[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2023111086A1 - Personal electronic devices comprising polyamide composition - Google Patents

Personal electronic devices comprising polyamide composition Download PDF

Info

Publication number
WO2023111086A1
WO2023111086A1 PCT/EP2022/085970 EP2022085970W WO2023111086A1 WO 2023111086 A1 WO2023111086 A1 WO 2023111086A1 EP 2022085970 W EP2022085970 W EP 2022085970W WO 2023111086 A1 WO2023111086 A1 WO 2023111086A1
Authority
WO
WIPO (PCT)
Prior art keywords
personal electronic
electronic device
mol
polyamide
polymer composition
Prior art date
Application number
PCT/EP2022/085970
Other languages
French (fr)
Inventor
Stéphane JEOL
Arthur René Henri BERTRAND
Véronique Bossennec
Lindsey ANDERSON
Xianhai FU
Xiaoling Xu
Original Assignee
Solvay Specialty Polymers Usa, Llc
Solvay Sa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay Specialty Polymers Usa, Llc, Solvay Sa filed Critical Solvay Specialty Polymers Usa, Llc
Publication of WO2023111086A1 publication Critical patent/WO2023111086A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005Stabilisers against oxidation, heat, light, ozone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/019Specific properties of additives the composition being defined by the absence of a certain additive
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/06Elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass

Definitions

  • PC polymer composition
  • PA polyamide
  • Personal electronic devices exposed to challenging environments e.g., those having high moisture (e.g., >50% humidity), high temperature (e.g., >35 °C), or comprising biological or environmental contaminants, must exhibit a diverse array of properties in order to garner commercial acceptance.
  • high moisture e.g., >50% humidity
  • high temperature e.g., >35 °C
  • biological or environmental contaminants must exhibit a diverse array of properties in order to garner commercial acceptance.
  • Moisture absorption can provide access for contaminants and cause surface irregularities that are visually unappealing, as well as a reduction in strength, rigidity and dimensional stability.
  • Portions of the devices in contact with heating elements or otherwise exposed to elevated temperatures are desirably heat resistant and/or flame retardant. Such devices must also be physically strong enough to tolerate routine handling, as well as accidentally applied forces, without breaking.
  • UV resistance of external surfaces of devices used outdoors or in areas with high UV exposure is also desirable, so that the devices retain their color and/or visual appeal for their useful life.
  • polysulfones Due to their inherent heat resistance, polysulfones have conventionally been used in the manufacture of personal electronic devices that incorporate heating elements. Polysulfones also typically have glass transition temperatures sufficiently high so that, even if some moisture absorption occurs, mechanical properties are not appreciably detrimentally impacted. However, many polysulfones may not naturally exhibit appreciable UV resistance. And so, while personal electronic devices comprising polysulfones enjoy commercial acceptance, some such devices may not possess the UV resistance needed to retain color integrity over their useful life. In these instances, additional ingredients, such as paints, stains or dyes, may be used in order to maintain visual appeal of the device for its lifetime. Though effective, this solution can add to the cost and complexity of the manufacturing process for the device.
  • Some semi-crystalline polyamides have also been used in the manufacture of personal electronic devices, and many perform very well in this capacity.
  • semi-crystalline polyamides have glass transition temperatures sufficient to provide devices comprising the polyamide with mechanical integrity at high temperatures.
  • some semi-crystalline polyamides may be prone to moisture absorption, which can lead not only to additive migration, but also, to a decrease in the glass transition temperature Tg.
  • Additive migration can provide the personal electronic device with a “mottled” or irregular surface appearance, which can result in a reduction in, or loss of, commercial acceptance.
  • a decrease in Tg can translate into changes in mechanical properties that may render the polyamides less suitable for certain applications.
  • the invention relates to a personal electronic device as defined in any one of claims 1-30.
  • the invention also relates to a flavor delivery system as defined in claim 31 .
  • the invention also relates to the use as defined in claim 30 or 31 . [0014] These subject-matters are defined more precisely below.
  • a personal electronic device comprises a polymer composition (PC).
  • the polymer composition (PC) comprises at least 30.0 wt.% of a polyamide (PA) comprising at least 70.0 mol% recurring units R(PAI) according to formula (VII): wherein R2 is a C4 to C30, Ce to C24, or Cs to C alkylene group, mol% is relative to the total moles of recurring units in the polyamide and wt.% is relative to the total weight of the polymer composition (PC).
  • PA polyamide
  • VII formula
  • the polymer composition (PC) optionally comprises at least one halogen free flame retardant, at least on reinforcing agent and at least one additive other than the halogen free flame retardant. More particularly, the polymer composition (PC) may comprise from 0 wt.% to 20 wt.% of the at least one halogen free flame retardant, from 0 wt.% to 50 wt.% of the at least one reinforcing agent, and from 0 wt.% to 30 wt.% of at least one additive other than the halogen free flame retardant.
  • Personal electronic devices that find particular benefit from this combination of properties include mobile phones, personal digital assistants, laptop or tablet computers, wearable computing devices, flavor delivery systems, cameras, portable audio players or radios, global position system receivers, medical devices/ medical equipment and portable game consoles.
  • the invention relates to a personal electronic device comprising a polymer composition (PC) comprising a polyamide (PA).
  • the polyamide (PA) is derived from the polycondensation of a diamine component (A) comprising 4,4- diaminodicyclohexylmethane (“PACM”) and a dicarboxylic acid component (B) comprising an aliphatic dicarboxylic acid (“X”).
  • the polyamide (PA) comprises at least 70.0 mol% of “PACMX” recurring units.
  • the diamine component (A) may optionally comprise an additional diamine and/or the dicarboxylic acid component (B) may comprise an additional dicarboxylic acid.
  • the polyamide thus comprises at least one other recurring unit comprising a diamine different from PACM and/or a dicarboxylic acid different from the aliphatic dicarboxylic acid.
  • the polymer composition (PC) comprising the polyamide (PA) exhibits a combination of properties such as impact, break and moisture resistance.
  • the polymer composition (PC) provides heat/flame resistance on par with that provided by the polysulfones conventionally used in applications where the same is desired.
  • the polymer composition (PC) also exhibits UV resistance better than that exhibited by polymer compositions not including polyamides comprising the PACMX recurring units. UV resistance can provide the polymer composition (PC) with color integrity (notably of the surface) that otherwise must be provided by paints, stains or dyes.
  • the personal electronic device comprising the polymer composition (PC)Zpolyamide (PA) also avoids the development of surface imperfections via the migration of additives upon exposure of the device to moisture. Such surface imperfections are significant factors leading to market rejection of personal electronic devices comprising polymer compositions/polyamides other than those provided here.
  • thermoplastic polymer The amount of energy in the form of heat required to bring about a change of state of a thermoplastic polymer from the solid to the liquid form is the heat of fusion (“AHf”) of the polymer, and the temperature at which this change of state occurs is called the melting temperature (“Tm”).
  • AHf heat of fusion
  • Tm melting temperature
  • Amorphous materials lack a measurable Tm and have a AHf less than 5.0 J/g.
  • halogen or “halo” include fluorine, chlorine, bromine and iodine.
  • aliphatic denotes an open chain chemical structure. Aliphatic compounds may be saturated or unsaturated, and linear or branched.
  • cycloaliphatic refers to an aliphatic compound that includes a nonaromatic ring structure.
  • alkyl as well as derivative terms such as “alkoxy”, “acyl” and “alkylthio”, include within their scope straight chain and branched chain. Examples of alkyl groups are methyl, ethyl, 1 -methylethyl, propyl and
  • aryl is inclusive of both mono- and polynuclear aryl groups.
  • aryl thus refers for instance to a phenyl, indanyl or naphthyl group.
  • the polyamide (PA) is formed and comprises recurring units formed from a reaction mixture (RM) comprising a diamine component (A) and a dicarboxylic acid component (B).
  • RM reaction mixture
  • A diamine component
  • B dicarboxylic acid component
  • the diamine component (A) contains each diamine in the reaction mixture and the dicarboxylic acid component (B) contains each dicarboxylic acid in the reaction mixture.
  • the diamine component (A) comprises 4,4-diaminodicyclohexylmethane (PACM) and optionally at least one diamine different from 4,4- diaminodicyclohexylmethane.
  • PAM 4,4-diaminodicyclohexylmethane
  • At least 30.0 mol%, at least 40.0 mol%, or at least 50.0 mol% of the 4,4-diaminodicyclohexylmethane are in the trans/trans configuration.
  • a trans/trans content of at least 30.0 mol% of the total isomer mol% of the 4,4-diaminodicyclohexylmethane i.e., trans- trans, cis-trans and cis-cis
  • a polyamide produced from a reaction mixture comprising the same is semi-crystalline.
  • the proportion of the 4,4-diaminodicyclohexylmethane in the diamine component (A) is at least 70.0 mol%, at least 75.0 mol%, at least 80.0 mol%, or at least 85.0 mol%.
  • the diamine component (A) consists essentially of 4,4-diaminodicyclohexylmethane.
  • the expression “consist essentially” means in the context of the invention in relation to the diamine component that the diamine component (A) comprises 4,4-diaminodicyclohexylmethane and may also comprise up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of at least another diamine, this proportion in mol% being based on the total amount of diamines in the diamine component (A).
  • the diamine component (A) consists of 4,4- diaminodicyclohexylmethane, i.e., the proportion of 4,4- diaminodicyclohexylmethane in the diamine component (A) is 100 mol%.
  • the proportion of 4,4-diaminodicyclohexylmethane in the diamine component is from 70.0 mol% to 100 mol%, from 75.0 mol% to 99.0 mol%, from 80.0 mol% to 98.0 mol%, or from 85.0 mol% to 97.0 mol%.
  • mol% of the referenced diamine is relative to the total number of moles of diamines in the diamine component.
  • the Dicarboxylic Acid Component (B) comprises an aliphatic dicarboxylic acid (“X”) of formula (III):
  • R2 is more particularly -(CH2)n- where n is an integer between 4 and 30 or between 6 and 24 or between 8 and 18.
  • n 12, 14, 15 or 16.
  • the dicarboxylic acid component (B) comprises at least one dicarboxylic acid(s), different from the aliphatic dicarboxylic acid of formula (III).
  • the dicarboxylic acid component (B) consists essentially of the aliphatic dicarboxylic acid (“X”) of formula (III).
  • the expression “consist essentially” means in the context of the invention in relation to the dicarboxylic acid component that the dicarboxylic acid component (B) comprises the aliphatic dicarboxylic acid (“X”) of formula (III) and may also comprise up to 2.0 mol%, preferably up to 1 .0 mol%, even more preferably up to 0.5 mol%, of at least another diacid, this proportion in mol% being based on the total amount of diacids in the dicarboxylic acid component (B).
  • the polyamide (PA) is formed by the polycondensation reaction of the components of the reaction mixture (RM), i.e., the diamine component (A), the dicarboxylic acid component (B). More specifically, the condensation leads to the formation of amide bonds.
  • the polyamide comprises recurring units R(PAI) represented by formula (VII): wherein R2 is as defined above.
  • RAI recurring units
  • the proportion of recurring units R( AI) according to formula (VII) in the polyamide (PA) is at least 70.0 mol%. This proportion may be at least 75.0 mol%, at least 80.0 mol% or at least 85.0 mol%.
  • the polyamide (PA) consists of the recurring units R(PAI) according to formula (VII), i.e. , the proportion of recurring units R( AI) in the polyamide (PA) is 100 mol%.
  • the proportion of recurring units R( AI) according to formula (VII) in the polyamide (PA) is no more than 99.0 mol%, no more than 98.0 mol%, or no more than 97.0 mol%. In some embodiments, the proportion of recurring units R( AI) according to formula (VII) in the polyamide (PA) is from 70.0 mol% to 100.0 mol%, from 75.0 mol% to 99.0 mol%, from 80.0 mol% to 98.0 mol%, or from 85.0 mol% to 97.0 mol%. [0055] As used herein, mol% in reference to a recurring unit of the polyamide (PA) is relative to the total moles of all recurring units in the polyamide.
  • the end-groups in the polyamide (PA) are selected in the group of -NH2, - COOH and amide end-groups. Indeed, the end-groups in the polyamide (PA) may be -NH2 or -COOH. Yet, when the polycondensation involves the addition of an end-capping agent, these end-groups may be converted, partially or totally, into amide end-groups.
  • R is more particularly a linear or branched C2-C18 alkyl group or a C5-C10 cycloalkyl group.
  • R' is more particularly a linear or branched C2-C18 alkyl group.
  • the monocarboxylic acid may advantageously be selected in the group consisting of benzoic acid; cyclohexanoic acid; R-COOH where R is a linear or branched C2-C18 alkyl group and combination of two or more of these acids.
  • R is the radical derived from the acid of formula R-COOH.
  • the monocarboxylic acid may more particularly be selected in the group consisting of acetic acid, propanoic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid and combination of two or more of these acids.
  • the monocarboxylic acid (end-capping agent) is more particularly of formula CH3-(CH2)n-COOH where n is an integer between 0 and 16.
  • the primary amine (end-capping agent) may advantageously be selected in the group consisting of the amines of formula R'-NH2 where R' is a linear or branched C2-C18 alkyl group. R' is the radical derived from the amine of formula R'-NH2.
  • the primary amine (end-capping agent) is more particularly of formula CH3- (CH2)n'-NH2 where n' is an integer between 2 and 18.
  • the primary amine may more particularly be selected in the group consisting of propyl amine, butylamine, pentylamine, hexylamine, 2- ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n- hexadecylamine, stearylamine, cyclohexylamine and combination of two or more of these amines.
  • the proportion of the end groups can be quantified by 1 H NMR or by potentiomtric techniques.
  • the polyamide (PA) generally has a glass transition temperature Tg of at least 90 °C.
  • the Tg may be at least 100 °C or at least 110 °C.
  • Tg is advantageously at least 120°C.
  • the Tg is generally no more than 200 °C.
  • the Tg may be no more than 190
  • the Tg may be from 90 °C to 200 °C, from 100 °C to 190 °C or from 110 °C to 180 °C.
  • the Tg may also be from 90 °C to 190 °C, from 90 °C to 180 °C, or from 90 °C to 170 °C.
  • Tg may more particularly be between 120°C and 140°C.
  • the polyamide (PA) has a Tm of at least 180 °C, at least 190 °C, or at least
  • Tm may also be at least 220°C.
  • the polyamide has a Tm of no more than 290 °C, no more than 285 °C, or no more than 280 °C. Tm may also be no more than 240°C.
  • Tm may be from 180 °C to 290 °C, from 190 °C to 285 °C or from 200 °C to 280 °C. Tm may also from 220°C to 240°C.
  • the polyamide (PA) is semi-crystalline or microcrystalline.
  • the polyamide has a AHf of at least 5.0 J/g, preferably at least 7.0 J/g, or at least 10.0 J/g. In some embodiments, the polyamide has a AHf of no more than 80.0 J/g, no more than 70.0 J/g or no more than 60.0 J/g. In some embodiments, the polyamide has a AHf of from 5.0 J/g to 80.0 J/g, from 7.0 J/g to 70.0 J/g, or from 10.0 J/g to 60.0 J/g. AHf may befrom 5.0 J/g to 50.0 J/g, from 5.0 J/g to 40.0 J/g, or from 5.0 J/g to 30.0 J/g.
  • Tg, Tm and AHf of the polyamide are measured according to ASTM D3418.
  • the polyamide (PA) has a number average molecular weight (“Mn”) from 1 ,000 g/mol to 40,000 g/mol.
  • Mn may be from 2,000 g/mol to 35,000 g/mol, from 4,000 to 30,000 g/mol, or from 5,000 g/mol to 20,000 g/mol.
  • Mn may also advantageously be between 10,000 and 20,000 g/mol.
  • the number average molecular weight Mn can be determined by gel permeation chromatography (GPC) using ASTM D5296.
  • the polyamide (PA) has preferably a water absorption, by immersion in water at 23°C of less than 8 wt.%, preferably less than 7.0 wt.%, preferably less than
  • the water absorption is most preferably lower than 3.0 wt%.
  • the water absorption at 23°C is determined by
  • Wbefore is the weight of the shaped specimen in its original dry state and Wafter is the weight of the shaped specimen after immersion for the specified time.
  • the polyamide (PA) described herein is prepared by polycondensation through reacting the components of the reaction mixture (RM).
  • the total number of moles of diamines in the reaction mixture is substantially equimolar to the total number of moles of dicarboxylic acids in the reaction mixture.
  • substantial equimolar denotes a value that is ⁇ 3.0% of the indicated number of moles.
  • total number of moles of diamines in the reaction mixture is ⁇ 3.0% of the total number of moles of dicarboxylic acids in the reaction mixture.
  • the polyamide (PA) is generally prepared by reacting the monomers (e.g. the diamines, dicarboxylic acids) of the reaction mixture (RM) in the presence of less than 40 wt.%, less than 30 wt.%, less than 20 wt.%, less than 10 wt.% or even with no added water.
  • the monomers e.g. the diamines, dicarboxylic acids
  • RM reaction mixture
  • Catalysts are usually added to the reaction mixture (RM).
  • catalysts are phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite such as sodium hypophosphite and phenylphosphinic acid. Phosphites are suitable stabilizers.
  • reaction mixture (RM) may also comprise at least one end capping agent as disclosed above.
  • the monomers may be caused to react by heating the reaction mixture (RM) to a temperature of at least Tm + 10°C, Tm being the melting temperature of the polyamide.
  • the temperature at which the reaction mixture is heated is generally at least 200°C or even at least 250°C.
  • the polyamide (PA) and/or the polymer composition (PC) of the invention exhibit(s) at least one, at least two, at least three, at least four, at least five, at least six or all of the following properties:
  • a glass transition temperature of greater than 90°C preferably greater than 100°C, preferably greater than 110°C, preferably greater than 120°C.
  • the polyamide (PA) and/or the polymer composition (PC) advantageously exhibit(s) a AE no more than 5.0, preferably no more than 4.0, preferably no more than 3.0, preferably no more than 2.0, after 240 hours as measured according to ISO4892-2:2013/AMD1 :2021.
  • Formula of AE is given in the experimental section.
  • the polyamide (PA) and/or the polymer composition (PC) advantageously exhibit(s) a break resistance, as evidenced by an IZOD impact strength of at least 50.0 KJ/m 2 , preferably at least 60.0 KJ/m 2 , preferably at least 70.0 KJ/m 2 , preferably at least 80.0 KJ/m 2 , as measured according to ISO180.
  • the polyamide (PA) and/or polymer composition (PC) advantageously exhibit(s) a flame resistance, as evidenced by a flammability rating of V1 or V2 measured according to the LIL94 standard.
  • UL 94 is the Standard for Safety of Flammability of Plastic Materials for Parts in Devices and Appliances testing, is a plastics flammability standard released by Underwriters Laboratories of the United States. The standard determines the material’s tendency to either extinguish or spread the flame once the specimen has been ignited.
  • the polyamide (PA) and/or polymer composition (PC) advantageously exhibit(s) an Elongation at Break of greater than 2.0%, or greater than 2.5%, or greater than 3.0%, as measured according to ISO527-2.
  • the polyamide (PA) and/or polymer composition (PC) advantageously exhibit(s) a strength at yield (Break) of greater than 45 MPa, preferably greater than 50 MPa, preferably greater than 55 MPa, as measured according to
  • the polymer composition (PC) consists of the polyamide (PA), i.e., the proportion of the polyamide (PA) in the polymer composition (PC) is 100 wt.%. As used herein and unless explicitly stated otherwise, the proportion of a component in the polymer composition (PC) is relative to the total weight of the polymer composition (PC).
  • the polymer composition (PC) may comprise the polyamide (PA) in a proportion of at least 30.0 wt.%, at least 35.0 wt.%, at least 40.0 wt.%, or at least 45.0 wt.%.
  • the proportion of polyamide (PA) in the polymer composition (PC) may be no more than 99.0 wt.%, no more than 95.0 wt.%, no more than 90.0 wt.%, or no more than 85.0 wt.%.
  • the proportion of the polyamide (PA) in the polymer composition (PC) is from 30.0 wt.% to 100.0 wt.%, from 35.0 wt.% to 99.0 wt.%, from 40.0 wt.% to 95.0 wt.%, or from 45.0 wt.% to 90.0 wt.%.
  • the polymer composition includes one or more polymeric materials in addition to the at least one polyamide described herein. Suitable additional polymeric material(s) include other polyamides, poly(arylene sulphides) poly(phenylene sulphides), poly(aryl ether sulfones), poly(biphenyl ether sulfones), polysulfones, poly(aryl ether ketones) and poly(ether ether ketones). [00101] In some embodiments, the polymer composition comprises a halogen free flame retardant, one or more reinforcing agents and/or one or more additives different from the halogen free flame retardant.
  • the polymer composition (PC) may optionally comprise at least one halogen free flame retardant.
  • halogen free flame retardants include, but are not limited to, metal dialkyl phosphinates (e.g. aluminum diethyl phosphinate), organophosphates (e.g. triphenylphosphates) and phosphonates (e.g. dimethyl methylphosphonates).
  • halogen free flame retardant may be selected in the group consisting of the compounds according to the formulae below:
  • R a and Rb are identical or different and are selected in the group consisting of linear or branched Ci-Cs-alkyl groups and aryl groups
  • R c is selected in the group consisting of linear or branched Ci-C -alkylene groups
  • M is a metal ion selected in the group of Al, Ca and
  • n is 1 or 3
  • x is 1 or 2.
  • the halogen free flame retardant may for instance be of formula [00106] If the polymer composition (PC) comprises at least one halogen free flame retardant, the total proportion of halogen free flame retardant(s) in the polymer composition (PC) is at least 1.0 wt.%, at least 2.0 wt.%, or at least 5.0 wt.%. The total proportion of halogen free flame retardant(s) may be no more than 20.0 wt. %, no more than 18.0 wt. %, nor more than 17.0 wt.%, or no more than 15.0 wt.
  • the total proportion of halogen free flame retardant(s) is from 0 wt.% to 20.0 wt.%, from 1.0 wt.% to 18.0 wt.%, from 2.0 wt.% to 17.0 wt. % or from 5.0 wt.% to 15.0 wt.%.
  • suitable reinforcing agents include, but are not limited to, mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, wollastonite and any combination of these.
  • mineral fillers such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate
  • Suitable reinforcing agents can be selected from fibrous and particulate reinforcing agents.
  • a fibrous reinforcing agent is considered herein to be a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness. Generally, such a material has an aspect ratio, defined as the average ratio between the length and the largest of the width and thickness of at least 5, at least 10, at least 20 or at least 50.
  • Suitable fibrous reinforcing agents e.g. glass fibers or carbon fibers
  • the fibers have an average length of from 3 mm to 10 mm, from 3 mm to 8 mm, from 3 mm to 6 mm, or from 3 mm to 5 mm. In other embodiments, the fibers have an average length of from 10 mm to 50 mm, from 10 mm to 45 mm, from 10 mm to 35 mm, from 10 mm to 30 mm, from 10 mm to 25 mm, or from 10 mm to 20 mm.
  • the average length of the fibers can be taken as the average length of the fibers prior to incorporation into the polymer composition or can be taken as the average length of the fibers within the polymer composition.
  • the reinforcing agent is desirably a fibrous filler and preferably a fibrous filler that is able to withstand the high temperature applications. Glass fibers are particularly preferred.
  • All glass fiber types such as A, C, D, E, M, S, R, T glass fibers (as described in chapter 5.2.3, pages 43-48 of Additives for Plastics Handbook, 2nd ed., John Murphy), or any mixtures thereof may be used. Additional descriptions of E, R, S and T glass fibers can be found in, e.g., Fiberglass and Glass Technology, Wallenberger, Frederick T.; Bingham, Paul A. (Eds.), 2010, XIV, chapter s, pages 197-225.
  • the glass fiber is a high modulus glass fiber.
  • High modulus glass fibers have an elastic modulus of at least 76, preferably at least 78, more preferably at least 80, and most preferably at least 82 GPa as measured according to ASTM D2343.
  • Examples of high modulus glass fibers include, but are not limited to, R, S and T glass fibers.
  • R, S and T glass fibers are composed essentially of oxides of silicon, aluminum and magnesium, and typically from 62-75 wt. % of SiO , from 16-28 wt. % of AI2O3 and from 5-14 wt. % of MgO.
  • R, S and T glass fibers comprise less than 10 wt. % of CaO.
  • High modulus glass fibers include S-1 and S-2 glass fibers, commercially available from Taishan and AGY, respectively.
  • the morphology of the glass fiber is not particularly limited and the glass fiber can be round, i.e. , have a circular cross-section, or flat, i.e. , have a non-circular (e.g., oval, elliptical or rectangular) cross-section.
  • the use of a reinforcing agent in the polymer composition is optional.
  • the total concentration of reinforcing agents in the polymer composition is at least 5 wt. %, at least 10 wt. %, or at least 15 wt. %.
  • the total concentration of reinforcing agents is no more than 50 wt. %, no more than 45 wt. %, or no more than 40 wt. %,
  • the total concentration of reinforcing agents is from 0 wt. % to 50 wt.%, from 5 wt.% to 50 wt.%, from 10 wt.% to 45 wt. % or from 15 wt.% to 40 wt.%, based upon the total weight of the polymer composition.
  • the polymer composition (PC) may optionally comprise one or more additives selected from the group consisting of tougheners, plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, nucleating agents, antioxidants and any combination thereof.
  • additives selected from the group consisting of tougheners, plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, nucleating agents, antioxidants and any combination thereof.
  • the polymer composition (PC) includes a toughener.
  • a toughener is generally a low Tg polymer, with a Tg for example below room temperature, below 0°C or even below -25°C. As a result of its low Tg, the toughener is typically elastomeric at room temperature. Tougheners can be functionalized polymers and are therefore typically reactive with other components of the polymer composition.
  • Suitable tougheners can be selected from polyethylenes and copolymers thereof, e.g. ethylene-butene; ethylene-octene; polypropylenes and copolymers thereof; polybutenes; polyisoprenes; ethylene-propylene-rubbers (EPR); ethylene-propylene-diene monomer rubbers (EPDM); ethyleneacrylate rubbers; butadiene-acrylonitrile rubbers, ethylene-acrylic acid (EAA), ethylene-vinylacetate (EVA); acrylonitrile-butadiene-styrene rubbers (ABS), block copolymers styrene ethylene butadiene styrene (SEBS); block copolymers styrene butadiene styrene (SBS); core-shell elastomers of methacrylate-butadiene-styrene (MBS) type, or mixture of one or more of the above.
  • EPR ethylene
  • a toughener can be functionalized by copolymerization of monomers containing reactive functionalities or from the grafting of reactive groups onto the toughener.
  • functionalized tougheners are notably terpolymers of ethylene, acrylic ester and glycidyl methacrylate, copolymers of ethylene and butyl ester acrylate; copolymers of ethylene, butyl ester acrylate and glycidyl methacrylate; ethylene-maleic anhydride copolymers; EPR grafted with maleic anhydride; styrene copolymers grafted with maleic anhydride; SEBS copolymers grafted with maleic anhydride; styreneacrylonitrile copolymers grafted with maleic anhydride; ABS copolymers grafted with maleic anhydride.
  • the total additive proportion in the polymer composition is at least 0.1 wt.%, at least 0.2 wt.%, at least 0.3 wt.%, at least 0.4 wt.%, or at least 0.5 wt.%.
  • the total additive concentration in the polymer composition is no more than 30 wt.%, no more than 25 wt.%., no more than 20 wt.%, no more than 15 wt.% or no more than 10 wt.%.
  • the total additive concentration in the polymer composition is from 0 wt.
  • % to 30 wt.% 0.1 wt.% to 30 wt.%, from 0.2 wt.% to 25 wt.%, from 0.3 wt.% to 20 wt.%, from 0.4 wt.% to 15 wt.% or from 0.5 wt.% to 10 wt.%.
  • the polymer composition (PC) can be prepared according to methods well known in the art.
  • the polymer composition (PC) can be made by melt-blending the polyamide (PA) and the other ingredients of the polymer composition (PC) (e.g. any desired halogen free flame retardants, reinforcing agents, and/or other additives).
  • Any melt-blending method may be used to combine the polyamide and any other desired components.
  • polymeric ingredients and non- polymeric ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer.
  • the ingredients may be fed all at once, via gradual addition, or in batches. If a reinforcing agent presents a long physical shape (for example, a long glass fiber), drawing extrusion molding may be used to prepare a reinforced composition.
  • the personal electronic device can be prepared in a two-step process wherein the polymer composition (PC) is formed into pellets, and then the pellets are injection molded to produce the personal electronic device.
  • the personal electronic device may be prepared directly from the polymer composition in an integrated, one-step process.
  • the personal electronic device can be made from the polymer composition (PC) by methods including, but not limited to, melt-mixing processes. Meltmixing processes are typically carried out by heating the polymer components above the highest melting temperature and glass transition temperature of the thermoplastic polymers thereby forming a melt of the thermoplastic polymers. In some embodiments, the processing temperature ranges from about 240- 400°C, preferably from about 250-380°C, from about 260-360°C.
  • the polymer composition (PC) is melt-mixed in an extruder, and the high temperature personal electronic device injection molded therefrom.
  • an extruder fitted with means for dosing all the desired components of the polymer composition to the extruder, whether to the extruder's throat or to the melt.
  • the components may be fed simultaneously as a powder or granule mixture, also known as dry-blend, or may be fed separately.
  • the order of combining the components during melt-mixing is not critical.
  • the components can be mixed in a single batch, such that the desired amounts of each component are added together and subsequently mixed. However, the total desired amount of each component does not have to be mixed as a single quantity.
  • a partial quantity of one or more components can be initially added and mixed and, subsequently, some or all of the remainder can be added and mixed.
  • the method may comprise if needed several successive steps of melt-mixing or extrusion under different conditions.
  • the method may also comprise one or more cooling steps.
  • Exemplary personal electronic devices that find particular benefit from the combination of properties exhibited by the present polyamide (PA) and polymer composition (PC) include personal electronic devices, and particularly those that incorporate a heating element or are exposed to high temperatures (e.g., greater than 40°C) during use.
  • Examples of such personal electronic devices include, but are not limited to, mobile phones, personal digital assistants, laptop or tablet computers, wearable computing devices (e.g., a smart watch, smart glasses and the like), flavor delivery systems, cameras, portable audio players or radios, global position system receivers, medical devices/medical equipment and portable game consoles.
  • the polymer composition (PC) can be used to form all, or a part of, any component of the personal electronic device. Significant benefit from the combination of properties provided by the polymer composition may be realized when the polymer composition (PC) is used in a component that is expected to be exposed to UV radiation, moisture, temperature and/or mechanical challenge in the course of its useful life. Housings or casings and parts thereof are but one example of a component wherein the advantages provided by the polymer composition (PC) may find particular applicability.
  • housing is meant to indicate any portion of a personal electronic device that provides cover and/or protection to the/other operative components of the device.
  • housings or parts thereof can function to protect internal and electronic components from impact or damage from environmental influences, such as moisture or UV radiation and can also function to give the personal electronic device strength.
  • Housings or housing parts include covers, cover plates, backbones (structural components to which other components attach), mouthpieces, hoods or lids, frames and parts or components that support these.
  • One example of a personal electronic device that finds particular advantage in the combination of properties provided by the present polyamide (PA) and polymer composition (PC) is a flavor delivery device. And so, in some embodiments, the personal electronic device is a flavor delivery device.
  • Flavor delivery devices can be used for delivery of an aerosol containing one or more active ingredients and/or flavors to the user of the flavor delivery system via inhalation.
  • Flavor delivery systems typically include a reservoir or compartment for holding a liquid, gel or solid flavor vehicle, a heating element operatively disposed relative to the reservoir or compartment, and a power source, among other components.
  • a plastic housing typically surrounds and supports the reservoir, heating element and power source.
  • An air inlet may be provided at an end of the plastic housing, with a mouthpiece provided at an opposing end.
  • the flavor delivery system may be activated by the press of a button, detection of an inhalation at the mouthpiece, or wireless communication with an external controller. Once activated, heat provided by the heating element releases the flavor from the flavor vehicle.
  • Flavor delivery devices are well known in the art and are described in, e.g., International Publication No. WO 2020/150400, US Publication No. 2015/025669 and US Publication No. 2018/0274110. The entire contents of each of these is hereby incorporated by reference herein, for any and all purposes.
  • the polymer composition (PC) or the polyamide (PA) can thus be used to form at least a portion of the housing of the flavor delivery device.
  • the polymer composition forms at least a portion of an exterior surface of the housing.
  • the housing of flavor delivery devices may be exposed to sweat, humidity, high temperature and/or UV exposure during use, the advantages of the polymer composition provided herein will be particularly appreciated by a user of such devices.
  • the polyamide composition (PC) is not used to form interior components.
  • the invention thus also relates to a flavor delivery system for delivery of an aerosol containing one or more active ingredients and/or flavors including a reservoir for holding the ingredient(s) and/or flavor(s), a heating element and a power source wherein the system also includes a housing made of or comprising the polymer composition (PC) of the invention.
  • PC polymer composition
  • PA10T (Vicnyl® 6100 Kingfa).
  • Test specimens according to Comparative Examples C1 and C2 and Inventive Example E1 were injection molded into standard dumbbell-shaped ISO type 1A tensile specimens on a Toshiba ISG 150 Injection Molder.
  • the test specimens has the following nominal dimensions: full length of 170 mm, gauge length of 75 mm, parallel section length of 80 mm, parallel section width of 10 mm, grip section width of 20 mm, and thickness of 4 mm.
  • IZOD impact strength of inventive and comparative unnotched samples was measured according to ISO180.
  • UV resistance was measured according to ISO4892-2:2013/AMD1 :2021 , Method B, cycle n.1 . Samples were visually inspected every 24 hours. Color parameters L*, a* and b* were measured after 96 hours, 168 hours, 216 hours and 240 hours. Delta E was calculated as follows:
  • the pH of the solution was adjusted to a value of 6.5 ⁇ 0.1 using ammonium hydroxide solution (1 % by weight).
  • a piece of cotton gauze was moistened with the sweat solution and placed over one end of the surface of the samples, covering no more than 20% of the length of the sample. The other end of each sample was placed into a bath of the solution. The samples and bath were placed into a sealed container and the sealed container placed into a temperature controlled chamber at 60C. After 48 hours, the samples were wiped dry with a clean cloth and allowed to cool to room temperature.
  • PC polymer compositions
  • the components were initially mixed in a plastic bucket and sealed.
  • the bucket was placed on a vibratory shaker for 2-3 minutes to assure homogeneity.
  • the so obtained mixture was then placed in a K-TronT-35 gravimetric feeder and fed into the Coperion ZSK-26 twin screw extruder, melted, and mixed with screws designed to achieve a homogeneous melt composition.
  • the melt stream was cooled and fed into a Maag Primo 60E pelletizer.
  • the pellets were collected and kept in sealed plastic buckets until used for injection molding.
  • Tg was measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418 using a heating and cooling rate of 20°C/min. Three scans were used for each DSC test: a first heat up to 340°C, followed by a first cool down to 30°C, followed by a second heat up to 350°C.
  • DSC Differential Scanning Calorimetry
  • the Tg was determined from the second heat up.
  • inventive sample E1 exhibits outstanding resistance to UV, especially as compared to comparative samples C1 and C2. Only sample E1 exhibited an elongation at yield, thereby exhibiting ductile behavior. Samples C1 and C2 broke before yielding, thereby exhibiting fragile behavior. Further, E1 could not be broken in the impact resistance test, indicating that this sample would provide a personal electronic device into which it is incorporated with robust protection against damage from impact.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

A personal electronic device is provided. The personal electronic device comprises a polymer composition. The polymer composition comprises at least 30 wt.% of a polyamide which in turn comprises at least 70 mol% of PACMX recurring units. The polyamide and/or polymer composition exhibit a unique combination of properties that render them suitable for use in personal electronic devices exposed to challenging environments. In particular, the polyamide/polymer compositions exhibit sufficient strength, rigidity, dimensional stability, moisture resistance, flame/heat resistance as well as UV stability to be used in personal electronic devices selected from the group consisting of mobile phones, personal digital assistants, laptop or tablet computers, wearable computing devices, flavor delivery systems, cameras, portable audio players or radios, global position system receivers, medical devices/medical equipment and portable game consoles.

Description

Personal Electronic Devices comprising Polyamide Composition
The present application claims the priority of European patent application EP 21306780.4 filed on 15 December 2021 , the content of which being entirely incorporated herein by reference for all purposes. In case of any incoherency between the present application and the PCT application that would affect the clarity of a term or expression, it should be made reference to the present application only.
Field
[0001] Personal electronic device components comprising a polymer composition (PC) comprising a polyamide (PA) are provided.
Background
[0002] Personal electronic devices exposed to challenging environments, e.g., those having high moisture (e.g., >50% humidity), high temperature (e.g., >35 °C), or comprising biological or environmental contaminants, must exhibit a diverse array of properties in order to garner commercial acceptance.
[0003] Moisture absorption can provide access for contaminants and cause surface irregularities that are visually unappealing, as well as a reduction in strength, rigidity and dimensional stability. [0004] Portions of the devices in contact with heating elements or otherwise exposed to elevated temperatures are desirably heat resistant and/or flame retardant. Such devices must also be physically strong enough to tolerate routine handling, as well as accidentally applied forces, without breaking.
[0005] UV resistance of external surfaces of devices used outdoors or in areas with high UV exposure is also desirable, so that the devices retain their color and/or visual appeal for their useful life.
[0006] The provision of this combination of properties via a single polymer composition is challenging.
[0007] Due to their inherent heat resistance, polysulfones have conventionally been used in the manufacture of personal electronic devices that incorporate heating elements. Polysulfones also typically have glass transition temperatures sufficiently high so that, even if some moisture absorption occurs, mechanical properties are not appreciably detrimentally impacted. However, many polysulfones may not naturally exhibit appreciable UV resistance. And so, while personal electronic devices comprising polysulfones enjoy commercial acceptance, some such devices may not possess the UV resistance needed to retain color integrity over their useful life. In these instances, additional ingredients, such as paints, stains or dyes, may be used in order to maintain visual appeal of the device for its lifetime. Though effective, this solution can add to the cost and complexity of the manufacturing process for the device. [0008] Some semi-crystalline polyamides have also been used in the manufacture of personal electronic devices, and many perform very well in this capacity. Typically, semi-crystalline polyamides have glass transition temperatures sufficient to provide devices comprising the polyamide with mechanical integrity at high temperatures. However, some semi-crystalline polyamides may be prone to moisture absorption, which can lead not only to additive migration, but also, to a decrease in the glass transition temperature Tg. Additive migration can provide the personal electronic device with a “mottled” or irregular surface appearance, which can result in a reduction in, or loss of, commercial acceptance. A decrease in Tg can translate into changes in mechanical properties that may render the polyamides less suitable for certain applications.
[0009] There is therefore a need in the art for materials for use in personal electronic devices that provide the desired strength, rigidity, dimensional stability, moisture and flame/heat resistance as well as UV stability.
Summary of the invention
[0010] The invention is set out in the appended set of claims.
[0011] The invention relates to a personal electronic device as defined in any one of claims 1-30.
[0012] The invention also relates to a flavor delivery system as defined in claim 31 .
[0013] The invention also relates to the use as defined in claim 30 or 31 . [0014] These subject-matters are defined more precisely below.
[0015] A personal electronic device is provided and comprises a polymer composition (PC). The polymer composition (PC), in turn, comprises at least 30.0 wt.% of a polyamide (PA) comprising at least 70.0 mol% recurring units R(PAI) according to formula (VII):
Figure imgf000005_0001
wherein R2 is a C4 to C30, Ce to C24, or Cs to C alkylene group, mol% is relative to the total moles of recurring units in the polyamide and wt.% is relative to the total weight of the polymer composition (PC).
[0016] The polymer composition (PC) optionally comprises at least one halogen free flame retardant, at least on reinforcing agent and at least one additive other than the halogen free flame retardant. More particularly, the polymer composition (PC) may comprise from 0 wt.% to 20 wt.% of the at least one halogen free flame retardant, from 0 wt.% to 50 wt.% of the at least one reinforcing agent, and from 0 wt.% to 30 wt.% of at least one additive other than the halogen free flame retardant.
[0017] The polyamide (PA) and polymer composition (PC) both exhibit a unique and advantageous combination of strength, rigidity, dimensional stability, moisture and flame/heat resistance as well as UV stability that renders a personal electronic device incorporating the same resistant or impervious to mechanical stress, moisture, temperature, UV and/or contaminant challenge. Personal electronic devices that find particular benefit from this combination of properties include mobile phones, personal digital assistants, laptop or tablet computers, wearable computing devices, flavor delivery systems, cameras, portable audio players or radios, global position system receivers, medical devices/ medical equipment and portable game consoles.
Detailed description
[0018] The invention relates to a personal electronic device comprising a polymer composition (PC) comprising a polyamide (PA). The polyamide (PA) is derived from the polycondensation of a diamine component (A) comprising 4,4- diaminodicyclohexylmethane (“PACM”) and a dicarboxylic acid component (B) comprising an aliphatic dicarboxylic acid (“X”). The polyamide (PA) comprises at least 70.0 mol% of “PACMX” recurring units.
[0019] The diamine component (A) may optionally comprise an additional diamine and/or the dicarboxylic acid component (B) may comprise an additional dicarboxylic acid. In such embodiments, the polyamide thus comprises at least one other recurring unit comprising a diamine different from PACM and/or a dicarboxylic acid different from the aliphatic dicarboxylic acid.
[0020] The polymer composition (PC) comprising the polyamide (PA) exhibits a combination of properties such as impact, break and moisture resistance. When formulated with halogen free flame retardants, the polymer composition (PC) provides heat/flame resistance on par with that provided by the polysulfones conventionally used in applications where the same is desired.
[0021] The polymer composition (PC) also exhibits UV resistance better than that exhibited by polymer compositions not including polyamides comprising the PACMX recurring units. UV resistance can provide the polymer composition (PC) with color integrity (notably of the surface) that otherwise must be provided by paints, stains or dyes.
[0022] Still further, the personal electronic device comprising the polymer composition (PC)Zpolyamide (PA) also avoids the development of surface imperfections via the migration of additives upon exposure of the device to moisture. Such surface imperfections are significant factors leading to market rejection of personal electronic devices comprising polymer compositions/polyamides other than those provided here.
[0023] Any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with descriptions of other embodiments.
[0024] Where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the individual recited elements or components, or can also be any combination of two or more of the explicitly listed elements or components. Further, any recited element or component may be omitted. [0025] Any recitation of numerical ranges includes all numbers and subranges subsumed within the recited ranges as well as the endpoints of the range.
[0026] The use of “a” or “an” in connection with a component is not intended to be limiting, and more than one of “a component” is contemplated, unless expressly stated otherwise. For example, a recitation that the polymer composition herein includes “an additive,” is inclusive both of embodiments wherein only one additive is present, as well as embodiments wherein two or more additives are used.
[0027] The amount of energy in the form of heat required to bring about a change of state of a thermoplastic polymer from the solid to the liquid form is the heat of fusion (“AHf”) of the polymer, and the temperature at which this change of state occurs is called the melting temperature (“Tm”). Amorphous materials lack a measurable Tm and have a AHf less than 5.0 J/g.
[0028] The terms “halogen” or “halo” include fluorine, chlorine, bromine and iodine.
[0029] The term “aliphatic” denotes an open chain chemical structure. Aliphatic compounds may be saturated or unsaturated, and linear or branched. The term “cycloaliphatic” refers to an aliphatic compound that includes a nonaromatic ring structure.
[0030] As used herein, the term “alkyl”, as well as derivative terms such as “alkoxy”, “acyl” and “alkylthio”, include within their scope straight chain and branched chain. Examples of alkyl groups are methyl, ethyl, 1 -methylethyl, propyl and
1 ,1 -dimethylethyl. [0031] Similarly, unless specifically stated otherwise, the term “aryl” is inclusive of both mono- and polynuclear aryl groups. The term “aryl” thus refers for instance to a phenyl, indanyl or naphthyl group.
[0032] THE REACTION MIXTURE (RM)
[0033] The polyamide (PA) is formed and comprises recurring units formed from a reaction mixture (RM) comprising a diamine component (A) and a dicarboxylic acid component (B).
[0034] The diamine component (A) contains each diamine in the reaction mixture and the dicarboxylic acid component (B) contains each dicarboxylic acid in the reaction mixture.
[0035] The Diamine Component (A)
[0036] The diamine component (A) comprises 4,4-diaminodicyclohexylmethane (PACM) and optionally at least one diamine different from 4,4- diaminodicyclohexylmethane.
[0037] 4,4-diaminodicyclohexylmethane is represented by the following formula (I):
Figure imgf000009_0001
[0038] In some embodiments of the present invention, at least 30.0 mol%, at least 40.0 mol%, or at least 50.0 mol% of the 4,4-diaminodicyclohexylmethane are in the trans/trans configuration. A trans/trans content of at least 30.0 mol% of the total isomer mol% of the 4,4-diaminodicyclohexylmethane (i.e., trans- trans, cis-trans and cis-cis) generally provides that a polyamide produced from a reaction mixture comprising the same is semi-crystalline.
[0039] The proportion of the 4,4-diaminodicyclohexylmethane in the diamine component (A) is at least 70.0 mol%, at least 75.0 mol%, at least 80.0 mol%, or at least 85.0 mol%.
[0040] According to an embodiment, the diamine component (A) consists essentially of 4,4-diaminodicyclohexylmethane. The expression "consist essentially" means in the context of the invention in relation to the diamine component that the diamine component (A) comprises 4,4-diaminodicyclohexylmethane and may also comprise up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of at least another diamine, this proportion in mol% being based on the total amount of diamines in the diamine component (A).
[0041] In a preferred embodiment, the diamine component (A) consists of 4,4- diaminodicyclohexylmethane, i.e., the proportion of 4,4- diaminodicyclohexylmethane in the diamine component (A) is 100 mol%.
[0042] In some embodiments, the proportion of 4,4-diaminodicyclohexylmethane in the diamine component is from 70.0 mol% to 100 mol%, from 75.0 mol% to 99.0 mol%, from 80.0 mol% to 98.0 mol%, or from 85.0 mol% to 97.0 mol%. As it pertains to the diamine component, mol% of the referenced diamine is relative to the total number of moles of diamines in the diamine component.
[0043] The Dicarboxylic Acid Component (B) [0044] The dicarboxylic acid component (B) comprises an aliphatic dicarboxylic acid (“X”) of formula (III):
HOOC-R2-COOH (III) wherein R2 is a C4 to C30, Ce to C24, or Cs to C alkylene group.
[0045] In the context of the invention, R2 is more particularly -(CH2)n- where n is an integer between 4 and 30 or between 6 and 24 or between 8 and 18.
[0046] More particularly, n is 12, 14, 15 or 16.
[0047] In some embodiments, the dicarboxylic acid component (B) comprises at least one dicarboxylic acid(s), different from the aliphatic dicarboxylic acid of formula (III).
[0048] According to an embodiment, the dicarboxylic acid component (B) consists essentially of the aliphatic dicarboxylic acid (“X”) of formula (III). The expression "consist essentially" means in the context of the invention in relation to the dicarboxylic acid component that the dicarboxylic acid component (B) comprises the aliphatic dicarboxylic acid (“X”) of formula (III) and may also comprise up to 2.0 mol%, preferably up to 1 .0 mol%, even more preferably up to 0.5 mol%, of at least another diacid, this proportion in mol% being based on the total amount of diacids in the dicarboxylic acid component (B).
[0049] THE POLYAMIDE (PA)
[0050] The polyamide (PA) is formed by the polycondensation reaction of the components of the reaction mixture (RM), i.e., the diamine component (A), the dicarboxylic acid component (B). More specifically, the condensation leads to the formation of amide bonds.
[0051] The polyamide comprises recurring units R(PAI) represented by formula (VII):
Figure imgf000012_0001
wherein R2 is as defined above. The person of ordinary skill in the art will recognize that recurring units (RPAI) are formed from the polycondensation reaction of 4,4-diaminodicyclohexylmethane and the aliphatic dicarboxylic acid according to formula (III).
[0052] The proportion of recurring units R( AI) according to formula (VII) in the polyamide (PA) is at least 70.0 mol%. This proportion may be at least 75.0 mol%, at least 80.0 mol% or at least 85.0 mol%.
[0053] In some embodiments, the polyamide (PA) consists of the recurring units R(PAI) according to formula (VII), i.e. , the proportion of recurring units R( AI) in the polyamide (PA) is 100 mol%.
[0054] In other embodiments, the proportion of recurring units R( AI) according to formula (VII) in the polyamide (PA) is no more than 99.0 mol%, no more than 98.0 mol%, or no more than 97.0 mol%. In some embodiments, the proportion of recurring units R( AI) according to formula (VII) in the polyamide (PA) is from 70.0 mol% to 100.0 mol%, from 75.0 mol% to 99.0 mol%, from 80.0 mol% to 98.0 mol%, or from 85.0 mol% to 97.0 mol%. [0055] As used herein, mol% in reference to a recurring unit of the polyamide (PA) is relative to the total moles of all recurring units in the polyamide.
[0056] End groups of the polyamide (PA)
[0057] The end-groups in the polyamide (PA) are selected in the group of -NH2, - COOH and amide end-groups. Indeed, the end-groups in the polyamide (PA) may be -NH2 or -COOH. Yet, when the polycondensation involves the addition of an end-capping agent, these end-groups may be converted, partially or totally, into amide end-groups.
[0058] The amide end groups are of formula -NH-C(=O)-R where R is an an alkyl group, an aryl group or a cycloalkyl group and/or of formula -C(=O)-NH-R' where R' is an alkyl group or a cycloalkyl group. R is more particularly a linear or branched C2-C18 alkyl group or a C5-C10 cycloalkyl group. R' is more particularly a linear or branched C2-C18 alkyl group.
[0059] The amide end groups of formula -NH-C(=O)-R result from the reaction of the end-groups -NH2 with a monocarboxylic acid (end-capping agent) of formula R-COOH.
[0060] The monocarboxylic acid (end-capping agent) may advantageously be selected in the group consisting of benzoic acid; cyclohexanoic acid; R-COOH where R is a linear or branched C2-C18 alkyl group and combination of two or more of these acids. R is the radical derived from the acid of formula R-COOH.
[0061 ] The monocarboxylic acid (end-capping agent) may more particularly be selected in the group consisting of acetic acid, propanoic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid and combination of two or more of these acids.
[0062] The monocarboxylic acid (end-capping agent) is more particularly of formula CH3-(CH2)n-COOH where n is an integer between 0 and 16. The amide end groups are then of formula -NH-C(=O)-(CH2)n-CH3.
[0063] The amide end groups of formula -C(=O)-NH-R' result from the reaction of the end-groups -COOH with a primary amine (end-capping agent) of formula R'- NH2. [0064] The primary amine (end-capping agent) may advantageously be selected in the group consisting of the amines of formula R'-NH2 where R' is a linear or branched C2-C18 alkyl group. R' is the radical derived from the amine of formula R'-NH2.
[0065] The primary amine (end-capping agent) is more particularly of formula CH3- (CH2)n'-NH2 where n' is an integer between 2 and 18. The amide end groups are then of formula -C(=O)-NH-(CH2)n'-CH3.
[0066] The primary amine (end capping agent) may more particularly be selected in the group consisting of propyl amine, butylamine, pentylamine, hexylamine, 2- ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n- hexadecylamine, stearylamine, cyclohexylamine and combination of two or more of these amines.
[0067] The proportion of the end groups can be quantified by 1H NMR or by potentiomtric techniques.
[0068] Thermal properties of the polyamide (PA)
[0069] The polyamide (PA) generally has a glass transition temperature Tg of at least 90 °C. The Tg may be at least 100 °C or at least 110 °C. Tg is advantageously at least 120°C.
[0070] The Tg is generally no more than 200 °C. The Tg may be no more than 190
°C, no more than 180 °C or no more than 170 °C.
[0071] The Tg may be from 90 °C to 200 °C, from 100 °C to 190 °C or from 110 °C to 180 °C. The Tg may also be from 90 °C to 190 °C, from 90 °C to 180 °C, or from 90 °C to 170 °C.
[0072] Tg may more particularly be between 120°C and 140°C.
[0073] The polyamide (PA) has a Tm of at least 180 °C, at least 190 °C, or at least
200 °C. Tm may also be at least 220°C. In some embodiments, the polyamide has a Tm of no more than 290 °C, no more than 285 °C, or no more than 280 °C. Tm may also be no more than 240°C.
[0074] Tm may be from 180 °C to 290 °C, from 190 °C to 285 °C or from 200 °C to 280 °C. Tm may also from 220°C to 240°C.
[0075] The polyamide (PA) is semi-crystalline or microcrystalline. The polyamide has a AHf of at least 5.0 J/g, preferably at least 7.0 J/g, or at least 10.0 J/g. In some embodiments, the polyamide has a AHf of no more than 80.0 J/g, no more than 70.0 J/g or no more than 60.0 J/g. In some embodiments, the polyamide has a AHf of from 5.0 J/g to 80.0 J/g, from 7.0 J/g to 70.0 J/g, or from 10.0 J/g to 60.0 J/g. AHf may befrom 5.0 J/g to 50.0 J/g, from 5.0 J/g to 40.0 J/g, or from 5.0 J/g to 30.0 J/g.
[0076] The Tg, Tm and AHf of the polyamide are measured according to ASTM D3418.
[0077] The polyamide (PA) has a number average molecular weight (“Mn”) from 1 ,000 g/mol to 40,000 g/mol. Mn may be from 2,000 g/mol to 35,000 g/mol, from 4,000 to 30,000 g/mol, or from 5,000 g/mol to 20,000 g/mol.
[0078] Mn may also advantageously be between 10,000 and 20,000 g/mol.
[0079] The number average molecular weight Mn can be determined by gel permeation chromatography (GPC) using ASTM D5296.
[0080] The polyamide (PA) has preferably a water absorption, by immersion in water at 23°C of less than 8 wt.%, preferably less than 7.0 wt.%, preferably less than
6.0 wt.%, or preferably less than 5.0 wt.%. The water absorption is most preferably lower than 3.0 wt%. The water absorption at 23°C is determined by
ASTM D570. Generally, a specimen (shaped according to ISO527) is provided in its dry state (moisture content of less than 0.2 wt.%), immersed in deionized water at 23°C, for 24 hours, or until reaching a constant weight. The water absorption is calculated according to the formula:
W „ - Wh f Water uptake - - ^-x1 00
Wbefore wherein Wbefore is the weight of the shaped specimen in its original dry state and Wafter is the weight of the shaped specimen after immersion for the specified time.
[0081] METHODS OF PREPARATION OF THE POLYAMIDE (PA)
[0082] The polyamide (PA) described herein is prepared by polycondensation through reacting the components of the reaction mixture (RM).
[0083] The total number of moles of diamines in the reaction mixture (RM) is substantially equimolar to the total number of moles of dicarboxylic acids in the reaction mixture. As used herein, substantial equimolar denotes a value that is ± 3.0% of the indicated number of moles. For example, in the context of the diamine and dicarboxylic acid concentrations in the reaction mixture, total number of moles of diamines in the reaction mixture is ± 3.0% of the total number of moles of dicarboxylic acids in the reaction mixture.
[0084] The polyamide (PA) is generally prepared by reacting the monomers (e.g. the diamines, dicarboxylic acids) of the reaction mixture (RM) in the presence of less than 40 wt.%, less than 30 wt.%, less than 20 wt.%, less than 10 wt.% or even with no added water.
[0085] Catalysts are usually added to the reaction mixture (RM). Examples of catalysts are phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite such as sodium hypophosphite and phenylphosphinic acid. Phosphites are suitable stabilizers.
[0086] The reaction mixture (RM) may also comprise at least one end capping agent as disclosed above.
[0087] The monomers may be caused to react by heating the reaction mixture (RM) to a temperature of at least Tm + 10°C, Tm being the melting temperature of the polyamide. The temperature at which the reaction mixture is heated is generally at least 200°C or even at least 250°C.
[0088] The conditions used in the experimental section may be followed to prepare the polyamide (PA).
[0089] THE POLYMER COMPOSITION (PC)
[0090] Advantageously, the polyamide (PA) and/or the polymer composition (PC) of the invention exhibit(s) at least one, at least two, at least three, at least four, at least five, at least six or all of the following properties:
• UV resistance, as evidenced by a AE no more than 5.0, preferably no more than 4.0, preferably no more than 3.0, preferably no more than 2.0 or less, after 240 hours as measured according to ISO4892-
2:2013/AMD1 :2021 ; • break resistance, as evidenced by an IZOD impact strength of at least 50.0 KJ/m2, preferably at least 60.0 KJ/m2, preferably at least 70.0 KJ/m2, preferably at least 80.0 KJ/m2, as measured according to ISO180;
• flame resistance, as evidenced by a flammability rating of V1 or V2 measured according to the LIL94 standard;
• an elongation at Break of greater than 2.0%, or greater than 2.5%, or greater than 3.0%, as measured according to ISO527-2;
• water absorption, by immersion in water at 25°C, as measured by ASTM D570 of less than 8.0 wt.%, preferably less than 7.0 wt.%, preferably less than 6.0 wt.%, preferably less than 5.0 wt.%, preferably less than 3.0%;
• strength at yield (Break) of greater than 45 MPa, preferably greater than 50 MPa, preferably greater than 55 MPa, as measured according to ISO527-2; and
• a glass transition temperature of greater than 90°C, preferably greater than 100°C, preferably greater than 110°C, preferably greater than 120°C.
[0091] The polyamide (PA) and/or the polymer composition (PC) advantageously exhibit(s) a AE no more than 5.0, preferably no more than 4.0, preferably no more than 3.0, preferably no more than 2.0, after 240 hours as measured according to ISO4892-2:2013/AMD1 :2021. Formula of AE is given in the experimental section.
[0092] The polyamide (PA) and/or the polymer composition (PC) advantageously exhibit(s) a break resistance, as evidenced by an IZOD impact strength of at least 50.0 KJ/m2, preferably at least 60.0 KJ/m2, preferably at least 70.0 KJ/m2, preferably at least 80.0 KJ/m2, as measured according to ISO180.
[0093] The polyamide (PA) and/or polymer composition (PC) advantageously exhibit(s) a flame resistance, as evidenced by a flammability rating of V1 or V2 measured according to the LIL94 standard. UL 94 is the Standard for Safety of Flammability of Plastic Materials for Parts in Devices and Appliances testing, is a plastics flammability standard released by Underwriters Laboratories of the United States. The standard determines the material’s tendency to either extinguish or spread the flame once the specimen has been ignited.
[0094] The polyamide (PA) and/or polymer composition (PC) advantageously exhibit(s) an Elongation at Break of greater than 2.0%, or greater than 2.5%, or greater than 3.0%, as measured according to ISO527-2.
[0095] The polyamide (PA) and/or polymer composition (PC) advantageously exhibit(s) a strength at yield (Break) of greater than 45 MPa, preferably greater than 50 MPa, preferably greater than 55 MPa, as measured according to
ISO527-2. [0096] This combination of these properties renders the personal electronic device comprising the polyamide (PA) and/or polymer composition (PC) suitable for use in even the most challenging of environments.
[0097] In some embodiments, the polymer composition (PC) consists of the polyamide (PA), i.e., the proportion of the polyamide (PA) in the polymer composition (PC) is 100 wt.%. As used herein and unless explicitly stated otherwise, the proportion of a component in the polymer composition (PC) is relative to the total weight of the polymer composition (PC).
[0098] The polymer composition (PC) may comprise the polyamide (PA) in a proportion of at least 30.0 wt.%, at least 35.0 wt.%, at least 40.0 wt.%, or at least 45.0 wt.%. The proportion of polyamide (PA) in the polymer composition (PC) may be no more than 99.0 wt.%, no more than 95.0 wt.%, no more than 90.0 wt.%, or no more than 85.0 wt.%.
[0099] The proportion of the polyamide (PA) in the polymer composition (PC) is from 30.0 wt.% to 100.0 wt.%, from 35.0 wt.% to 99.0 wt.%, from 40.0 wt.% to 95.0 wt.%, or from 45.0 wt.% to 90.0 wt.%.
[00100] In some embodiments, the polymer composition includes one or more polymeric materials in addition to the at least one polyamide described herein. Suitable additional polymeric material(s) include other polyamides, poly(arylene sulphides) poly(phenylene sulphides), poly(aryl ether sulfones), poly(biphenyl ether sulfones), polysulfones, poly(aryl ether ketones) and poly(ether ether ketones). [00101] In some embodiments, the polymer composition comprises a halogen free flame retardant, one or more reinforcing agents and/or one or more additives different from the halogen free flame retardant.
[00102] Halogen Free Flame Retardant
[00103] The polymer composition (PC) may optionally comprise at least one halogen free flame retardant. Examples of desirable halogen free flame retardants include, but are not limited to, metal dialkyl phosphinates (e.g. aluminum diethyl phosphinate), organophosphates (e.g. triphenylphosphates) and phosphonates (e.g. dimethyl methylphosphonates).
[00104] The halogen free flame retardant may be selected in the group consisting of the compounds according to the formulae below:
[RaRbP(=O)O]m M
[RaP(=O)O-Rc-P(=O)ORb]n M where Ra and Rb are identical or different and are selected in the group consisting of linear or branched Ci-Cs-alkyl groups and aryl groups, Rc is selected in the group consisting of linear or branched Ci-C -alkylene groups, Ce-C -arylene groups, M is a metal ion selected in the group of Al, Ca and
Zn, m is 2 or 3, n is 1 or 3, x is 1 or 2.
[00105] The halogen free flame retardant may for instance be of formula
Figure imgf000021_0001
[00106] If the polymer composition (PC) comprises at least one halogen free flame retardant, the total proportion of halogen free flame retardant(s) in the polymer composition (PC) is at least 1.0 wt.%, at least 2.0 wt.%, or at least 5.0 wt.%. The total proportion of halogen free flame retardant(s) may be no more than 20.0 wt. %, no more than 18.0 wt. %, nor more than 17.0 wt.%, or no more than 15.0 wt. %, In some embodiments, the total proportion of halogen free flame retardant(s) is from 0 wt.% to 20.0 wt.%, from 1.0 wt.% to 18.0 wt.%, from 2.0 wt.% to 17.0 wt. % or from 5.0 wt.% to 15.0 wt.%.
[00107] Reinforcing Agents
[00108] Examples of suitable reinforcing agents include, but are not limited to, mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, wollastonite and any combination of these.
[00109] Suitable reinforcing agents can be selected from fibrous and particulate reinforcing agents. A fibrous reinforcing agent is considered herein to be a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness. Generally, such a material has an aspect ratio, defined as the average ratio between the length and the largest of the width and thickness of at least 5, at least 10, at least 20 or at least 50. Suitable fibrous reinforcing agents (e.g. glass fibers or carbon fibers) can have an average length of from 3 mm to 50 mm. In some embodiments including fibrous reinforcing agents, the fibers have an average length of from 3 mm to 10 mm, from 3 mm to 8 mm, from 3 mm to 6 mm, or from 3 mm to 5 mm. In other embodiments, the fibers have an average length of from 10 mm to 50 mm, from 10 mm to 45 mm, from 10 mm to 35 mm, from 10 mm to 30 mm, from 10 mm to 25 mm, or from 10 mm to 20 mm. The average length of the fibers can be taken as the average length of the fibers prior to incorporation into the polymer composition or can be taken as the average length of the fibers within the polymer composition.
[00110] In embodiments including a reinforcing agents, the reinforcing agent is desirably a fibrous filler and preferably a fibrous filler that is able to withstand the high temperature applications. Glass fibers are particularly preferred.
[00111] All glass fiber types, such as A, C, D, E, M, S, R, T glass fibers (as described in chapter 5.2.3, pages 43-48 of Additives for Plastics Handbook, 2nd ed., John Murphy), or any mixtures thereof may be used. Additional descriptions of E, R, S and T glass fibers can be found in, e.g., Fiberglass and Glass Technology, Wallenberger, Frederick T.; Bingham, Paul A. (Eds.), 2010, XIV, chapter s, pages 197-225.
[00112] In some embodiments, the glass fiber is a high modulus glass fiber. High modulus glass fibers have an elastic modulus of at least 76, preferably at least 78, more preferably at least 80, and most preferably at least 82 GPa as measured according to ASTM D2343. Examples of high modulus glass fibers include, but are not limited to, R, S and T glass fibers. R, S and T glass fibers are composed essentially of oxides of silicon, aluminum and magnesium, and typically from 62-75 wt. % of SiO , from 16-28 wt. % of AI2O3 and from 5-14 wt. % of MgO. R, S and T glass fibers comprise less than 10 wt. % of CaO. High modulus glass fibers include S-1 and S-2 glass fibers, commercially available from Taishan and AGY, respectively.
[00113] The morphology of the glass fiber is not particularly limited and the glass fiber can be round, i.e. , have a circular cross-section, or flat, i.e. , have a non-circular (e.g., oval, elliptical or rectangular) cross-section.
[00114] The use of a reinforcing agent in the polymer composition is optional. In those embodiments comprising the same, the total concentration of reinforcing agents in the polymer composition is at least 5 wt. %, at least 10 wt. %, or at least 15 wt. %. In some embodiments, the total concentration of reinforcing agents is no more than 50 wt. %, no more than 45 wt. %, or no more than 40 wt. %, In some embodiments, the total concentration of reinforcing agents is from 0 wt. % to 50 wt.%, from 5 wt.% to 50 wt.%, from 10 wt.% to 45 wt. % or from 15 wt.% to 40 wt.%, based upon the total weight of the polymer composition.
[00115] Additives
[00116] The polymer composition (PC) may optionally comprise one or more additives selected from the group consisting of tougheners, plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, nucleating agents, antioxidants and any combination thereof.
[00117] In some embodiments, the polymer composition (PC) includes a toughener. A toughener is generally a low Tg polymer, with a Tg for example below room temperature, below 0°C or even below -25°C. As a result of its low Tg, the toughener is typically elastomeric at room temperature. Tougheners can be functionalized polymers and are therefore typically reactive with other components of the polymer composition.
[00118] Suitable tougheners can be selected from polyethylenes and copolymers thereof, e.g. ethylene-butene; ethylene-octene; polypropylenes and copolymers thereof; polybutenes; polyisoprenes; ethylene-propylene-rubbers (EPR); ethylene-propylene-diene monomer rubbers (EPDM); ethyleneacrylate rubbers; butadiene-acrylonitrile rubbers, ethylene-acrylic acid (EAA), ethylene-vinylacetate (EVA); acrylonitrile-butadiene-styrene rubbers (ABS), block copolymers styrene ethylene butadiene styrene (SEBS); block copolymers styrene butadiene styrene (SBS); core-shell elastomers of methacrylate-butadiene-styrene (MBS) type, or mixture of one or more of the above.
[00119] A toughener can be functionalized by copolymerization of monomers containing reactive functionalities or from the grafting of reactive groups onto the toughener. Specific examples of functionalized tougheners are notably terpolymers of ethylene, acrylic ester and glycidyl methacrylate, copolymers of ethylene and butyl ester acrylate; copolymers of ethylene, butyl ester acrylate and glycidyl methacrylate; ethylene-maleic anhydride copolymers; EPR grafted with maleic anhydride; styrene copolymers grafted with maleic anhydride; SEBS copolymers grafted with maleic anhydride; styreneacrylonitrile copolymers grafted with maleic anhydride; ABS copolymers grafted with maleic anhydride.
[00120] In some embodiments, the total additive proportion in the polymer composition (PC) is at least 0.1 wt.%, at least 0.2 wt.%, at least 0.3 wt.%, at least 0.4 wt.%, or at least 0.5 wt.%. In some embodiments, the total additive concentration in the polymer composition is no more than 30 wt.%, no more than 25 wt.%., no more than 20 wt.%, no more than 15 wt.% or no more than 10 wt.%. In some embodiments, the total additive concentration in the polymer composition is from 0 wt. % to 30 wt.%, 0.1 wt.% to 30 wt.%, from 0.2 wt.% to 25 wt.%, from 0.3 wt.% to 20 wt.%, from 0.4 wt.% to 15 wt.% or from 0.5 wt.% to 10 wt.%.
[00121] METHODS OF PREPARATION OF THE POLYMER COMPOSITION (PC)
[00122] The polymer composition (PC) can be prepared according to methods well known in the art. For example, the polymer composition (PC) can be made by melt-blending the polyamide (PA) and the other ingredients of the polymer composition (PC) (e.g. any desired halogen free flame retardants, reinforcing agents, and/or other additives). [00123] Any melt-blending method may be used to combine the polyamide and any other desired components. For example, polymeric ingredients and non- polymeric ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer. The ingredients may be fed all at once, via gradual addition, or in batches. If a reinforcing agent presents a long physical shape (for example, a long glass fiber), drawing extrusion molding may be used to prepare a reinforced composition.
[00124] The personal electronic device can be prepared in a two-step process wherein the polymer composition (PC) is formed into pellets, and then the pellets are injection molded to produce the personal electronic device. Alternatively, the personal electronic device may be prepared directly from the polymer composition in an integrated, one-step process.
[00125] The personal electronic device can be made from the polymer composition (PC) by methods including, but not limited to, melt-mixing processes. Meltmixing processes are typically carried out by heating the polymer components above the highest melting temperature and glass transition temperature of the thermoplastic polymers thereby forming a melt of the thermoplastic polymers. In some embodiments, the processing temperature ranges from about 240- 400°C, preferably from about 250-380°C, from about 260-360°C.
[00126] In some embodiments, the polymer composition (PC) is melt-mixed in an extruder, and the high temperature personal electronic device injection molded therefrom. Preferably, use is made of an extruder fitted with means for dosing all the desired components of the polymer composition to the extruder, whether to the extruder's throat or to the melt.
[00127] The components may be fed simultaneously as a powder or granule mixture, also known as dry-blend, or may be fed separately. The order of combining the components during melt-mixing is not critical. In some embodiments, the components can be mixed in a single batch, such that the desired amounts of each component are added together and subsequently mixed. However, the total desired amount of each component does not have to be mixed as a single quantity. In other embodiments, a partial quantity of one or more components can be initially added and mixed and, subsequently, some or all of the remainder can be added and mixed.
[00128] The method may comprise if needed several successive steps of melt-mixing or extrusion under different conditions. The method may also comprise one or more cooling steps.
PERSONAL ELECTRONIC DEVICE
[00129] Exemplary personal electronic devices that find particular benefit from the combination of properties exhibited by the present polyamide (PA) and polymer composition (PC) include personal electronic devices, and particularly those that incorporate a heating element or are exposed to high temperatures (e.g., greater than 40°C) during use. 1 [00130] Examples of such personal electronic devices include, but are not limited to, mobile phones, personal digital assistants, laptop or tablet computers, wearable computing devices (e.g., a smart watch, smart glasses and the like), flavor delivery systems, cameras, portable audio players or radios, global position system receivers, medical devices/medical equipment and portable game consoles.
[00131] The polymer composition (PC) can be used to form all, or a part of, any component of the personal electronic device. Significant benefit from the combination of properties provided by the polymer composition may be realized when the polymer composition (PC) is used in a component that is expected to be exposed to UV radiation, moisture, temperature and/or mechanical challenge in the course of its useful life. Housings or casings and parts thereof are but one example of a component wherein the advantages provided by the polymer composition (PC) may find particular applicability.
[00132] As used herein, the term “housing” is meant to indicate any portion of a personal electronic device that provides cover and/or protection to the/other operative components of the device. In particular, housings or parts thereof can function to protect internal and electronic components from impact or damage from environmental influences, such as moisture or UV radiation and can also function to give the personal electronic device strength. Housings or housing parts include covers, cover plates, backbones (structural components to which other components attach), mouthpieces, hoods or lids, frames and parts or components that support these.
[00133] Flavor delivery device
[00134] One example of a personal electronic device that finds particular advantage in the combination of properties provided by the present polyamide (PA) and polymer composition (PC) is a flavor delivery device. And so, in some embodiments, the personal electronic device is a flavor delivery device.
[00135] Flavor delivery devices can be used for delivery of an aerosol containing one or more active ingredients and/or flavors to the user of the flavor delivery system via inhalation. Flavor delivery systems typically include a reservoir or compartment for holding a liquid, gel or solid flavor vehicle, a heating element operatively disposed relative to the reservoir or compartment, and a power source, among other components. A plastic housing typically surrounds and supports the reservoir, heating element and power source. An air inlet may be provided at an end of the plastic housing, with a mouthpiece provided at an opposing end. In use, the flavor delivery system may be activated by the press of a button, detection of an inhalation at the mouthpiece, or wireless communication with an external controller. Once activated, heat provided by the heating element releases the flavor from the flavor vehicle. The air drawn in at the air intake upon inhalation mixes with the vaporized flavor providing an inhalable aerosol that is delivered to the user through the mouthpiece. Flavor delivery devices are well known in the art and are described in, e.g., International Publication No. WO 2020/150400, US Publication No. 2015/025669 and US Publication No. 2018/0274110. The entire contents of each of these is hereby incorporated by reference herein, for any and all purposes.
[00136] The polymer composition (PC) or the polyamide (PA) can thus be used to form at least a portion of the housing of the flavor delivery device. In some embodiments, the polymer composition forms at least a portion of an exterior surface of the housing. As the housing of flavor delivery devices may be exposed to sweat, humidity, high temperature and/or UV exposure during use, the advantages of the polymer composition provided herein will be particularly appreciated by a user of such devices. In some embodiments, the polyamide composition (PC) is not used to form interior components.
[00137] The invention thus also relates to a flavor delivery system for delivery of an aerosol containing one or more active ingredients and/or flavors including a reservoir for holding the ingredient(s) and/or flavor(s), a heating element and a power source wherein the system also includes a housing made of or comprising the polymer composition (PC) of the invention.
[00138] Exemplary embodiments will now be described in the following non-limiting examples.
EXPERIMENTAL SECTION
[00139] Materials • 4,4’-methylene-bis-cyclohexylamine (PACM) (45-50 mol% trans/trans isomer, BASF).
• hexadecanedioic acid (C16) (Cathay Biotech Inc.).
• PA6T/10T/1 ,3-BACT (57/35/8, Solvay Specialty Polymers, USA, LLC).
• PA10T (Vicnyl® 6100 Kingfa).
• halogen free flame retardant (Exolit® CP1400 Clariant).
• additive Package o heat stabilizer (Irganox® B1171 , BASF) o UV stabilizers (Chimassorb® 944 LD and Tinuvin® 234 BASF). o calcium stearate (lubricant, BASF) o red pigment
[00140] Methods
[00141] Sample preparation
[00142] Test specimens according to Comparative Examples C1 and C2 and Inventive Example E1 were injection molded into standard dumbbell-shaped ISO type 1A tensile specimens on a Toshiba ISG 150 Injection Molder. The test specimens has the following nominal dimensions: full length of 170 mm, gauge length of 75 mm, parallel section length of 80 mm, parallel section width of 10 mm, grip section width of 20 mm, and thickness of 4 mm.
[00143] Tensile Testing [00144] Tensile modulus and strength of inventive and comparative samples were measured at a testing temperature of 23 °C and speeds according to ISO 527- 2.
[00145] Impact Testing
[00146] IZOD impact strength of inventive and comparative unnotched samples was measured according to ISO180.
[00147] Flammability Testing
[00148] The flammability rating of the inventive and comparative samples was measured according to the LIL94 standard.
[00149] LIV Resistance Testing
[00150] UV resistance was measured according to ISO4892-2:2013/AMD1 :2021 , Method B, cycle n.1 . Samples were visually inspected every 24 hours. Color parameters L*, a* and b* were measured after 96 hours, 168 hours, 216 hours and 240 hours. Delta E was calculated as follows:
Figure imgf000033_0001
[00151] The lower the AE, the lower the color shift and the better the UV resistance.
[00152] Moisture Testing
[00153] This test was conducted to evaluate the stability of the exterior appearance of the samples under simulated long duration hand held conditions. The solution shown in Table 1 was prepared:
Table 1
Figure imgf000034_0001
[00154] The pH of the solution was adjusted to a value of 6.5 ± 0.1 using ammonium hydroxide solution (1 % by weight).
[00155] A piece of cotton gauze was moistened with the sweat solution and placed over one end of the surface of the samples, covering no more than 20% of the length of the sample. The other end of each sample was placed into a bath of the solution. The samples and bath were placed into a sealed container and the sealed container placed into a temperature controlled chamber at 60C. After 48 hours, the samples were wiped dry with a clean cloth and allowed to cool to room temperature.
[00156] The exterior surface of each sample was visually evaluated before and after testing. Any change in appearance, whether color change, mottling, formation of surface defects such as mottling, voids or bubbling resulted in a fail.
[00157] Preparation of Polyamide PACM16: a stainless steel reactor was charged with a diamine component consisting of 95.5 grams (0.45 mol) of PACM, a dicarboxylic acid component consisting of 128.4 g (0.44 mol) grams of hexadecanedioic acid and 4.16 gram of an aqueous solution of sodium hypophosphite monohydrate (5%wt, 2 mmol). The reactor was sealed, purged with nitrogen 3 times and heated to 275°C. The reaction proceeded at atmospheric pressure. Condensation water as well as water from the catalyst solution were distilled off. The reaction mixture was kept at 275°C for 30 min. The resulting polymer was then discharged as a strand and pelletized. The number average molecular weight of the PACM16 obtained is Mn=16.2 kg/mol.
[00158] Preparation of the polymer compositions (PC): the compositions shown in Table 2, below, were prepared by blending the components in a Coperion ZSK-26 twin screw extruder.
Table 2
Figure imgf000035_0001
The components were initially mixed in a plastic bucket and sealed. The bucket was placed on a vibratory shaker for 2-3 minutes to assure homogeneity. The so obtained mixture was then placed in a K-TronT-35 gravimetric feeder and fed into the Coperion ZSK-26 twin screw extruder, melted, and mixed with screws designed to achieve a homogeneous melt composition. The melt stream was cooled and fed into a Maag Primo 60E pelletizer. The pellets were collected and kept in sealed plastic buckets until used for injection molding.
[00159] Results
[00160] Data from the moisture, as well as the Tg of the polyamide of each sample, is shown in Table 3. Tg was measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418 using a heating and cooling rate of 20°C/min. Three scans were used for each DSC test: a first heat up to 340°C, followed by a first cool down to 30°C, followed by a second heat up to 350°C.
The Tg was determined from the second heat up.
Table 3
Figure imgf000036_0001
[00161] As shown in Table 3, all samples passed the moisture test. Specifically, samples E1 , C1 and C2 all retained a homogeneous surface appearance.
[00162] Data from the tensile, impact, flammability and UV resistance testing of samples E1 , C1 and C2 is shown in Table 4. [00163] Table 4
Figure imgf000037_0001
NB = non-break
*the lower the Delta E, the lower the color shift and the better the UV resistance
While E1 , C1 and C2 all have an adequate flammability rating (LIL94 V1 or V2) to be considered suitable for use in the present personal electronic devices, inventive sample E1 exhibits outstanding resistance to UV, especially as compared to comparative samples C1 and C2. Only sample E1 exhibited an elongation at yield, thereby exhibiting ductile behavior. Samples C1 and C2 broke before yielding, thereby exhibiting fragile behavior. Further, E1 could not be broken in the impact resistance test, indicating that this sample would provide a personal electronic device into which it is incorporated with robust protection against damage from impact.

Claims

1 . A personal electronic device comprising a polymer composition (PC), the polymer composition comprising:
• at least 30.0 wt.% of a polyamide (PA) comprising at least 70.0 mol% of recurring units R(PAI) according to formula (VII):
Figure imgf000039_0001
• from 0 wt.% to 20 wt.% of at least one halogen free flame retardant;
• from 0 wt.% to 50 wt.% of at least one reinforcing agent; and
• from 0 wt.% to 30 wt.% of at least one additive other than the halogen free flame retardant; wherein:
• R2 is a C4 to C30;
• mol% is relative to the total moles of recurring units in the polyamide (PA);
• wt.% is relative to the total weight of the polymer composition (PC); and wherein the personal electronic device is selected from the group consisting of a mobile phone, a personal digital assistant, a laptop computer, a tablet computer, a wearable computing device, a flavor delivery system, a camera, a portable audio
38 player, a portable radio, a global position system receiver, a medical device/piece of medical equipment and a portable game console. The personal electronic device of claim 1 , wherein the polyamide is the condensation product of a reaction mixture (RM) comprising
• a diamine component (A) comprising from 70 mol% to 100 mol%, from
75 mol% to 99 mol%, from 80 mol% to 98 mol%, or from 85 mol% to 97 mol% 4,4'-diaminodicyclohexylmethane of formula (I):
Figure imgf000040_0001
wherein o at least 30 mol% at least 40 mol%, or at least 50 mol% of the 4,4- diaminodicyclohexylmethane is in a trans/trans configuration; and o mol% is relative to the total moles of diamines in the diamine component; and
• a dicarboxylic acid component (B) comprising from 70 mol% to 100 mol%, from 75 mol% to 99 mol%, from 80 mol% to 98 mol%, or from 85 mol% to 97 mol% of an aliphatic dicarboxylic acid (“X”) of formula (III):
HOOC-R2-COOH (HI) wherein o R2 is a C4 to C30 alkylene group; and o mol% is relative to the total moles of dicarboxylic acids in the dicarboxylic acid component. The personal electronic device of any one of claims 1-2, wherein R2 is a Ce to C24, or Cs to C18 alkylene group. The personal electronic device of any one of claims 2-3, wherein the diamine component (A) consists of or consists essentially of 4,4- diaminodicyclohexylmethane. e personal electronic device of any one of claims 2-4, wherein the the dicarboxylic acid component (B) consists of or consists essentially of the aliphatic dicarboxylic acid (“X”) of formula (III). e personal electronic device of any one of claims 2-5, wherein the reaction mixture
(RM) does not comprise aromatic diamines, aromatic dicarboxylic acids and/or amino acids/lactams. e personal electronic device of claim 1 , wherein the polyamide (PA) does not comprise recurring units derived from an aromatic diamine, from an aromatic dicarboxylic acid, from an amino acids and from a lactam.
40 he personal electronic device of claim 1 , wherein the recurring units of the polyamide (PA) consist of the recurring units R(PAI) of formula (VII). The personal electronic device of any one the preceding claims, wherein R2 is of formula -(CH2)n- wherein n is an integer between 4 and 30 or between 6 and 24 or between 8 and 18. he personal electronic device of claim 9, wherein n is 12, 14, 15 or 16. he personal electronic device of any one the preceding claims, wherein the polyamide (PA) has a melting point Tm of from 180 °C to 290 °C, from 190 °C to 285 °C, or from 200 °C to 280 °C, as measured according to ASTM D3418. he personal electronic device of any one the preceding claims, wherein the polyamide (PA) has a melting point Tm of at least 220°C, as measured according to ASTM D3418. The personal electronic device of any one the preceding claims, wherein the polyamide (PA) has a melting point Tm of no more than 240°C, as measured according to ASTM D3418. he personal electronic device of any one the preceding claims, wherein the polyamide (PA) has a glass transition temperature Tg of from 90 °C to 200 °C, from 100 °C to 190 °C, or from 110 °C to 180 °C, as measured according to ASTM D3418. he personal electronic device of any one the preceding claims, wherein the polyamide (PA) has a glass transition temperature Tg between 120°C and 140°C, as measured according to ASTM D3418. The personal electronic device of any one the preceding claims, wherein the polyamide (PA) is crystalline or microcrystalline. he personal electronic device of any one the preceding claims, wherein the polyamide (PA) has a heat of fusion of from 5.0 J/g to 80.0 J/g, from 7.0 J/g to 70.0 J/g, or from 10.0 J/g to 60.0 J/g, as measured according to ASTM D3418. The personal electronic device of any one the preceding claims, wherein the polyamide (PA) exhibits a number average molecular weight Mn between 10,000 and 20,000 g/mol. he personal electronic device of any one the preceding claims, wherein the polyamide (PA) exhibits a water absorption, by immersion in water at 23°C of less than 8 wt.%, preferably less than 7.0 wt.%, preferably less than 6.0 wt.%, preferably less than 5.0 wt.%, preferably less than 3.0 wt%. he personal electronic device of any one the preceding claims, wherein the polymer composition (PC) comprises at least one reinforcing agent, notably selected from the group consisting of mineral fillers, glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, wollastonite and any combination of two or more thereof. he personal electronic device of any one the preceding claims, wherein the polymer composition (PC) comprises from 5.0 wt.% to 50.0 wt.%, from 10.0 wt.% to 45.0 wt. % or from 15.0 wt.% to 40.0 wt.% of the at least one reinforcing agent, based upon the total weight of the polymer composition, wherein the at least one reinforcing agent is selected from the group consisting of mineral fillers, glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, wollastonite and any combination of two or more thereof. The personal electronic device according to any one of claims 20 or 21 , wherein the reinforcing agent is selected in the group consisting of carbon fibers and glass fibers.
43 The personal electronic device of any one of claims 1-20, wherein the polymer composition is substantially free of reinforcing agent(s). The personal electronic device of any one the preceding claims, wherein the polymer composition (PC) comprises at least one halogen free flame retardant, notably selected in the group of metal dialkyl phosphinates, organophosphates and phosphonates. The personal electronic device of claim 24, wherein the halogen free flame retardant may be selected in the group consisting of the compounds according to the formulae below:
[RaRbP(=O)O]m M
[RaP(=O)O-Rc-P(=O)ORb]n M where Ra and Rb are identical or different and are selected in the group consisting of linear or branched Ci-Cs-alkyl groups and aryl groups, Rc is selected in the group consisting of linear or branched Ci-C -alkylene groups, Ce-C -arylene groups, M is a metal ion selected in the group of Al, Ca and Zn, m is 2 or 3, n is 1 or 3, x is 1 or 2. he personal electronic device of claim 24 or 25, wherein the total proportion of the halogen free flame retardant(s) in the polymer composition (PC) is at least
1.0 wt.%.
44 e personal electronic device of any one the preceding claims, from 0.1 wt.% to
30 wt.%, from 0.2 wt.% to 25 wt.%, from 0.3 wt.% to 20 wt.%, from 0.4 wt.% to 15 wt.% or from 0.5 wt.% to 10 wt.% of the at least one additive other than a halogen free flame retardant, based upon the total weight of the polymer composition, wherein the at least one additive is selected from the group consisting of tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, nucleating agents, antioxidants and any combination thereof. he personal electronic device of any one the preceding claims, wherein the polyamide (PA) and/or the polymer composition (PC) exhibit(s) at least one, at least two, at least three, at least four, at least five, at least six or all of the following properties:
• UV resistance, as evidenced by a AE no more than 5.0, preferably no more than 4.0, preferably no more than 3.0, preferably no more than 2.0 or less, after 240 hours as measured according to ISO4892- 2:2013/AMD1 :2021 ;
• break resistance, as evidenced by an IZOD impact strength of at least 50.0 KJ/m2, preferably at least 60.0 KJ/m2, preferably at least 70.0
45 KJ/m2, preferably at least 80.0 KJ/m2, as measured according to
ISO180;
• flame resistance, as evidenced by a flammability rating of V1 or V2 measured according to the LIL94 standard;
• an elongation at break of greater than 2.0%, or greater than 2.5%, or greater than 3%, as measured according to ISO527-2;
• water absorption, by immersion in water at 25°C, as measured by ASTM D570 of less than 8.0 wt.%, preferably less than 7.0 wt.%, preferably less than 6.0 wt.%, preferably less than 5.0 wt.%, preferably less than 3.0 wt%;
• strength at yield (break) of greater than 45 MPa, or 50 MPa, or 55 MPa, as measured according to ISO527-2; and
• a glass transition temperature of greater than 90°C, preferably greater than 100°C, preferably greater than 110°C, preferably greater than 120°C. e personal electronic device of any one the preceding claims, wherein the polymer composition (PC) is present in a housing of the personal electronic device. e personal electronic device of any one the preceding claims, wherein the device is a a flavor delivery system.
46 flavor delivery system for delivery of an aerosol containing one or more active ingredients and/or flavors including a reservoir for holding the ingredient(s) and/or flavor(s), a heating element and a power source wherein the system also includes a housing made of or comprising the polymer composition (PC) as defined in any one of claims 1-28. e of a polymer composition (PC) as disclosed in any one of claims 1 -28 for the preparation of a housing of a personal electronic device selected from the group consisting of a mobile phone, a personal digital assistant, a laptop computer, a tablet computer, a wearable computing device, a flavor delivery system, a camera, a portable audio player, a portable radio, a global position system receiver, a medical device/piece of medical equipment and a portable game console. e of a polyamide (PA) as disclosed in any one of of the preceding claims for the preparation of a housing of a personal electronic device selected from the group consisting of a mobile phone, a personal digital assistant, a laptop computer, a tablet computer, a wearable computing device, a flavor delivery system, a camera, a portable audio player, a portable radio, a global position system receiver, a medical device/piece of medical equipment and a portable game console.
47
PCT/EP2022/085970 2021-12-15 2022-12-14 Personal electronic devices comprising polyamide composition WO2023111086A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21306780 2021-12-15
EP21306780.4 2021-12-15

Publications (1)

Publication Number Publication Date
WO2023111086A1 true WO2023111086A1 (en) 2023-06-22

Family

ID=79021515

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2022/085970 WO2023111086A1 (en) 2021-12-15 2022-12-14 Personal electronic devices comprising polyamide composition

Country Status (1)

Country Link
WO (1) WO2023111086A1 (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001323159A (en) * 2000-05-16 2001-11-20 Daicel Chem Ind Ltd Flame-retardant resin composition
US20100062272A1 (en) * 2006-12-13 2010-03-11 Evonik Degussa Gmbh Transparent part
US20140179850A1 (en) * 2012-12-21 2014-06-26 Ems-Patent Ag Stain-resistant article and use thereof
US20150025669A1 (en) 2013-07-17 2015-01-22 Shenzhen China Star Optoelectronics Technology Co., Ltd. Production Line System and Controlling Method Thereof
US20180274110A1 (en) 2017-03-23 2018-09-27 Kabushiki Kaisha Toshiba Laminated electrolyte membrane, membrane electrode assembly, water electrolysis cell, stack, and water electrolysis apparatus
WO2020150400A1 (en) 2019-01-15 2020-07-23 Juul Labs, Inc. Vaporizer devices
US20210032465A1 (en) * 2017-12-22 2021-02-04 Ems-Patent Ag Polyamide molding compound

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001323159A (en) * 2000-05-16 2001-11-20 Daicel Chem Ind Ltd Flame-retardant resin composition
US20100062272A1 (en) * 2006-12-13 2010-03-11 Evonik Degussa Gmbh Transparent part
US20140179850A1 (en) * 2012-12-21 2014-06-26 Ems-Patent Ag Stain-resistant article and use thereof
US20150025669A1 (en) 2013-07-17 2015-01-22 Shenzhen China Star Optoelectronics Technology Co., Ltd. Production Line System and Controlling Method Thereof
US20180274110A1 (en) 2017-03-23 2018-09-27 Kabushiki Kaisha Toshiba Laminated electrolyte membrane, membrane electrode assembly, water electrolysis cell, stack, and water electrolysis apparatus
US20210032465A1 (en) * 2017-12-22 2021-02-04 Ems-Patent Ag Polyamide molding compound
WO2020150400A1 (en) 2019-01-15 2020-07-23 Juul Labs, Inc. Vaporizer devices

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOHN MURPHY: "Fiberglass and Glass Technology", 2010, article "XIV", pages: 197 - 225

Similar Documents

Publication Publication Date Title
CN101765639B (en) Poly(arylene sulfide) resin composition, process for production thereof, and surface mount electronic component
JP4148774B2 (en) polyamide
JP5276000B2 (en) Flame retardant polyamide composition
US6184282B1 (en) Flameproof polyamide moulding compounds containing melamine cyanurate
JP5271894B2 (en) Flame retardant polyamide composition
US7645825B2 (en) Flame-retardant polyamide composition
TWI470027B (en) Flame-retadrant polyamide composition, molded article, method of facricating molded article by polyamide composition and electronics element
KR100436618B1 (en) A polyamide resin composition and moldings thereof
EP2414446A1 (en) Flame resistant semiaromatic polyamide resin composition and articles therefrom
JP2014122321A (en) Article having stain resistance and its use
EP2180018A1 (en) Polyamide composition
JP5853021B2 (en) Reinforced polyamide resin pellets
KR20000053601A (en) Polyamide composition
EP2871201A1 (en) Polyamide, polyamide composition, and molded article
JP2009263635A (en) Thermoplastic resin composition, process for producing the same, and electronic component for surface mounting
CN1454230A (en) Flame-retardant reinforced polyamide resin composition
CN110964316B (en) Polyamide composition, molded article, and semi-aromatic polyamide
KR101500824B1 (en) Polyamide and polyamide composition
JP2004107576A (en) Polyamide composition
CN110964315B (en) Polyamide composition, method for producing same, and molded article
JP2019014808A (en) Polyamide composition and molded article
WO2023111086A1 (en) Personal electronic devices comprising polyamide composition
JP2009203472A (en) Polyarylene sulfide resin composition, its preparing method and surface mount electronic component
JP5304040B2 (en) Thermoplastic resin composition with reduced gas generation and molded article using the same
JP6420995B2 (en) Flame-retardant polyamide resin composition and molded article thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22839223

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE