-09-29|Ykk Corporation|Resin Slider for Slide Fasteners and Slide Fastener Provided Therewith|
    JPS5523520B2|1975-02-12|1980-06-23|
    WO2007138966A1|2006-05-25|2007-12-06|Mitsubishi Engineering-Plastics Corporation|Moldings of fiber-reinforced thermoplastic resin|
    EP2060596B1|2007-11-16|2012-06-13|Ems-Patent Ag|Filled polyamide moulding compositions|
    EP2060607B2|2007-11-16|2019-11-27|Ems-Patent Ag|Filled polyamide moulding materials|
    JP5526500B2|2008-07-04|2014-06-18|東洋紡株式会社|Fiber reinforced polyamide resin composition|
    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|
    WO2014050303A1|2012-09-25|2014-04-03|三菱瓦斯化学株式会社|Fiber-reinforced polyamide resin material|
    WO2014118275A1|2013-01-30|2014-08-07|Dsm Ip Assets B.V.|Pa-mxdt/zt copolymers|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|
    FR3097226B1|2019-06-11|2021-11-26|Arkema France|POLYAMIDE COMPOSITIONS WITH HIGH MODULE AND LOW DIELECTRIC CONSTANT AND THEIR USE|
    WO2020258266A1|2019-06-28|2020-12-30|Arkema France|Use of a reinforced thermoplastic composition|
    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|
    FR3111351A1|2020-06-10|2021-12-17|Arkema France|POLYAMIDE COMPOSITIONS WITH HIGH MODULE AND LOW DIELECTRIC CONSTANT AND THEIR USE|
    CN113583440B|2021-09-26|2022-01-04|江苏博云塑业股份有限公司|Nylon 66 material and preparation method 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
    FR1660125A|FR3057572A1|2016-10-19|2016-10-19|USE OF A SEMI-AROMATIC POLYAMIDE IN AN ALIPHATIC POLYAMIDE MIXTURE COMPRISING CIRCULAR SECTION GLASS FIBERS FOR LIMITING WEIGHT|
    FR1660125|2016-10-19|PCT/FR2017/052866| WO2018073536A1|2016-10-19|2017-10-18|Use of a semi-aromatic polyamide in an aliphatic polyamide mixture comprising glass fibres with a circular cross-section for limiting warping|
    EP17797675.0A| EP3529312A1|2016-10-19|2017-10-18|Use of a semi-aromatic polyamide in an aliphatic polyamide mixture comprising glass fibres with a circular cross-section for limiting warping|
    CA3040609A| CA3040609A1|2016-10-19|2017-10-18|Use of a semi-aromatic polyamide in an aliphatic polyamide mixture comprising glass fibres with a circular cross-section for limiting warping|
    KR1020197013966A| KR20190069497A|2016-10-19|2017-10-18|Use of a semi-aromatic polyamide in an aliphatic polyamide mixture comprising glass fibers having a circular cross section for limiting warping|
    US16/342,359| US20190241738A1|2016-10-19|2017-10-18|Use of a semi-aromatic polyamide in a mixture of aliphatic polyamide comprising circular-section glass fibres to limit warping|
    JP2019520729A| JP2019531394A|2016-10-19|2017-10-18|Use of semi-aromatic polyamides in mixtures of aliphatic polyamides containing circular cross-section glass fibers to limit warpage|
    CN201780064413.8A| CN109844025A|2016-10-19|2017-10-18|Partially aromatic polyamide limits the purposes of warpage in the mixture of the aliphatic polyamide of the glass fibre comprising circular cross section|
    [返回顶部]