# US 2014/0194570 A1 · Production method of crystalline polyamide resin > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0194570 A1 - Document ID: US20140194570A1 - Status: Published application - Kind: A1 - Application number: 14/237,300 - Filed: 2012-08-13 - Published: 2014-07-10 - Earliest claimed: 2011-08-17 - Assignees: Toray Industries, Inc. - Inventors: Koya Kato; Atsushi Masunaga; Eri Hatano; Hideo Matsuoka - Web page: https://patentgrep.com/patent/US20140194570A1 ## CPC - C08G 69/28: Preparatory processes - C08G 69/265: {from at least two different diamines or at least two different dicarboxylic acids} - C08G 69/36: derived from amino acids, polyamines and polycarboxylic acids - C08K 7/06: Elements - C08K 7/14: Glass - C08L 77/06: Polyamides derived from polyamines and polycarboxylic acids (C08L77/10 takes precedence) - C08K 5/005: {Stabilisers against oxidation, heat, light, ozone} - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract There is provided a production method of a crystalline polyamide resin by thermal polycondensation of a mixture including at least a diamine component, a dicarboxylic acid component and water as a starting material, wherein the diamine component includes (A) pentamethylene diamine at a ratio that is equal to or greater than 10 mol % and less than 80 mol % relative to a gross amount of the diamine component; and the dicarboxylic acid component includes (B) at least one selected from the group consisting of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid and dialkyl ester derivatives thereof at a ratio that is equal to or greater than 76 mol % and equal to or less than 100 mol % relative to a gross amount of the dicarboxylic acid component, the production method comprising: a first step that heats the above mixture, which has a water content equal to or less than 30% by weight, at a temperature equal to or higher than 200° C. under a pressure of 1.8 to 3.5 MPa to perform polycondensation with distillation of water; a second step that releases pressure to an atmospheric pressure level, subsequent to the first step; and a third step that continues thermal polycondensation subsequent to the second step, so as to obtain the crystalline polyamide resin, the third step performing high-degree melt polymerization at a temperature that is equal to or higher than a melting point of the crystalline polyamide resin until a relative viscosity at 25° C. of a solution prepared by dissolving the obtained crystalline polyamide resin at a concentration of 0.01 mg/mL in 98% sulfuric acid reaches between 1.8 and 3.5. ## Claims ### Claim 1 A production method of a crystalline polyamide resin by thermal polycondensation of a mixture including at least a diamine component, a dicarboxylic acid component and water as a starting material, wherein the diamine component includes (A) pentamethylene diamine at a ratio that is equal to or greater than 10 mol % and less than 80 mol % relative to a gross amount of the diamine component, and the dicarboxylic acid component includes (B) at least one selected from the group consisting of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid and dialkyl ester derivatives thereof at a ratio that is equal to or greater than 76 mol % and equal to or less than 100 mol % relative to a gross amount of the dicarboxylic acid component, the production method comprising: a first step that heats the mixture, which has a water content equal to or less than 30% by weight, at a temperature equal to or higher than 200° C. under a pressure of 1.8 to 3.5 MPa to perform polycondensation with distillation of water; a second step that releases pressure to an atmospheric pressure level, subsequent to the first step; and a third step that continues thermal polycondensation subsequent to the second step, so as to obtain the crystalline polyamide resin, the third step performing high-degree melt polymerization at a temperature that is equal to or higher than a melting point of the crystalline polyamide resin until a relative viscosity at 25° C. of a solution prepared by dissolving the obtained crystalline polyamide resin at a concentration of 0.01 mg/mL in 98% sulfuric acid reaches between 1.8 and 3.5. ### Claim 2 (depends on 1) The production method of the crystalline polyamide resin according to claim 1, wherein the crystalline polyamide resin has a temperature of an endothermic peak corresponding to the melting point measured by using a differential scanning calorimeter, which is equal to or higher than 270° C. when temperature is decreased from a molten state to 30° C. at a temperature decrease rate of 20° C./minute and is subsequently increased at a temperature increase rate of 20° C./minute. ### Claim 3 (depends on 1) The production method of the crystalline polyamide resin according to claim 1, wherein the crystalline polyamide resin has heat of fusion measured by using a differential scanning calorimeter, which is equal to or greater than 30 J/g when temperature is decreased from a molten state to 30° C. at a temperature decrease rate of 20° C./minute and is subsequently increased at a temperature increase rate of 20° C./minute. ### Claim 4 (depends on 1) The production method of the crystalline polyamide resin according to claim 1, wherein a temperature at a start of pressure relief is equal to or lower than 295° C., and a temperature at an end of pressure relief is equal to or higher than the melting point in the second step. ### Claim 5 (depends on 1) The production method of the crystalline polyamide resin according to claim 1, wherein the high-degree melt polymerization in the third step is performed under reduced pressure or under an inert gas atmosphere. ### Claim 6 A crystalline polyamide resin produced by thermal polycondensation of at least a diamine component and a dicarboxylic acid component, wherein the diamine component includes (A) pentamethylene diamine at a ratio that is equal to or greater than 10 mol % and less than 80 mol % relative to a gross amount of the diamine component, and the dicarboxylic acid component includes (B) at least one selected from the group consisting of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid and dialkyl ester derivatives thereof at a ratio that is equal to or greater than 76 mol % and equal to or less than 100 mol % relative to a gross amount of the dicarboxylic acid component, the crystalline polyamide resin having a relative viscosity between 1.8 and 3.5 at 25° C. of a solution prepared by dissolving the crystalline polyamide resin at a concentration of 0.01 mg/mL in 98% sulfuric acid, and having a degree of dispersion (weight-average molecular weight/number-average molecular weight) equal to or less than 3.5 measured by gel permeation chromatography. ### Claim 7 (depends on 6) The crystalline polyamide resin according to claim 6, the crystalline polyamide resin having a temperature of an endothermic peak corresponding to a melting point measured by using a differential scanning calorimeter, which is equal to or higher than 270° C. when temperature is decreased from a molten state to 30° C. at a temperature decrease rate of 20° C./minute and is subsequently increased at a temperature increase rate of 20° C./minute. ### Claim 8 (depends on 6) The crystalline polyamide resin according to claim 6, the crystalline polyamide resin having heat of fusion measured by using a differential scanning calorimeter, which is equal to or greater than 30 J/g measured by using a differential scanning calorimeter when temperature is decreased from a molten state to 30° C. at a temperature decrease rate of 20° C./minute and is subsequently increased at a temperature increase rate of 20° C./minute. ### Claim 9 (depends on 6) The crystalline polyamide resin according to claim 6, the crystalline polyamide resin having a piperidine content that is equal to or less than 10.0×10−5 mol/g. ### Claim 10 (depends on 6) The crystalline polyamide resin according to claim 6, wherein (B) the at least one selected from the group consisting of the aromatic dicarboxylic acid, the alicyclic dicarboxylic acid and the dialkyl ester derivatives thereof includes at least an aromatic dicarboxylic acid, and the aromatic dicarboxylic acid is terephthalic acid and/or isophthalic acid. ### Claim 11 (depends on 6) A molded product produced by molding the crystalline polyamide resin according to claim 6. ### Claim 12 (depends on 6) A polyamide resin composition produced by further adding an inorganic filler to the crystalline polyamide resin according to claim 6. ### Claim 13 (depends on 6) A polyamide resin composition produced by further adding an impact modifier to the crystalline polyamide resin according to claim 6. ### Claim 14 (depends on 12) A molded product produced by molding the crystalline polyamide resin composition according to claim 12. ### Claim 15 (depends on 13) A molded product produced by molding the crystalline polyamide resin composition according to claim 13.