Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

• the present invention relates to a polyamide resin, a resin composition, and a molded article.
• Crystalline polyamide resins such as nylon 6 and nylon 66
• polyamide resins With the increase in demand for polyamide resins, there is a demand for novel polyamide resins having new functions.
• Patent Document 1 describes a polyamide resin (A) containing 95 to 99.95 mass % of polyamide (a-1) having a number average molecular weight of 2000 or more and 0.05 to 5 mass % of polyamide oligomer (a-2) having a number average molecular weight of 500 or more and less than 2000, in which 25 mol % or more of all monomer units constituting the polyamide (a-1) and the polyamide oligomer (a-2) are structural units derived from an alicyclic monomer represented by the following general formula (I) or general formula (II), and the content of trans isomer structural units derived from the alicyclic monomer is 50 to 85 mol %.
• polyamide resin (A) containing 95 to 99.95 mass % of polyamide (a-1) having a number average molecular weight of 2000 or more and 0.05 to 5 mass % of polyamide oligomer (a-2) having a number average molecular weight of 500 or more and less than 2000, in which 25 mol % or more
• X represents a carboxyl group or an amino group
• Z represents an alicyclic structure having 3 or more carbon atoms.
• X and Z are as defined above, and R1 and R2 each independently represent an alkylene group having one or more carbon atoms.
• the present invention has an object to solve the above problems, and to provide a polyamide resin having a fast crystallization rate and a high glass transition temperature, as well as a resin composition and a molded article using the polyamide resin.
• the inventors have conducted research and found that the above problems can be solved by replacing a portion of the dicarboxylic acid in a polyamide resin synthesized from bisaminomethylcyclohexane and an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms with cyclohexanedicarboxylic acid. Specifically, the above problems were solved by the following means.
• ⁇ 1> Contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, 70 mol % or more of the diamine-derived structural units are derived from bisaminomethylcyclohexane, A polyamide resin in which 99 to 60 mol % of the dicarboxylic acid-derived structural units are derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and 1 to 40 mol % are derived from cyclohexanedicarboxylic acid (however, the total of the structural units derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms and the structural units derived from cyclohexanedicarboxylic acid does not exceed 100 mol %).
• ⁇ 2> The polyamide resin according to ⁇ 1>, wherein the bisaminomethylcyclohexane includes 1,4-bisaminomethylcyclohexane.
• ⁇ 3> The polyamide resin according to ⁇ 2>, wherein the ratio of the trans isomer of the 1,4-bisaminomethylcyclohexane is 35 to 55 mol %.
• ⁇ 4> The polyamide resin according to ⁇ 2> or ⁇ 3>, in which 1 to 20 mol % of the dicarboxylic acid-derived structural units are derived from cyclohexanedicarboxylic acid.
• ⁇ 5> The polyamide resin according to ⁇ 1>, wherein the bisaminomethylcyclohexane includes 1,3-bisaminomethylcyclohexane.
• ⁇ 6> The polyamide resin according to ⁇ 5>, wherein the ratio of the trans isomer of the 1,3-bisaminomethylcyclohexane is 0 to 40 mol %.
• ⁇ 7> The polyamide resin according to ⁇ 5> or ⁇ 6>, in which 1 to 40 mol % of the dicarboxylic acid-derived structural units are derived from cyclohexanedicarboxylic acid.
• ⁇ 8> The polyamide resin according to any one of ⁇ 1> to ⁇ 7>, wherein the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms includes adipic acid.
• ⁇ 9> The polyamide resin according to any one of ⁇ 1> to ⁇ 8>, wherein the polyamide resin has a glass transition temperature (Tg) of 113 to 200° C. as measured by differential scanning calorimetry (DSC).
• Tg glass transition temperature
• DSC differential scanning calorimetry
• a resin composition comprising the polyamide resin according to any one of ⁇ 1> to ⁇ 9> and a reinforcing filler.
• ⁇ 11> A molded article formed from the polyamide resin according to any one of ⁇ 1> to ⁇ 9>.
• ⁇ 12> A molded article formed from the resin composition according to ⁇ 10>.
• the present invention makes it possible to provide a polyamide resin with a fast crystallization rate and a high glass transition temperature, as well as a resin composition and a molded article using the polyamide resin.
• the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
• the use of "to” means that the numerical values before and after it are included as the lower limit and upper limit.
• various physical properties and characteristic values are those at 23° C. unless otherwise specified.
• the number average molecular weight can be measured according to the description in paragraph 0047 of JP2018-165298A, the contents of which are incorporated herein by reference. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they will be based on the standards as of January 1, 2022, unless otherwise specified.
• the polyamide resin of the present embodiment contains diamine-derived structural units and dicarboxylic acid-derived structural units, and is characterized in that 70 mol % or more of the diamine-derived structural units are derived from bisaminomethylcyclohexane, and 99 to 60 mol % of the dicarboxylic acid-derived structural units are derived from an ⁇ , ⁇ -straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and 1 to 40 mol % are derived from cyclohexanedicarboxylic acid (however, the total of the structural units derived from an ⁇ , ⁇ -straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms and the structural units derived from cyclohexanedicarboxylic acid does not exceed 100 mol %).
• a polyamide resin having a high crystallization rate and a high glass transition temperature can be obtained.
• the diamine-derived structural units are derived from bisaminomethylcyclohexane, and depending on the application, etc., more preferably 90 mol % or more, even more preferably 95 mol % or more, and even more preferably 99 mol % or more are derived from bisaminomethylcyclohexane.
• the bisaminomethylcyclohexane is preferably 1,3-bisaminomethylcyclohexane and/or 1,4-bisaminomethylcyclohexane, and more preferably 1,4-bisaminomethylcyclohexane.
• the ratio of the trans isomer of the bisaminomethylcyclohexane (the ratio when the total of the trans isomer and the cis isomer is taken as 100 mol%) is preferably 5 mol% or more, and may be 12 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol%, 30 mol% or more, 35 mol% or more, 38 mol% or more, 42 mol%, or 48 mol% or more depending on the application.
• the upper limit of the ratio of the trans isomer of the bisaminomethylcyclohexane (the ratio when the total of the trans isomer and the cis isomer is taken as 100 mol%) is preferably 55 mol% or less, and may be 52 mol% or less, 48 mol% or less, 43 mol% or less, 38 mol% or less, 35 mol% or less, 30 mol% or less, 25 mol% or less, 20 mol% or less, or 15 mol% or less depending on the application.
• examples of diamines other than bisaminomethylcyclohexane include aliphatic diamines, alicyclic diamines other than bisaminomethylcyclohexane, and aromatic diamines.
• the aliphatic diamine is preferably an aliphatic diamine having 6 to 12 carbon atoms, and examples thereof include linear aliphatic diamines such as 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine, and branched aliphatic diamines such as 2-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, 2,2,4-/2,4,4-trimethylhexanediamine, 2-methyl-1,5-pentanediamine, 2-methyl-1,6-hexanediamine, and 2-methyl-1,7-heptanediamine.
• linear aliphatic diamines such as 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-n
• alicyclic diamines other than bisaminomethylcyclohexane examples include isophoronediamine, 4,4'-thiobis(cyclohexane-1-amine), 4,4'-thiobis(cyclohexane-1-amine), and the like.
• An example of the aromatic diamine is xylylenediamine.
• the proportion of the constituent units derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms in the dicarboxylic acid-derived constituent units in the polyamide resin of this embodiment is 60 mol% or more, preferably 65 mol% or more, more preferably 68 mol% or more, even more preferably 72 mol% or more, even more preferably 77 mol% or more, and even more preferably 82 mol% or more.
• the thermal stability during production of the resin composition tends to be further improved.
• the proportion of the constituent units derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms in the dicarboxylic acid-derived constituent units in the polyamide resin of this embodiment is 99 mol% or less, preferably 96 mol% or less, more preferably 94 mol% or less, and even more preferably 88 mol% or less. By making it equal to or less than the upper limit, the crystallization rate tends to be further improved.
• the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is preferably an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 15 carbon atoms, and more preferably an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 8 carbon atoms.
• Specific examples of the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. At least one selected from adipic acid, sebacic acid, and dodecanedioic acid is preferred, adipic acid and/or sebacic acid is more preferred, and adipic acid is even more preferred.
• the proportion of the constituent units derived from cyclohexanedicarboxylic acid in the constituent units derived from the dicarboxylic acid is 1 mol% or more, preferably 4 mol% or more, more preferably 6 mol% or more, and even more preferably 12 mol% or more.
• the proportion of the constituent units derived from cyclohexanedicarboxylic acid in the constituent units derived from the dicarboxylic acid is 40 mol% or less, preferably 35 mol% or less, more preferably 32 mol% or less, even more preferably 28 mol% or less, even more preferably 23 mol% or less, and even more preferably 18 mol% or less.
• Cyclohexanedicarboxylic acid is preferably 1,3-cyclohexanedicarboxylic acid and/or 1,4-cyclohexanedicarboxylic acid, more preferably 1,4-cyclohexanedicarboxylic acid.
• Examples of the ⁇ , ⁇ -straight-chain aliphatic dicarboxylic acids and cyclohexanedicarboxylic acids having 4 to 20 carbon atoms include alicyclic dicarboxylic acids other than cyclohexanedicarboxylic acid, phthalic acid compounds such as isophthalic acid, terephthalic acid, and orthophthalic acid, and isomers of naphthalenedicarboxylic acid such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid,
• the total amount of constituent units derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms and constituent units derived from cyclohexanedicarboxylic acid is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more, out of a total of 100 mol% of constituent units derived from dicarboxylic acids.
• the total amount of constituent units derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms and constituent units derived from cyclohexanedicarboxylic acid does not exceed 100 mol%.
• the polyamide resin of this embodiment is mainly composed of diamine units and dicarboxylic acid units, but does not exclude the inclusion of other monomer units, and may of course include lactams such as ⁇ -caprolactam and laurolactam, and aliphatic aminocarboxylic acid units such as aminocaproic acid and aminoundecanoic acid.
• the main component means that, among the monomer units constituting the polyamide resin, the total number of diamine units and dicarboxylic acid units is the largest among all monomer units.
• the total of diamine units and dicarboxylic acid units in the polyamide resin preferably accounts for 90.0% by mass or more of the total monomer units, more preferably 95.0% by mass or more, and even more preferably 98.0% by mass or more.
• the polyamide resin of this embodiment preferably has a lower limit of number average molecular weight (Mn) of 5,000 or more, and more preferably 10,000 or more.
• Mn number average molecular weight
• the upper limit of the Mn is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.
• the polyamide resin of the present embodiment preferably has a melting point (Tm) of 150° C. or higher.
• Tm melting point
• the upper limit of the melting point is not particularly limited, but is practically 300° C. or lower. be.
• the polyamide resin of the present embodiment preferably has a glass transition temperature (Tg) of 113° C. or higher.
• Tg glass transition temperature
• the upper limit of the glass transition temperature is not particularly limited, but is practically 200° C. or lower.
• the polyamide resin of this embodiment preferably has a crystallization temperature (Tcc) upon cooling according to differential scanning calorimetry (DSC) of 180°C or higher, and preferably 260°C or lower.
• Tcc crystallization temperature
• the polyamide resin of this embodiment preferably has a difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature (Tcc) during cooling according to differential scanning calorimetry (DSC) of 58°C or less.
• DSC differential scanning calorimetry
• the lower limit of the difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature during cooling (Tcc) is not particularly set, but may be, for example, 5°C or more, or further 10°C or more, 15°C or more, or 18°C or more.
• the melting point (Tm), glass transition temperature (Tg), and crystallization temperature during cooling (Tcc) are measured according to the description in the Examples section below (hereinafter the same applies to the melting point, glass transition temperature, and crystallization temperature during cooling).
• the bisaminomethylcyclohexane contains 1,4-bisaminomethylcyclohexane.
• preferably 70 mol % or more, more preferably 80 mol % or more, even more preferably 90 mol % or more, still more preferably 95 mol % or more, and even more preferably 99 mol % or more of the bisaminomethylcyclohexane is 1,4-bisaminomethylcyclohexane.
• the ratio of the trans isomer of 1,4-bisaminomethylcyclohexane (the ratio when the total of the trans isomer and the cis isomer is 100 mol%) is preferably 35 mol% or more, more preferably 38 mol% or more, even more preferably 42 mol% or more, even more preferably 46 mol% or more, and preferably 55 mol% or less, more preferably 53 mol% or less.
• the ratio of the trans isomer of 1,4-bisaminomethylcyclohexane is preferably 35 mol% or more, more preferably 38 mol% or more, even more preferably 42 mol% or more, even more preferably 46 mol% or more, and preferably 55 mol% or less, more preferably 53 mol% or less.
• the proportion of the constituent units derived from cyclohexanedicarboxylic acid in the constituent units derived from the dicarboxylic acid is 1 mol% or more, preferably 4 mol% or more, more preferably 6 mol% or more, and even more preferably 12 mol% or more.
• the proportion of the constituent units derived from cyclohexanedicarboxylic acid in the constituent units derived from the dicarboxylic acid is preferably 20 mol% or less, and more preferably 18 mol% or less.
• the polyamide resin of the first embodiment preferably has a melting point of 250° C. or higher, and more preferably 255° C. or higher.
• the upper limit of the melting point is not particularly set, but is practically 350° C. or lower.
• the polyamide resin of the first embodiment preferably has a glass transition temperature of 111° C. or higher, more preferably 113° C. or higher, even more preferably 118° C. or higher, and even more preferably 120° C. or higher.
• the upper limit of the glass transition temperature is not particularly limited, but is practically 140° C. or lower.
• the polyamide resin of the first embodiment preferably has a crystallization temperature (Tcc) during cooling according to differential scanning calorimetry (DSC) of 200°C or higher, and more preferably 210°C or higher.
• the upper limit of the crystallization temperature (Tcc) during cooling of the polyamide resin of the first embodiment is preferably 260°C or lower, more preferably 255°C or lower, even more preferably 251°C or lower, and even more preferably 248°C or lower.
• the polyamide resin of the first embodiment preferably has a difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature (Tcc) when cooled according to differential scanning calorimetry (DSC) of 44°C or less, more preferably 40°C or less, even more preferably 38°C or less, and even more preferably 35°C or less.
• the lower limit of the difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature when cooled (Tcc) is preferably 5°C or more, more preferably 10°C or more, even more preferably 15°C or more, and even more preferably 20°C or more.
• the bisaminomethylcyclohexane contains 1,3-bisaminomethylcyclohexane.
• preferably 70 mol % or more, more preferably 80 mol % or more, even more preferably 90 mol % or more, still more preferably 95 mol % or more, and even more preferably 99 mol % or more of the bisaminomethylcyclohexane is 1,3-bisaminomethylcyclohexane.
• the ratio of the trans isomer of 1,3-bisaminomethylcyclohexane (the ratio when the sum of the trans isomer and the cis isomer is 100 mol%) is 0 mol% or more, preferably 5 mol% or more, more preferably 8 mol% or more, even more preferably 12 mol% or more, even more preferably 15 mol% or more, even more preferably 20 mol% or more, even more preferably 25 mol% or more, and preferably 40 mol% or less, preferably 35 mol% or less, and more preferably 30 mol% or less.
• the lower limit there is a tendency that the thermal deterioration of the resin composition can be effectively suppressed.
• the upper limit a faster crystallization rate can be realized.
• the proportion of the constituent units derived from cyclohexanedicarboxylic acid in the constituent units derived from the dicarboxylic acid is 1 mol% or more, preferably 4 mol% or more, more preferably 6 mol% or more, even more preferably 12 mol% or more, even more preferably 16 mol% or more, even more preferably 21 mol% or more, and even more preferably 26 mol% or more.
• the proportion of the constituent units derived from cyclohexanedicarboxylic acid in the constituent units derived from the dicarboxylic acid is 40 mol% or less, preferably 35 mol% or less, and more preferably 32 mol% or less.
• the polyamide resin of the second embodiment has a melting point of preferably 240° C. or higher, more preferably 250° C. or higher, even more preferably 255° C. or higher, and even more preferably 260° C. or higher.
• the upper limit of the melting point is not particularly set, but is practically 300° C. or lower.
• the polyamide resin of the second embodiment has a glass transition temperature of preferably 110° C. or higher, more preferably 115° C. or higher, even more preferably 121° C. or higher, and still more preferably 125° C. or higher.
• the upper limit of the glass transition temperature is not particularly limited, but is practically 150° C. or lower.
• the polyamide resin of the second embodiment preferably has a crystallization temperature (Tcc) during cooling according to differential scanning calorimetry (DSC) of 183°C or higher, more preferably 190°C or higher, even more preferably 200°C or higher, and even more preferably 220°C or higher.
• the upper limit of the crystallization temperature (Tcc) during cooling of the polyamide resin of the second embodiment is preferably 255°C or lower, more preferably 250°C or lower, even more preferably 245°C or lower, and even more preferably 240°C or lower.
• the polyamide resin of the second embodiment preferably has a difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature (Tcc) when cooled according to differential scanning calorimetry (DSC) of 64°C or less, more preferably 60°C or less, even more preferably 56°C or less, and even more preferably 52°C or less.
• the lower limit of the difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature when cooled (Tcc) is preferably 5°C or more, more preferably 10°C or more, even more preferably 15°C or more, and even more preferably 20°C or more.
• the polyamide resin of this embodiment is preferably the polyamide resin of the first embodiment.
• the polyamide resin of the first embodiment is more effective in accelerating the crystallization rate when made into a resin composition containing a nucleating agent.
• the polyamide resin of this embodiment can be synthesized according to a known method. For example, it can be synthesized according to the description in paragraphs 0016 to 0018 of WO 2018/074234, the contents of which are incorporated herein by reference.
• the resin composition of this embodiment contains the polyamide resin of this embodiment.
• the resin composition of this embodiment may contain only one or more of the polyamide resins of this embodiment, or may contain other components.
• the total amount of the polyamide resin of this embodiment and the reinforcing filler blended as necessary is preferably 90% by mass or more in the resin composition.
• other components include polyamide resins other than the polyamide resin of the present embodiment, thermoplastic resins other than polyamide resins, reinforcing fillers, and resin additives.
• thermoplastic resins other than polyamide resins include polyphenylene ether resins and polyester resins.
• resin additives include nucleating agents, flame retardants, stabilizers, release agents, alkalis, elastomers, titanium oxide, hydrolysis resistance improvers, matting agents, plasticizers, dispersants, antistatic agents, coloring inhibitors, gelling inhibitors, colorants, and the like.
• nucleating agents include nucleating agents, flame retardants, stabilizers, release agents, alkalis, elastomers, titanium oxide, hydrolysis resistance improvers, matting agents, plasticizers, dispersants, antistatic agents, coloring inhibitors, gelling inhibitors, colorants, and the like.
• An example of the resin composition of this embodiment is that it contains a nucleating agent as a resin additive.
• the total amount of the other components is preferably 20.0 mass% or less of the resin composition, more preferably 15.0 mass% or less, even more preferably 10.0 mass% or less, and even more preferably 5.0 mass% or less.
• the lower limit of the content of the other components is preferably 0.1 mass% or more. Only one type of other component may be used, or two or more types may be used in combination.
• the other polyamide resin may be an aliphatic polyamide resin or a semi-aromatic polyamide resin.
• aliphatic polyamide resins include polyamide 6, polyamide 66, polyamide 46, polyamide 6/66 (a copolymer consisting of a polyamide 6 component and a polyamide 66 component), polyamide 610, polyamide 612, polyamide 410, polyamide 1010, polyamide 11, polyamide 12, and polyamide 9C (a polyamide consisting of a mixed diamine consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,4-cyclohexanedicarboxylic acid).
• semi-aromatic polyamide resins include polyamide 6I, polyamide 6T/6I, polyamide 9N (a polyamide composed of a mixed diamine composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine and 2,6-naphthalenedicarboxylic acid), MXD6 which is a polycondensate of metaxylylenediamine and adipic acid, MXD6I which is a polycondensate of metaxylylenediamine, adipic acid and isophthalic acid, MP6 which is a polycondensate of metaxylylenediamine, paraxylylenediamine and adipic acid, MXD10 which is a polycondensate of metaxylylenediamine and sebacic acid, MP10 which is a polycondensate of metaxylylenediamine, paraxylylenediamine and sebacic acid, and PXD10 which is a polycondensate of
• the content thereof is preferably 1 part by mass or more, and may be 5 parts by mass or more, relative to 100 parts by mass of the polyamide resin of this embodiment, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.
• the resin composition of the present embodiment may contain only one type of other polyamide resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
• thermoplastic resins other than polyamide resins include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc. These thermoplastic resins other than polyamide resins may be one type or two or more types.
• the resin composition of the present embodiment may contain a reinforcing filler.
• a reinforcing filler By containing a reinforcing filler, the mechanical strength of the obtained molded article can be improved.
• the reinforcing filler that can be used in this embodiment is not particularly limited in terms of type, and may be any of fibers, fillers, flakes, beads, etc., with fibers being preferred.
• the reinforcing filler When the reinforcing filler is a fiber, it may be a short fiber or a long fiber.
• the resin composition of this embodiment may be, for example, in the form of pellets, powder of the pellets, or a film formed from the pellets.
• examples of the reinforcing filler include long fibers for so-called UD materials (Uni-Directional), sheet-like long fibers such as woven fabrics and knitted fabrics, etc.
• the components other than the reinforcing filler of the resin composition of the present embodiment can be impregnated into the sheet-like reinforcing filler, which is the long fiber, to form a sheet-like resin composition (for example, a prepreg).
• the raw materials for the reinforcing filler include inorganic substances such as glass, carbon (carbon fiber, etc.), alumina, boron, ceramics, metals (steel, etc.), asbestos, clay, zeolite, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide, etc., and organic substances such as plants (including kenaf, bamboo, etc.), aramid, polyoxymethylene, aromatic polyamide, polyparaphenylene benzobisoxazole, ultra-high molecular weight polyethylene, etc., with glass being preferred.
• the resin composition of the present embodiment preferably contains glass fibers as a reinforcing filler.
• the glass fibers are selected from glass compositions such as A-glass, C-glass, E-glass, R-glass, D-glass, M-glass, and S-glass, with E-glass (alkali-free glass) being particularly preferred.
• Glass fiber refers to a fibrous material whose cross section cut perpendicularly to the length direction is a perfect circle or polygon.
• the number average fiber diameter of the single fiber of the glass fiber is usually 1 to 25 ⁇ m, preferably 5 to 17 ⁇ m. By making the number average fiber diameter 1 ⁇ m or more, the moldability of the resin composition tends to be further improved.
• the glass fiber may be a single fiber or a plurality of single fibers twisted together.
• the form of the glass fiber may be any of glass rovings obtained by continuously winding single fibers or multiple twisted fibers, chopped strands cut to a length of 1 to 10 mm (i.e., glass fibers having a number average fiber length of 1 to 10 mm), and milled fibers pulverized to a length of about 10 to 500 ⁇ m (i.e., glass fibers having a number average fiber length of 10 to 500 ⁇ m), but chopped strands cut to a length of 1 to 10 mm are preferred.
• Glass fibers of different forms can also be used in combination. Glass fibers having an irregular cross-sectional shape are also preferred.
• the irregular cross-sectional shape has a flattening ratio, which is the long axis/short axis ratio of a cross section perpendicular to the longitudinal direction of the fiber, of, for example, 1.5 to 10, preferably 2.5 to 10, more preferably 2.5 to 8, and even more preferably 2.5 to 5.
• the glass fibers may be surface-treated with, for example, silane-based compounds, epoxy-based compounds, urethane-based compounds, or the like, or may be oxidized to improve their affinity with the resin components, as long as this does not significantly impair the properties of the resin composition of this embodiment.
• the content of the reinforcing filler (preferably glass fiber) in the resin composition is preferably 10% by mass or more in the resin composition, more preferably 20% by mass or more, and even more preferably 25% by mass or more. By making it equal to or more than the lower limit, the mechanical strength of the obtained molded article tends to be further increased.
• the content of the reinforcing filler (preferably glass fiber) in the resin composition is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less, and may be 40% by mass or less or 35% by mass or less depending on the application. By making it equal to or less than the upper limit, the appearance of the molded article is improved and the flowability of the resin composition tends to be further improved.
• the resin composition of the present embodiment may contain only one type of reinforcing filler (preferably glass fiber), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
• the resin composition of the present embodiment may contain a nucleating agent. By containing a nucleating agent, the crystallization rate of the resin composition can be increased.
• the nucleating agent is not particularly limited as long as it is unmelted during melt processing and can become a crystal nucleus during the cooling process, and may be either an organic nucleating agent or an inorganic nucleating agent, with an inorganic nucleating agent being preferred.
• inorganic nucleating agents include graphite, molybdenum disulfide, barium sulfate, talc, calcium carbonate, sodium phosphate, mica and kaolin, and at least one selected from talc and calcium carbonate is more preferred, with talc being even more preferred.
• the organic nucleating agent is not particularly limited, and any known nucleating agent can be used.
• the nucleating agent is preferably at least one selected from dibenzylidene sorbitol-based nucleating agents, nonitol-based nucleating agents, phosphate ester salt-based nucleating agents, rosin-based nucleating agents, and metal benzoate salt-based nucleating agents.
• the number average particle size of the nucleating agent has a lower limit of preferably 0.1 ⁇ m or more.
• the number average particle size of the nucleating agent has an upper limit of preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, even more preferably 28 ⁇ m or less, even more preferably 15 ⁇ m or less, and even more preferably 10 ⁇ m or less.
• the content of the nucleating agent in the resin composition of this embodiment is 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, relative to 100 parts by mass of the polyamide resin of this embodiment. By making it equal to or more than the lower limit, the crystalline state of the resin composition can be more sufficiently stabilized.
• the content of the nucleating agent in the resin composition of this embodiment is 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 4 parts by mass or less, relative to 100 parts by mass of the total amount of the polyamide resin of this embodiment.
• the resin composition of the present embodiment contains a nucleating agent, it may contain only one type of nucleating agent, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.
• the resin composition of the present embodiment preferably has a glass transition temperature (Tg) according to differential scanning calorimetry (DSC) of 111° C. or more, more preferably 115° C. or more, and even more preferably 118° C. or more.
• Tg glass transition temperature
• the upper limit of the glass transition temperature (Tg) is, for example, 200° C. or less, and even if it is 150° C. or less, and even if it is 140° C. or less, the required performance is sufficiently satisfied.
• the resin composition of this embodiment preferably has a melting point (Tm) according to differential scanning calorimetry (DSC) of 264°C or higher, more preferably 265°C or higher, and preferably 350°C or lower, more preferably 330°C or lower, and may be 300°C or lower.
• Tm melting point
• DSC differential scanning calorimetry
• the resin composition of this embodiment preferably has a crystallization temperature (Tcc) on cooling according to differential scanning calorimetry (DSC) of 230°C or higher, more preferably 235°C or higher, and even more preferably 238°C or higher, and preferably 250°C or lower, and more preferably 245°C or lower.
• Tcc crystallization temperature
• the resin composition of this embodiment preferably has a difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature (Tcc) when cooled according to differential scanning calorimetry (DSC) of 33°C or less, more preferably 32°C or less, even more preferably 30°C or less, even more preferably 28°C or less, and even more preferably 27°C or less.
• DSC differential scanning calorimetry
• the lower limit of the difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature when cooled (Tcc) is not particularly set, but may be, for example, 5°C or more, or further 10°C or more, 15°C or more, or 18°C or more.
• the method for producing the resin composition is not particularly specified, and a wide variety of known methods for producing thermoplastic resin compositions can be used.
• the resin composition can be produced by mixing the components in advance using various mixers such as a tumbler or a Henschel mixer, and then melt-kneading the components using a Banbury mixer, a roll, a Brabender, a single-screw extruder, a twin-screw extruder, a kneader, or the like.
• the resin composition can be produced by not mixing the components in advance, or by mixing only some of the components in advance, feeding the mixture to an extruder using a feeder, and melt-kneading the mixture. It is preferred that the reinforcing filler (especially glass fiber) be side fed. In addition, for example, some of the components may be mixed in advance, fed to an extruder, and melt-kneaded to obtain a masterbatch composition, which may then be mixed again with the remaining components and melt-kneaded to produce pellets.
• the molded article of this embodiment is formed from the resin of this embodiment or the resin composition of this embodiment.
• the method for producing the molded article of the present embodiment is not particularly limited.
• an injection molded article produced by injection molding is exemplified.
• the molded product of this embodiment may be produced by melt-kneading the components and then directly molding the components using various molding methods, or by melt-kneading the components and pelletizing them, and then melting them again and molding them using various molding methods.
• the method for forming the molded product is not particularly limited, and any conventionally known molding method can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multi-layer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding.
• any conventionally known molding method can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multi-layer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding.
• the shape of the molded product of this embodiment is not particularly limited and can be appropriately selected depending on the application and purpose of the molded product. Examples include plate-like, plate-like, rod-like, sheet-like, film-like, cylindrical, annular, circular, elliptical, gear-like, polygonal, irregularly shaped, hollow, frame-like, box-like, panel-like, etc.
• the fields of use of the molded products of this embodiment are not particularly specified, and they are widely used in automobile and other transport vehicle parts, general machine parts, precision machine parts, electronic and electrical equipment parts, office equipment parts, building materials and housing-related parts, medical equipment, leisure and sporting goods, play equipment, medical supplies, everyday items such as food packaging films, defense and aerospace products, etc.
• bisaminomethylcyclohexane may be referred to as BAC, cyclohexanedicarboxylic acid as CHDA, and adipic acid as AdA.
• the DSC (Differential Scanning Calorimetry) measurement was performed in accordance with JIS K7121 and K7122.
• the obtained resin pellets or resin composition pellets were crushed and placed in the measurement pan of the differential scanning calorimeter, and heated to the melting point of each resin + 20 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere.
• the measurement pan was removed and pressed against dry ice to rapidly cool.
• the measurement conditions were as follows: the temperature was increased to a temperature above the melting point at a rate of 10° C./min, and then the temperature was decreased to 100° C. at a rate of ⁇ 5° C./min, and each thermal property value was determined.
• Tm-Tcc (unit: ° C.) was calculated from the above measured values.
• the differential scanning calorimeter used was a "DSC-60" manufactured by Shimadzu Corporation.
• Example 1 A 3L reaction vessel equipped with a stirrer, a cooling tube, a thermometer, a dropping tank and a pump, and a nitrogen inlet tube was charged with precisely weighed 585.0g (4.003mol) of adipic acid, 36.3g (0.211mol) of 1,4-cyclohexanedicarboxylic acid (manufacturer: Nikko Rika Corporation, product name: 1,4-CHDA, trans isomer ratio 36 mol%), 0.876g (0.00051mol) of calcium hypophosphite, and 0.056g (0.00069mol) of sodium acetate, and the reaction vessel was heated to 200°C under stirring while flowing nitrogen in the reaction vessel.
• Comparative Examples 1 to 7 Polyamide resins were obtained in the same manner as in Example 1, except that the raw material monomers were changed as shown in Tables 1 to 3. In Comparative Examples 5 and 7, decomposition occurred during the synthesis, and no polyamide resin was obtained.
• Examples 16 to 18, Comparative Examples 8 to 10 ⁇ Compound>
• the types of polyamide resins and glass fibers and/or nucleating agents shown in Table 4 were weighed out. The amount of polyamide resin was determined so that all components other than the glass fibers and nucleating agent were polyamide resin.
• 1,4-BAC6C CHDA: 10 mol%) is the polyamide resin obtained in Example 5
• 1,4-BAC6 is the polyamide resin obtained in Comparative Example 3.
• the polyamide resin and the nucleating agent, which may be added as required, were blended in a tumbler, and then fed into a twin-screw extruder (TEM26SS, manufactured by Shibaura Machine Co., Ltd.) from the base and melted.
• TEM26SS twin-screw extruder
• the glass fiber When glass fiber was added, the glass fiber was side-fed to prepare pellets of the resin composition.
• the temperature of the twin-screw extruder was set to 290°C.
• the glass fiber used was E-glass fiber (T-296GH, manufactured by Nippon Electric Glass Co., Ltd.), and the nucleating agent used was talc (Micron White #5000A, manufactured by Hayashi Kasei Co., Ltd.). As described above, the thermal properties of the resulting resin composition (pellets) were measured.
• a small Tm-Tcc indicates a high crystallization rate.
• the polyamide resin and resin composition of the present invention have a high crystallization rate.
• the polyamide resin and resin composition are highly valuable in that the crystallization rate can be increased without decreasing the glass transition temperature of the polyamide resin and resin composition.

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• 2023
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