# US 10,767,011 B2 · Transparent polyamide moulding compositions with high tensile strain at break > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,767,011 B2 - Document ID: US10767011B2 - Status: Granted - Kind: B2 - Application number: 15/842,959 - Filed: 2017-12-15 - Published: 2018-06-21 - Granted: 2020-09-08 - Earliest claimed: 2016-12-16 - Assignees: Ems-Patent AG - Applicants: Ems-Patent AG - Inventors: Thomas Wiedemann; Manfred Hewel - Web page: https://patentgrep.com/patent/US10767011B2 ## CPC - C08G 69/265: {from at least two different diamines or at least two different dicarboxylic acids} - C08G 69/28: Preparatory processes - B29B 9/06: in the form of filamentary material, e.g. combined with extrusion - B29K 2077/00: Use of {PA, i.e.} polyamides, e.g. polyesteramides {or derivatives thereof}, as moulding material - B29K 2995/0026: Transparent - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - B29B: PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS - B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS ## Abstract A polyamide moulding composition with particularly good tensile strain at break consisting of the following constituents: (A) 50 to 100% by weight of at least one transparent polyamide composed of: (a1) 55 to 77 mol % of acyclic, aliphatic diamine having 5-10 carbon atoms; (a2) 23 to 45 mol % of cycloaliphatic diamine having 6-36 C atoms, where the proportions of (a1) and (a2) are based on the entirety of the diamines used; (a3) 40 to 80 mol % of aromatic dicarboxylic acid or a mixture of such dicarboxylic acids; and (a4) 20 to 60 mol % of acyclic, aliphatic dicarboxylic acid having 8 to 16 carbon atoms, or a mixture of such dicarboxylic acids, where the proportions of (a3) and (a4) are based on the entirety of the dicarboxylic acids used; and (B) 0-50% by weight of additives; where the entirety of components (A) and (B) gives 100% by weight. ## Claims ### Claim 1 A polyamide moulding composition consisting of the following constituents: (A) 50 to 100% by weight of at least one transparent polyamide composed of: (a1) 60 to 77 mol % of a linear aliphatic diamine having 6 to 10 carbon atoms; (a2) 23 to 33 mol % of exclusively bis(4-amino-3-methylcyclohexyl)methane (MACM), where the proportions of (a1) and (a2) are based on an entirety of the diamines used and give a total of 100 mol %; (a3) 40 to 80 mol % of a mixture of terephthalic acid and isophthalic acid in a molar ratio of 1.5:1-1:1.5; and (a4) 20 to 60 mol % of an acyclic, linear aliphatic dicarboxylic acid selected from the group consisting of decanedioic acid, undecanedioic acid, dodecanedioic acid, and mixtures thereof; where the proportions of (a3) and (a4) are based on an entirety of the dicarboxylic acids used and give a total of 100 mol %; and (B) 0 to 50% by weight of additives; wherein an entirety of components (A) and (B) gives 100% by weight. ### Claim 2 (depends on 1) The polyamide moulding composition according to claim 1, wherein the proportion of (a3) is in the range 40-78 mol %, and/or wherein the proportion of (a4) is in the range 22-60 mol %, where the proportions of (a3) and (a4) are based on the entirety of the dicarboxylic acids used and give a total of 100 mol %. ### Claim 3 (depends on 1) The polyamide moulding composition according to claim 1, wherein the proportion of component (A) is in the range 60 to 99.9% by weight, based on the moulding composition made of (A) and (B), and/or wherein the proportion of component (B) is in the range 0-50% by weight, based on the moulding composition made of (A) and (B). ### Claim 4 (depends on 1) The polyamide moulding composition according to claim 1, wherein (a1) is selected to be 1,6-hexamethylenediamine; and (a4) is selected to be dodecanedioic acid. ### Claim 5 (depends on 1) The polyamide moulding composition according to claim 1, wherein the additives of component (B) are selected from the group consisting of: polyamides different from (A); UV stabilizers; heat stabilizers; free-radical scavengers, processing aids; inclusion preventers; lubricants; demoulding aids, inclusive of metal stearates and metal montanates, mineral oils and fatty acid amides; plasticizers; functional additives for influencing optical properties; impact modifiers; fillers and/or aggregates; optical brighteners; dyes and mixtures thereof. ### Claim 6 (depends on 1) A process for the production of a polyamide moulding composition according to claim 1, wherein the production of polymer component (A) takes place in pressure vessels, with a pressure phase at 270° C. to 330° C. followed by depressurization at 260° C. to 320° C., followed by devolatilization at 260° C. to 320° C., and also discharge of the polyamide moulding composition in strand form, cooling, pelletization and drying of the pellets, compounding of component (A), and if present (B), in the form of pellets and moulding in an extruder at melt temperatures of 250° C. to 350° C. to give a strand, and chopping by suitable pelletizers to give pellets. ### Claim 7 (depends on 1) A moulding, obtained from a polyamide moulding composition according to claim 1 by means of injection-moulding processes and/or injection-compression-moulding processes at melt temperatures of 230° C. to 320° C., where the mould is adjusted to temperatures of 40° C. to 130° C. and where optionally the mould at temperatures of 40° C. to 130° C. after filling of the cavity applies compression to the hot moulding. ### Claim 8 (depends on 7) The moulding according to claim 7, wherein the moulding has a light transmittance, measured in accordance with ASTM D1003, determined on plaques measuring 2×60×60 mm or on discs measuring 2×70 mm, at a temperature of 23° C., with haze-gard plus measurement equipment from the company Byk Gardner using CIE illuminant C, of at least 85%, and/or characterized by haze measured in accordance with ASTM D1003 of at most 5%, of a plaque of thickness 2 mm produced from the transparent polyamide moulding composition. ### Claim 9 (depends on 7) The moulding according to claim 7, wherein the moulding has a tensile strain at break of at least 100%, measured in accordance with ISO 527 at a tensile testing velocity of 50 mm/min on an ISO tensile specimen of type Al, 170×20/10×4 mm, at a temperature of 23° C., and/or a tensile modulus of elasticity of more than 2000 MPa measured in accordance with ISO 527 with a tensile testing velocity of 1 mm/min on an ISO tensile specimen of type Al, 170×20/10×4 mm, at a temperature of 23° C. ### Claim 10 (depends on 7) The moulding according claim 7, wherein said moulding is a housing element or display element or a component element of a machine, of an automobile, of a household device, of a toy, of a sports item or of an electrical or electronic device or is a spectacle frame, a spectacle lens or other lens, a binocular, a viewing window for heating systems with direct oil contact, a filter cup for drinking-water treatment, a feeding bottle, carbonization bottle, crockery, flow meter for gases or liquids, clock casing, watch casing, lamp housing or reflector for automobile lamps or element thereof. ### Claim 11 (depends on 1) The polyamide moulding composition according to claim 1, wherein the starting material (a1) is a linear diamine having 6-8 carbon atoms. ### Claim 12 (depends on 1) The polyamide moulding composition according to claim 1, wherein the starting material (a1) is at least one of 1,6-hexamethylenediamine and 2-methyl-1,5-pentanediamine. ### Claim 13 (depends on 1) The polyamide moulding composition according to claim 1, wherein the proportion of (a1) is in the range 60-72 mol %, and/or wherein the proportion of (a2) is in the range 28-40 mol %, where the proportions of (a1) and (a2) are based on the entirety of the diamines used and give a total of 100 mol %, and/or wherein the proportion of (a3) is in the range 60-75 mol %, and/or wherein the proportion of (a4) is in the range 25-40 mol %, where the proportions of (a3) and (a4) are based on the entirety of the dicarboxylic acids used and give a total of 100 mol %. ### Claim 14 (depends on 1) The polyamide moulding composition according to claim 1, wherein the starting material (a3) is an equimolar mixture of terephthalic acid and isophthalic acid. ### Claim 15 (depends on 1) The polyamide moulding composition according to claim 1, wherein the starting material (a4) is exclusively dodecanedioic acid. ### Claim 16 (depends on 1) The polyamide moulding composition according to claim 1, wherein the proportion of component (A) is in the range 97.0 to 99.5% by weight, based in each case on the moulding composition made of (A) and (B), and/or wherein the proportion of component (B) is in the range 0.5-20% by weight, based in each case on the moulding composition made of (A) and (B). ### Claim 17 (depends on 1) The polyamide moulding composition according to claim 1, wherein component (B) is present in proportions of at most 3% by weight, based on the moulding composition made of (A) and (B). ### Claim 18 (depends on 1) The polyamide moulding composition according to claim 1, wherein (a1) is selected to be 1,6-hexamethylenediamine; (a2) is exclusively MACM; (a3) is selected to be a mixture of terephthalic acid and isophthalic acid in a ratio of 1.5:1-1:1.5; and (a4) is selected to be dodecanedioic acid. ### Claim 19 (depends on 1) The polyamide moulding composition according to claim 1, wherein (a1) is selected to be 1,6-hexamethylenediamine; (a2) is exclusively MACM; (a3) is selected to be a mixture of terephthalic acid and isophthalic acid in a ratio of 1.5:1-1:1.5; and (a4) is selected to be dodecanedioic acid, where the proportions of the components are selected as follows: (a1) in the range 60-75 mol %; (a2) in the range 25-40 mol %; (a3) in the range 60-75 mol %; (a4) in the range 25-40 mol %; and where the proportions of (a1) and (a2) are based on the entirety of the diamines used and give a total of 100 mol %, and where the proportions of (a3) and (a4) are based on the entirety of the dicarboxylic acids used and give a total of 100 mol %. ### Claim 20 (depends on 1) The polyamide moulding composition according to claim 1, wherein the additives of component (B) are selected from the group consisting of: polyamides different from (A); UV stabilizers; heat stabilizers; free-radical scavengers, processing aids; inclusion preventers; lubricants; demoulding aids, inclusive of metal stearates and metal montanates, where the metal is selected from the group consisting of magnesium, calcium, barium, mineral oils and fatty acid amides; plasticizers; functional additives for influencing optical properties including refractive index; impact modifiers; fillers and/or aggregates; optical brighteners; dyes and mixtures thereof, where the fillers and/or aggregates are nanoscale and/or selected from the following group: glass fibres, glass beads, carbon fibres, carbon black, graphite, flame retardants, mineral inclusive of titanium dioxide, calcium carbonate and barium sulphate. ### Claim 21 (depends on 7) The moulding according to claim 7, having a light transmittance, measured in accordance with ASTM D1003, determined on plaques measuring 2×60×60 mm or on discs measuring 2×70 mm, at a temperature of 23° C., with haze-gard plus measurement equipment from the company Byk Gardner using CIE illuminant C, of at least 90%, and/or having a haze measured in accordance with ASTM D1003 of at most 2%, of a plaque of thickness 2 mm produced from the transparent polyamide moulding composition. ### Claim 22 (depends on 7) The moulding according to claim 7, wherein the moulding has a tensile strain at break of at least 130%, measured in accordance with ISO 527 at a tensile testing velocity of 50 mm/min on an ISO tensile specimen of type Al, 170×20/10×4 mm, at a temperature of 23° C., and/or a tensile modulus of elasticity of more than 2100 MPa, measured in accordance with ISO 527 with a tensile testing velocity of 1 mm/min on an ISO tensile specimen of type Al, 170×20/10×4 mm, at a temperature of 23° C. ### Claim 23 (depends on 7) The moulding according to claim 7, wherein the moulding is a housing element or display element or a component element of a machine, of an automobile, of a household device, of a toy, of a sports item or of a portable electrical or electronic device, including a mobile phone, computer, laptop, GPS device, MP3 player, camera, optical device or combination thereof, or is a spectacle frame, a spectacle lens or other lens, a binocular, a viewing window for heating systems with direct oil contact, a filter cup for drinking-water treatment, a feeding bottle, carbonization bottle, crockery, flow meter for gases or liquids, clock casing, watch casing, lamp housing or reflector for automobile lamps or element thereof. ### Claim 24 A polyamide moulding composition consisting of the following constituents: (A) 50 to 100% by weight of at least one transparent polyamide composed of: (a1) 60 to 77 mol % of 1,6-hexamethylenediamine; (a2) 23 to 33 mol % of exclusively bis(4-amino-3-methylcyclohexyl)methane (MACM), where the proportions of (a1) and (a2) are based on an entirety of the diamines used and give a total of 100 mol %; (a3) 40 to 80 mol % of a mixture of terephthalic acid and isophthalic acid in a molar ratio of 1.5:1-1:1.5; and (a4) 20 to 60 mol % of exclusively dodecanedioic acid; where the proportions of (a3) and (a4) are based on the entirety of the dicarboxylic acids used and give a total of 100 mol %; and (B) 0 to 3% by weight of additives; wherein an entirety of components (A) and (B) gives 100% by weight. ### Claim 25 A polyamide moulding composition consisting of the following constituents: (A) 50 to 100% by weight of at least one transparent polyamide composed of: (a1) 63 to 75 mol % of 1,6-hexamethylenediamine; (a2) 25 to 33 mol % of exclusively bis(4-amino-3-methylcyclohexyl)methane (MACM), where the proportions of (a1) and (a2) are based on an entirety of the diamines used and give a total of 100 mol %; (a3) 60 to 75 mol % of a mixture of terephthalic acid and isophthalic acid in an equimolar ratio; and (a4) 25 to 40 mol % of exclusively dodecanedioic acid; where the proportions of (a3) and (a4) are based on the entirety of the dicarboxylic acids used and give a total of 100 mol %; and (B) 0 to 3% by weight of additives; wherein an entirety of components (A) and (B) gives 100% by weight.