Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/10—Transparent films; Clear coatings; Transparent materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to a transparent composition
• a transparent composition comprising a mixture of at least one (co)polyamide of formula PACMY/Z and at least one copolyamide of formula A/WS exhibiting good resistance to alcohol, in particular to ethanol or isopropanol, low haze and improved fatigue resistance.
• PA Transparent polyamides
• PCM bis(4-aminocyclohexyl)-methane
• MACM bis(4-amino-3-methylcyclohexyl)methane
• BMACM bis(4-amino-3-methylcyclohexyl)methane
• patent US5360891 describes compositions comprising PACM and an aliphatic dicarboxylic acid such as dodecanedioic acid to lead to a polyamide P12 which has good resistance to ethanol but has the disadvantage of having a processability and a resistance insufficient fatigue.
• the transparent polyamide based on MACM (B12) is known from EP0725101 but has less good resistance to ethanol than P12.
• compositions of the MACMX/10Y/L type in particular comprising B12/1012 improving the resistance to alcohol compared to B12 but having a resistance to ethanol lower than that of P12.
• the present invention therefore relates to a transparent molding composition, comprising by weight:
• P ACM represents bis(4-aminocyclohexyl)-methane consisting of at least 30% by moles of trans, trans-bis(4-aminocyclohexyl)-methane relative to the sum of all the isomers of PACM, preferably 35 to 60% by mole, in particular from 40 to 55% by mole, in particular from 45 to 50.5% by mole,
• Y represents at least one aliphatic dicarboxylic acid
• Z represents a repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or an XY1 unit obtained from the polycondensation of at least one aliphatic diamine X and at least one aliphatic dicarboxylic acid Y1,
• W being chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (MACM) and PACM as defined above, preferably W being 3,3'-dimethyl-4,4'- diamino- dicyclohexylmethane (MACM),
• S being an aromatic dicarboxylic acid
• said aromatic dicarboxylic acid being chosen in particular from isophthalic acid and terephthalic acid and mixtures thereof, in particular said aromatic dicarboxylic acid being isophthalic acid
• the resistance to alcohol is determined by optical observation (Transmittance and Haze) on plates injected into a mirror polished mold of 100 x 100 x 1 mm 3 after placing under stress (plate fixed on an elliptical mandrel imposing a deformation of up to 3%) in a given environment (ESC), i.e. in the present case placed in ethanol for 24 hours, according to ISO 22088: 2006.
• the measurement of the transmittance and the measurement of the Haze (haze) on the injected plates, in a mirror polished mold, 1 mm thick having a width and a length of 100 mm*100 mm are determined according to ASTM D 1003, before and after alcohol testing, from said composition of the invention.
• the resistance to ethanol is advantageously considered to be good when the transmittance determined according to ASTM D 1003, after testing with alcohol, is greater than or equal to 90%.
• the resistance to ethanol is considered to be good when the veil (Haze) determined according to ASTM D 1003, after alcohol test, is less than 5%.
• the resistance to ethanol is advantageously considered to be good when the transmittance determined according to ASTM D 1003, after alcohol test, is greater than or equal to 90% and the veil (Haze) determined according to ASTM D 1003, after alcohol test is less than 5%.
• a mixture of at least one (co)polyamide PACMY/Z with at least one particular semi-crystalline copolyamide makes it possible to obtain a composition having not only good resistance to ethanol, low haze, but also improved fatigue strength, processability and moldability, especially compared to P12.
• compositions of the invention are in particular improved compared to that of a composition of P12.
• P12 has the defect of crystallizing hot and the injection of the compositions of the invention can be carried out at a temperature lower than that of P12 and in particular in a wider injection temperature range.
• the injection rate and the injection speed of the compositions of the invention are higher than those of the injection of P12.
• the present invention leads to lower injection pressures than those used for PACMYs, in particular for P12.
• the overmolding of the compositions of said invention, in particular on polyamide, is also improved compared to the overmolding of P12 on the same polyamides.
• the composition is free of glass fibers.
• fiberglass is meant any fiberglass, in particular as described by Frederick T. Wallenberger, James C. Watson and Hong Li, PPG industries Inc. (ASM Handbook, Vol 21: composites (#06781 G), 2001 ASM International).
• PACMY/Z The nomenclature used to define polyamides is described in standard ISO 1874-1:2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation” and is well known to those skilled in the art.
• PACM (P) represents bis(4-aminocyclohexyl)-methane and consists of four isomers: a trans, trans isomer, a cis,cis isomer, a cis,trans isomer and a cis,trans isomer.
• the PACM entering into the constitution of the present composition therefore comprises at least 30% in moles of trans, trans-bis(4-aminocyclohexyl)-methane relative to the sum of all the isomers of the PACM, preferably from 35 to 60% in moles, in particular from 40 to 55% in moles, in particular from 45 to 50.5% in moles.
• Y is at least one aliphatic dicarboxylic acid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms.
• Y is at least one aliphatic dicarboxylic acid comprising from 8 to 18 carbon atoms, advantageously from 9 to 16 carbon atoms.
• Y is an aliphatic dicarboxylic acid in C10 or C12, in particular in C12.
• the dicarboxylic acid Y can be chosen from aliphatic, linear or branched, in particular linear, dicarboxylic acids.
• the dicarboxylic acid Y is aliphatic and linear, it can be chosen from succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (11), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid (14), hexadecanedioic acid (16), octadecanedioic acid (18), octadecanedioic acid (18), eicosanedioic acid (20), docosanedioic acid (22) and fatty acid dimers containing 36 carbons.
• succinic acid (4) pentanedioic acid (5), adipic acid (6), heptanedioic acid (7)
• Z represents a repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or an XY1 unit obtained from the polycondensation of at least one aliphatic diamine X and of at least one aliphatic dicarboxylic acid Y1.
• said amino acid comprises from 6 to 18 carbon atoms, preferentially from 8 to 12 carbon atoms, more preferentially from 10 to 12 carbon atoms. It can thus be chosen from 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, 13-aminotridecanoic acid, 14-aminotetradecanoic acid, 15-aminopentadecanoic acid, 16-aminohexadecanoic acid, 17-aminoheptadecanoic acid and 18-aminooctadecanoic acid.
• Z represents a repeating unit which is a single aminocarboxylic acid.
• said lactam comprises from 6 to 18 carbon atoms, preferentially from 8 to 12 carbon atoms, more preferentially from 10 to 12 carbon atoms.
• Z represents a repeating unit which is a single lactam.
• Z represents a repeating unit chosen from a unit obtained from a Cn amino acid or a unit obtained from a C12 lactam, preferably a unit obtained from a Cn amino acid.
• Z is an XY1 unit obtained from the polycondensation of at least one aliphatic diamine X and at least one aliphatic dicarboxylic acid Y1
• said at least one aliphatic diamine X comprises from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, advantageously from 6 to 12 carbon atoms, advantageously from 10 to 12 carbon atoms
• said at least one aliphatic dicarboxylic acid Y1 comprises from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, advantageously from 6 to 12 carbon atoms, advantageously from 8 to 12 carbon atoms.
• the aliphatic diamine used to obtain this repeating unit XY1 is an aliphatic diamine which has a linear main chain comprising at least 4 carbon atoms.
• This linear main chain may, where appropriate, comprise one or more methyl and/or ethyl substituents; in this last configuration, one speaks of "branched aliphatic diamine". In the case where the main chain contains no substituent, the aliphatic diamine is called “linear aliphatic diamine”.
• the aliphatic diamine used to obtain this repeating unit XY1 comprises from 4 to 36 carbon atoms, advantageously from 4 to 18 carbon atoms, advantageously from 6 to 18 carbon atoms, advantageously from 6 to 14 carbon atoms.
• this diamine is a linear aliphatic diamine, it then corresponds to the formula H2N- (CH2) x -NH2 and can be chosen for example from butanediamine (4), pentanediamine (5), hexanediamine (6), heptanediamine (7), octanediamine (8), nonanediamine (9), decanediamine (10), undecanediamine (11), dodecanediamine (12), tridecanediamine (13), tetradecanediamine (14) , hexadecanediamine (16), octadecanediamine (18) and octadecanediamine (18).
• linear aliphatic diamines which have just been cited can all be bioresourced within the meaning of standard ASTM D6866.
• this diamine is a branched aliphatic diamine, it may in particular be 2-methylpentanediamine, 2-methyl-1,8-octanediamine or trimethylene (2,2,4 or 2,4,4) hexanediamine.
• the dicarboxylic acid Y1 can be chosen from aliphatic, linear or branched dicarboxylic acids.
• the dicarboxylic acid Y1 is aliphatic and linear, it can be chosen from succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (11), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid (14), hexadecanedioic acid (16), octadecanedioic acid (18), octadecanedioic acid (18), eicosanedioic acid (20), docosanedioic acid (22) and fatty acid dimers containing 36 carbons.
• succinic acid (4) pentanedioic acid (5), adipic acid (6), heptanedioic acid
• the fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in the document EP 0 471 566.
• Z may or may not be present. If present, Z is present up to 15% by weight in the (co)polyamide relative to the sum of the constituents of the (co)polyamide.
• PACMY/Z is chosen from PACM10, PACM12, PACM13, PACM14, PACM10/11, PACM12/11, PACM13/11, PACM14/11, PACM10/12, PACM12/12, PACM13/12 and PACM14/12.
• PACMY is chosen from PACM10, PACM12, PACM13, PACM14.
• the average number of carbon atoms per nitrogen atom of Z is greater than or equal to 6, preferably greater than or equal to 8.
• a semi-crystalline copolyamide within the meaning of the invention, denotes a copolyamide which has a melting point (Tm) measured according to standard ISO 11357-3:2013 by DSC, and a crystallization enthalpy measured during the step of cooling at a rate of 20 K/min by DSC according to standard ISO 1 1357-3 of 2013 greater than 25 J/g, preferably greater than 40 J/g.
• Tm melting point measured according to standard ISO 11357-3:2013 by DSC
• crystallization enthalpy measured during the step of cooling at a rate of 20 K/min by DSC according to standard ISO 1 1357-3 of 2013 greater than 25 J/g, preferably greater than 40 J/g.
• the A unit in said copolyamide is as defined for Z above except that A is always present.
• the W unit is chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (MACM) and PACM as defined above, preferably W is 3,3'-dimethyl-4,4 '-diamino-dicyclohexylmethane (MACM).
• W is PACM
• the copolyamide A/WS is then different from PACMY/Z.
• S is an aromatic dicarboxylic acid.
• the aromatic dicarboxylic acid S can be chosen from terephthalic acid (denoted T), isophthalic acid (denoted I) and 2,6-naphthalene dicarboxylic acid (denoted N) or mixtures thereof.
• S is an aromatic dicarboxylic acid is chosen from terephthalic acid (denoted T), isophthalic acid (denoted I) or mixtures thereof, in particular said aromatic dicarboxylic acid is isophthalic acid.
• the content by weight of A in the copolyamide A/WS is greater than or equal to 70% relative to the sum of the constituents of the copolyamide.
• the content by weight of A is from 70 to 95%, more particularly from 70 to 90%
• A/WS is chosen from 11/BI, 12/BI, 11/BT, 12/BT, 11/BI/BT and 12/BI/BT, in particular 11/BI, 12/BI, 11 /BI/BT and 12/BI/BT, in particular 11/BI and 12/BI.
• the impact modifier may or may not be present and when present its proportion is up to 10% by weight.
• the impact modifier is chosen from poly ether block amides (PEBA) and core-shell polymers.
• polyolefins and SEBS are excluded from the compositions of the invention.
• Poly ether block amides are copolymers with amide units (Ba1) and polyether units (Ba2), said amide unit (Ba1) corresponding to an aliphatic repeating unit chosen from a unit obtained from at least one amino acid or a pattern obtained from at least one lactam, or a pattern obtained from polycondensation:
• diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture thereof, and
• said diacid being preferably chosen from: a linear or branched aliphatic diacid, or a mixture thereof, said diamine and said diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms; said polyether units (Ba2) being in particular derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol,
• PEBAs result in particular from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as, among others: 1) Polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends.
• Polyamide sequences with dicarboxylic chain ends with polyoxyalkylene sequences with diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxylated alpha-omega polyoxyalkylene sequences called polyalkylene ether diols (polyether diols).
• polyamide sequences with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.
• the polyamide sequences with diamine chain ends come, for example, from the condensation of polyamide precursors in the presence of a diamine chain limiter.
• the polymers containing polyamide blocks and polyether blocks can also comprise randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
• polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted.
• a polymer is obtained having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents having reacted randomly which are distributed randomly (statistically) along the polymer chain.
• polyetherdiamine polyamide precursors and a chain-limiting diacid.
• a polymer is obtained having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents having reacted randomly which are distributed randomly (statistically) along the polymer chain.
• the amide unit (Ba1) corresponds to an aliphatic repeating unit as defined above.
• the amide unit (Ba1) is chosen from polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, in particular polyamide 11.
• the amide unit (Ba1) is chosen from polyamide 11 and polyamide 12.
• Polyether unit (Ba2) The polyether units are in particular derived from at least one polyalkylene ether polyol, in particular they are derived from at least one polyalkylene ether polyol, in other words, the polyether units consist of at least one polyalkylene ether polyol.
• the expression “of at least one polyalkylene ether polyol” means that the polyether units consist exclusively of alcohol chain ends and therefore cannot be a compound of the triblock polyetherdiamine type.
• composition of the invention is therefore devoid of triblock polyetherdiamine.
• the polyether units (Ba2) are chosen from polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG) and their mixtures or their copolymers, in particular PTMG.
• PEG polyethylene glycol
• PPG polypropylene glycol
• PO3G polytrimethylene glycol
• PTMG polytetramethylene glycol
• the number-average molecular mass (Mn) of the polyether blocks is advantageously from 200 to 4000 g/mole, preferably from 250 to 2500 g/mole, in particular from 300 and 1100 g/mole.
• PEBA can be prepared by the following process:
• the polyamide blocks (Ba1) are prepared by polycondensation of the lactam(s), or of the amino acid(s), or of the diamine(s) and of the diacid(s) carboxylic(s); and, where appropriate, comonomer(s) chosen from lactams and alpha-omega aminocarboxylic acids; in the presence of a chain limiter chosen from dicarboxylic acids; then
• polyamide blocks (Ba1) obtained are reacted with polyether blocks (Ba2), in the presence of a catalyst.
• the block formation reaction (Ba1) usually takes place between 180 and 300°C, preferably between 200 and 290°C, the pressure in the reador is established between 5 and 30 bars, and it is maintained for around 2 to 3 time. The pressure is slowly reduced by bringing the reactor to atmospheric pressure, then the excess water is distilled, for example, for an hour or two.
• the polyamide with carboxylic acid ends having been prepared, the polyether and a catalyst are then added.
• the polyether can be added in one or more stages, likewise for the catalyst.
• the polyether is first added, the reaction of the OH ends of the polyether and the COOH ends of the polyamide begins with formation of ester bonds and elimination of water. As much water as possible is removed from the reaction medium by distillation, then the catalyst is introduced to complete the bonding of the polyamide blocks and the polyether blocks.
• This second stage is carried out with stirring, preferably under a vacuum of at least 15 mm Hg (2000 Pa) at a temperature such that the reactants and the copolymers obtained are in the molten state.
• this temperature may be between 100 and 400°C and most often 200 and 300°C.
• the reaction is monitored by measuring the torque exerted by the molten polymer on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the target torque or power.
• said dicarboxylic acid is used as a chain limiter, which is introduced in excess relative to the stoichiometry of the diamine(s).
• the catalyst used is a derivative of a metal chosen from the group formed by titanium, zirconium and hafnium or a strong acid such as phosphoric acid, hypophosphorous acid or boric acid.
• the polycondensation can be carried out at a temperature of 240 to 280°C.
• known copolymers with ether and amide units consist of linear and semi-crystalline aliphatic polyamide sequences (for example “Pebax®” from Arkema).
• the poly ether block amide (PEBA) has a flexural modulus of less than 200 MPa, in particular less than 100 MPa, as measured according to standard ISO 178:2010 at 23°C.
• the PEBA has a density greater than or equal to 1, as determined according to ISO 1183-3: 1999.
• the core-shell has a density greater than or equal to 1, as determined according to ISO 1183-3: 1999.
• the impact modifier can also be a modifier of the “core-shell” type, also referred to as “copolymer of the core-shell type” or polymeric particle.
• the weight average particle size of the polymer is between 20 nm and 400 nm, more preferably between 20 nm and 350 nm and advantageously between 20 nm and 300 nm.
• the polymeric particle has a multilayer structure comprising at least one layer (A) comprising a polymer (A1) having a glass transition temperature below 0°C and another layer (B) comprising a polymer (B1) having a transition temperature vitreous above 60°C.
• the polymer (B1) having a glass transition temperature greater than 60° C. is the outer layer of the polymer particle with a multilayer structure.
• the polymeric particle according to the invention is obtained by a multi-step process, such as two or three or more steps.
• the polymer (A1) having a glass transition temperature below 0° C. in the layer (A) is manufactured during the first stage of the multi-stage process forming the core of the polymer particle with a multilayer structure.
• the polymer (A1) has a glass transition temperature below -5°C, more preferably below -15°C, advantageously below -25°C.
• the polymer (B1) having a glass transition temperature above 60° C. is manufactured during the last stage of the multi-stage process forming the outer layer of the polymer particle with a multilayer structure.
• One or more additional intermediate layers obtained by one or more intermediate steps may be present.
• the glass transition temperature Tg of the multilayer polymer can be estimated for example by dynamic methods such as thermomechanical analysis.
• the polymer (A1) and the layer (A) comprise from 0% by weight to less than 50% by weight of monomers containing aromatic groups.
• the polymer (B1) and the layer (B) comprise from 0% by weight to less than 50% by weight of monomers containing aromatic groups.
• the polymer (B1) and the layer (B) do not include monomers containing aromatic groups.
• the polymer (A1) having a glass transition temperature below 0°C it comprises at least 50% by weight of polymer units derived from isoprene or butadiene and the layer (A) is the innermost layer of the polymer particle with a multilayer structure.
• the layer (A) comprising the polymer (A1) is the core of the polymeric particle.
• the polymer (A1) of the core can consist of isoprene homopolymers or of butadiene homopolymers, of isoprene-butadiene copolymers, of isoprene copolymers with at most 98% by weight of a vinyl monomer and copolymers of butadiene with at most 98% by weight of a vinyl monomer.
• the vinyl monomer can be styrene, an alkylstyrene, acrylonitrile, an alkyl (meth)acrylate or butadiene or isoprene or mixtures thereof, insofar as the polymer (A1) comprises less than 50% by weight monomers containing aromatic groups.
• the polymer (A1) can be crosslinked.
• Cross-linking monomers useful in the present invention include, but are not limited to, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, trimethacrylates, triacrylates, allyl carboxylates such as allyl acrylate and allyl methacrylate, and di- and tri-allylic compounds such as diallyl phthalate, diallyl sebacate and triallyltriazine.
• aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene
• polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate
• trimethacrylates trimethacrylates
• triacrylates allyl carboxylates
• allyl acrylate and allyl methacrylate and di- and tri-allylic compounds
• the impact modifiers of the core-shell type can be functionalized or non-functionalized. In the case where the core-shell is functionalized, this allows better compatibility with the polyamide matrix of said invention.
• a functionalization of the maleic anhydride type is preferred.
• the additive is optional and comprised from 0 to 2%, in particular from 0.1 to 1% by weight.
• the additive does not disturb the transparency of said composition.
• the additive is selected from colorants, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, lubricants, flame retardants, natural waxes, additives for laser marking, and their mixtures.
• the stabilizer can be a UV stabilizer, an organic stabilizer or more generally a combination of organic stabilizers, such as a phenol-type antioxidant (for example of the type of that of irganox 245 or 1098 or 1010 of the company Ciba-BASF), a phosphite-type antioxidant (for example irgafos® 126 or Irgafos® 168 from Ciba-BASF) and even possibly other stabilizers such as a HALS, which means Hindered Amine Light Stabilizer or stabilizer light of the hindered amine type (for example Tinuvin 770 from the company Ciba-BASF), an anti-UV (for example Tinuvin 312 from the company Ciba), a stabilizer based on phosphorus.
• a phenol-type antioxidant for example of the type of that of irganox 245 or 1098 or 1010 of the company Ciba-BASF
• a phosphite-type antioxidant for example
• This stabilizer can also be an inorganic stabilizer, such as a copper-based stabilizer.
• a copper-based stabilizer By way of example of such inorganic stabilizers, mention may be made of copper halides and acetates. Incidentally, one can possibly consider other metals such as silver, but these are known to be less effective. These copper-based compounds are typically associated with alkali metal halides, particularly potassium.
• the plasticizers are chosen from benzene sulfonamide derivatives, such as n-butyl benzene sulfonamide (BBSA); ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide; hydroxybenzoic acid esters, such as ethyl-2-hexyl parahydroxybenzoate and decyl-2-hexyl parahydroxybenzoate; tetrahydrofurfuryl alcohol esters or ethers, such as oligoethyleneoxytetrahydrofurfuryl alcohol; and esters of citric acid or hydroxy-malonic acid, such as oligoethyleneoxy malonate.
• BBSA n-butyl benzene sulfonamide
• ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide hydroxybenzoic acid esters, such
• the prepolymer can be present from 0 to 5% by weight in the composition.
• the prepolymer can be chosen from aliphatic, linear or branched, cycloaliphatic, semi-aromatic or even aromatic polyamide oligomers.
• the prepolymer can also be a copolyamide oligomer or a mixture of polyamide and copolyamide oligomers.
• the prepolymer has a number-average molar mass Mn ranging from 1000 to 10000 g/mole, in particular from 1000 to 5000 g/mole. It can in particular be monofunctional NH2 if the chain limiter used is a monoamine for example.
• the prepolymer is a linear aliphatic oligomer, in particular a mono NH2 aliphatic oligomer, in particular a PA11 mono NH2.
• the transparent molding composition comprises by weight:
• the composition comprises by weight:
• composition comprises by weight:
• the composition comprises by weight:
• composition comprises by weight:
• the composition comprises by weight:
• composition comprises by weight:
• the composition comprises by weight: (a) from 30 to 86.8%, in particular from 35 to 81.8%, in particular from 35 to 51.9% of at least one (co)polyamide of formula PACMY/Z,
• composition comprises by weight:
• said composition is devoid of glass fibers.
• the transparent molding composition consists by weight:
• A/WS is chosen from 11/BI, 12/BI, 11/PI, 12/PI, 11/BT, 12/BT, 11/BI/BT, 11/PI/BT, 11/BI/PT , 1 1/PI/PT, 12/BI/BT, 12/PI/BT, 12/BI/PT and 12/PI/PT in particular 1 1/BI, 12/BI, 1 1/PI, 12/PI, 11/BI/BT, 11/PI/BT, 11/BI/PT, 11 ZPI/PT, 12/BI/BT, 12/PI/BT, 12/BI/PT and 12/PI/PT.
• Z may or may not be present. If present, the content by weight of Z in PACMY/Z copolyamide is up to 15%.
• PACMY/Z is chosen from PACM10, PACM12, PACM13, PACM14, PACM10/11, PACM12/11, PACM13/11, PACM14/11, PACM10/12, PACM12/12, PACM13/12 and PACM14/12.
• PACMY/Z is chosen from PACM12, PACM13, PACM14, PACM10/11, PACM12/11, PACM13/11, PACM14/11, PACM10/12, PACM12/12, PACM13/12 and PACM14/12.
• PACMY is chosen from PACM10, PACM12, PACM13, PACM14.
• PACMY is chosen from PACM12, PACM13, PACM14.
• A/WS is chosen from 11/BI, 12/BI, 11/PI, 12/PI, 11/BT, 12/BT, 11/BI/BT, 11/PI/BT, 11/PI/PT, 11/PI/PT, 12/BI/BT, 12/PI/BT, 12/BI/PT and 12/PI/PT including 11/BI, 12/BI, 11/PI, 12/PI, 11/BI /BT, 11/PI/BT, 11/BI/PT, 11 ZPI/PT, 12/BI/BT, 12/PI/BT, 12/BI/PT and 12/PI/PT, and PACMY/Z is chosen from PACM10, PACM12, PACM13, PACM14, PACM10/11, PACM12/11, PACM13/11, PACM14/11, PACM10/12, PACM12/12, PACM13/12 and PACM14/12.
• A/WS is chosen from 11/BI, 12/BI, 11/PI, 12/PI, 11/BT, 12/BT, 11/BI/BT, 11/PI/BT, 11/BI /PT, 11/PI/PT, 12/BI/BT, 12/PI/BT, 12/BI/PT and 12/PI/PT in particular 1 1/BI, 12/BI, 1 1/PI, 12/PI , 11/BI/BT, 11/PI/BT, 11/BI/PT, 11/PI/PTJ 2/BI/BT, 12/PI/BT, 12/BI/PT and 12/PI/PT, and PACMY /Z is chosen from PACM12, PACM13, PACM14, PACM10/11, PACM12/11, PACM13/11, PACM14/11, PACM10/12, PACM12/12, PACM13/12 and PACM14/12.
• A/WS is chosen from 1 1/BI, 12/BI, 11/PI, 12/PI, 1 1 /BT, 12/BT, 11/BI/BT, 11/PI/BT, 11 /BI/PT, 11/PI/PT, 12/BI/BT, 12/PI/BT, 12/BI/PT and 12/PI/PT in particular 11/BI, 12/BI, 11/PI, 12/ PI, 11/BI/BT, 11/PI/BT, 11/BI/PT, 1 1/PI/PT 2/BI/BT, 12/PI/BT, 12/BI/PT and 12/PI/PT and PACMY is preferably chosen from PACM10, PACM12, PACM13 and PACM14.
• A/WS is chosen from 11/BI, 12/BI, 11/PI, 12/PI, 11/BT, 12/BT, 11/BI/BT, 11/PI/BT, 11/PI/PT, 11/PI/PT, 12/BI/BT, 12/PI/BT, 12/BI/PT and 12/PI/PT in particular 11/BI, 12/BI, 1 1/PI, 12/PI, 11/BI/BT, 11/PI/BT, 1 1/BI/PT, 11/PI/PTJ 2/BI/BT, 12/PI/BT, 12 /BI/PT and 12/PI/PT and PACMY is preferably chosen from PACM12, PACM13 and PACM14.
• said composition is devoid of impact modifier.
• said composition defined above in each of the embodiments and the associated variants has a transmittance at 560 nm on a plate 1 mm thick greater than 91% determined according to standard ISO 13468-2:2006 before said test resistance to ethanol.
• said composition defined above in each of the embodiments has a transmittance at 560 nm on a plate 1 mm thick greater than 90% determined according to standard ISO 13468-2:2006 after said resistance test to ethanol.
• said composition defined above in each of the embodiments and the associated variants has a transmittance at 560 nm on a plate 1 mm thick greater than 91% determined according to standard ISO 13468-2:2006 before said test of resistance to ethanol and a transmittance at 560 nm on a plate 1 mm thick greater than 90% determined according to standard ISO 13468-2:2006 after said test of resistance to ethanol.
• said composition defined above in each of the embodiments and the associated variants has a veil (Haze) determined according to ASTM D 1003, after alcohol test of less than 5%.
• said composition defined above in each of the embodiments and the associated variants has a transmittance at 560 nm on a plate 1 mm thick greater than 91% determined according to standard ISO 13468-2:2006 before said test of resistance to ethanol and a transmittance at 560 nm on a 1 mm thick plate greater than 90% determined according to standard ISO 13468-2:2006 after said test of resistance to ethanol and said composition also exhibits haze (Haze) determined according to ASTM D 1003, after alcohol test less than 5%.
• haze Haze
• Said composition defined above exhibits good resistance to fatigue as determined by a resistance test in which the number of minimum cycles at 18 MPa is 350,000 cycles.
• the resistance test is carried out on notched bars or notched dumbbells, in particular on notched dumbbells. It is carried out at room temperature at a frequency of 5 Hz and during voltage stress. The number of cycles is determined for a fixed stress, here 18 MPa, before the rupture of the sample.
• the composition defined above has a Tg greater than or equal to 90°C, as determined by dynamic mechanical analysis (DMA) according to ISO 6721-11:2019, in particular comprised from 100 to 140°C.
• the composition has an HDT (A) greater than or equal to 65°C, as determined according to ISO 75 f, in particular comprised from 70 to 110°C, in particular from 80 to 110°C.
• the HDT deflection temperature under load
• ISO 75 f bars laid flat method A (load 1.8 MPa)
• said composition has a good capacity for overmolding with a material such as polyamides and PEBAX®, in particular a rigid matrix, as determined according to a corner cleavage test.
• rigid matrix is meant a polyamide reinforced with or without fillers such as glass fibers, and more particularly a reinforced semi-crystalline aliphatic polyamide.
• the good ability to overmold is characterized by no delamination or little delamination after overmolding of a composition of the invention with a rigid matrix as determined by a wedge cleavage test which is carried out according to ISO 10354:1992 with: Dynamometer: MTS370 - Test speed: 5 mm/min Temperature: 23 Q C - Load cell: 100 KN Steel wedge thickness: 3 mm
• the adhesion will be rated OK if there is no delamination after the corner cleavage test. Adhesion will be rated NOK in the case of very poor adhesion leading to no force detected during the wedge cleavage test.
• the present invention relates to the use for the manufacture of an article, in particular for electronics, for sports, cosmetics, automobiles, household appliances, optics or industry.
• the article is manufactured by injection molding.
• the present invention relates to the article obtained by injection molding with a composition as defined above.
• compositions in Table 1 were prepared by mixing in the molten state the granules of the various constituents.
• PACM12 Produced by the applicant
• PACM10 Produced by the applicant
• PACM10/11 (97.5/2.5% by weight): Produced by applicant 11/BI (93/7% by weight): Produced by applicant 11/B10 (80/20% by weight): Produced by the applicant PA1 1: Rilsan® Arkema
• the resistance to alcohol is determined by optical observation (Transmittance and Haze) on plates injected into a mirror polished mold of 100 x 100 x 1 mm 3 after stressing (plate fixed on an elliptical mandrel imposing a deformation up to 3%) in a given environment (ESC), that is to say in the present case placed in ethanol for 24 hours, according to ISO 22088:2006.
• the measurement of the transmittance and the measurement of the Haze (haze) on the injected plates, in a mirror polished mold, 1 mm thick having a width and a length of 100 mm*100 mm are determined according to ASTM D 1003, before and after alcohol testing, from said composition of the invention.
• the resistance to ethanol is advantageously considered to be good when the transmittance determined according to ASTM D 1003, after testing with alcohol, is greater than or equal to 90%.
• the resistance to ethanol is advantageously considered to be good when the haze is less than 5%.
• the resistance to ethanol is advantageously considered to be good when the transmittance determined according to ASTM D 1003, after alcohol testing, is greater than or equal to 90% and when the haze is less than 5%.
• the wedge split test is performed according to ISO 10354:1992 with:
• NOK means: Bad adhesion. Unable to detect a force value. Peeling possible with the hands.
• compositions of the invention systematically present the four criteria: 1) Transmittance before ethanol test greater than 91%, and
• compositions of the invention have a resistance to ethanol (Table 1) superior to the comparative compositions (a PACMY mixture with an aliphatic polyamide, a PACMY mixture with 11/B10 or a PACMY alone).

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• 2020
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• 2021
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