Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to a resin composition and a molded article.
• the present invention relates to a resin composition whose main component is a polyamide resin.
• Crystalline polyamide resins such as nylon 6 and nylon 66
• a high crystallization rate may be required.
• Patent Document 1 discloses a polyamide resin composition having a high crystallization rate, which is a polyamide resin composition containing (A) polyamide resin obtained from xylylenediamine and sebacic acid and polyamide 66 (B), characterized in that the melting point of polyamide 66 (B) is higher than the melting point of polyamide resin (A) by more than 50°C, and the temperature difference between the crystallization temperature of polyamide resin (A) and the crystallization temperature of polyamide 66 (B) is 50°C or less.
• the present invention has an object to solve the above problems, and to provide a resin composition having a fast crystallization rate while maintaining a high glass transition temperature, and a molded article thereof.
• the present inventors have conducted research and found that the above problems can be solved by blending a polyamide resin composed of bisaminomethylcyclohexane and an aliphatic dicarboxylic acid, etc. with a polyamide resin composed of an aliphatic diamine and terephthalic acid, etc., in a predetermined ratio. Specifically, the above problems were solved by the following means.
• the (A) polyamide resin contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol % or more of the diamine-derived structural units are derived from bisaminomethylcyclohexane, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms;
• the (B) polyamide resin contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol % or more of the diamine-derived structural units are derived from an aliphatic diamine having 4 to 20 carbon atoms, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from terephthalic acid.
• Resin composition ⁇ 2> The resin composition according to ⁇ 1>, in which, in the polyamide resin (A), the bisaminomethylcyclohexane includes 1,3-bisaminomethylcyclohexane and/or 1,4-bisaminomethylcyclohexane.
• the resin composition according to ⁇ 1> wherein in the polyamide resin (A), the bisaminomethylcyclohexane includes 1,3-bisaminomethylcyclohexane and/or 1,4-bisaminomethylcyclohexane, the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms includes adipic acid, and in the polyamide resin (B), the aliphatic diamine having 4 to 20 carbon atoms includes at least one selected from 1,6-hexanediamine, 1,9-nonanediamine, and 1,10-decanediamine.
• ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the resin composition has a glass transition temperature (Tg) of 100 to 200° C. as measured by differential scanning calorimetry (DSC).
• Tg glass transition temperature
• DSC differential scanning calorimetry
• Tm melting point
• Tcc crystallization temperature
• the present invention makes it possible to provide a resin composition and molded article that maintains a high glass transition temperature while exhibiting a fast crystallization rate.
• 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 weight average molecular weight and 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.
• BAC bisaminomethylcyclohexane
• CHDA cyclohexanedicarboxylic acid
• the resin composition of the present embodiment comprises 75 to 99 parts by mass of (A) polyamide resin and 25 to 1 part by mass of (B) polyamide resin
• the (A) polyamide resin comprises diamine-derived structural units and dicarboxylic acid-derived structural units, 70 mol % or more of the diamine-derived structural units are derived from bisaminomethylcyclohexane, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms
• the (B) polyamide resin comprises diamine-derived structural units and dicarboxylic acid-derived structural units, 70 mol % or more of the diamine-derived structural units are derived from an aliphatic diamine having 4 to 20 carbon atoms, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from terephthalic acid.
• a resin composition having a high crystallization rate can be obtained while maintaining a high glass transition temperature.
• the crystallization rate can be increased by blending a polyamide resin having a high crystallization rate with a polyamide resin having a low crystallization rate, but the glass transition temperature is usually lowered.
• a resin composition having a high crystallization rate can be obtained while achieving a high glass transition temperature, which is highly valuable.
• the (A) polyamide resin contains diamine-derived structural units and dicarboxylic acid-derived structural units, with 70 mol % or more of the diamine-derived structural units being derived from bisaminomethylcyclohexane and 70 mol % or more of the dicarboxylic acid-derived structural units being derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• the total of the diamine-derived structural units is 100 mol %
• the total of the dicarboxylic acid-derived structural units is also 100 mol %.
• 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.
• a first preferred embodiment of the bisaminomethylcyclohexane is one containing 1,3-bisaminomethylcyclohexane.
• a second preferred embodiment of the bisaminomethylcyclohexane is one containing 1,4-bisaminomethylcyclohexane.
• a third preferred embodiment of the bisaminomethylcyclohexane is when it comprises a mixture of 1,3-bisaminomethylcyclohexane and 1,4-bisaminomethylcyclohexane.
• the ratio of the trans isomer of the bisaminomethylcyclohexane (the ratio when the sum of the trans and cis isomers is taken as 100 mol%) may be, for example, 0 mol% or more, and further, 10 mol% or more, 20 mol% or more, 25 mol% or more, 30 mol% or more, 35 mol% or more, 40 mol% or more, or, for example, 100 mol% or less, 50 mol% or less, 45 mol% or less, 40 mol% or less, 35 mol% or less, 30 mol% or less, 25 mol% or less, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 3 mol% or less.
• the ratio of the trans isomer is preferably 0 to 50 mol %, may be 0 to 20 mol %, or may be 0 to 10 mol %. By making it equal to or greater than the lower limit, it is possible to make the resin less susceptible to thermal degradation during molding.
• the ratio of the trans isomer is preferably 35 to 55 mol %, more preferably 40 to 50 mol %. By keeping it below the upper limit, thermal degradation during molding can be suppressed.
• 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 dicarboxylic acid-derived constitutional units are derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, more preferably 90 mol % or more, even more preferably 95 mol % or more, and even more preferably 99 mol % or more are derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• 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. Of these, adipic acid, sebacic acid, or dodecanedioic acid is preferred, adipic acid or sebacic acid is more preferred, and adipic acid is even more preferred.
• dicarboxylic acids other than ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms include alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, phthalic acid compounds such as isophthalic acid, terephthalic acid, and orthophthalic acid, and isomers of naphthalene dicarboxylic acid such as 1,2-naphthalene dicarboxylic acid, 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic
• the first embodiment of the polyamide resin (A) used in this embodiment is one in which 90 mol% or more (preferably 95 mol% or more, more preferably 99 mol% or more) of the diamine-derived structural units are derived from bisaminomethylcyclohexane, and 70 mol% or more (preferably 95 mol% or more, more preferably 99 mol% or more) of the dicarboxylic acid-derived structural units are derived from adipic acid.
• the bisaminomethylcyclohexane is preferably 1,3-bisaminomethylcyclohexane and/or 1,4-bisaminomethylcyclohexane.
• the second embodiment of the polyamide resin (A) used in this embodiment is such that 90 mol% or more (preferably 95 mol% or more, more preferably 99 mol% or more) of the diamine-derived structural units are derived from bisaminomethylcyclohexane, 99 to 70 mol% of the dicarboxylic acid-derived structural units are derived from ⁇ , ⁇ -straight-chain aliphatic dicarboxylic acids having 4 to 20 carbon atoms, and 1 to 30 mol% are derived from cyclohexanedicarboxylic acid (preferably 1,4-cyclohexanedicarboxylic acid) (however, the total of the structural units derived from ⁇ , ⁇ -straight-chain aliphatic dicarboxylic acids having 4 to 20 carbon atoms and the structural units derived from cyclohexanedicarboxylic acid does not exceed 100 mol%).
• the proportion of the structural units derived from cyclohexanedicarboxylic acid in the dicarboxylic acid-derived structural units is preferably 5 mol% or more, more preferably 20 mol% or less, and even more preferably 15 mol% or less.
• the polyamide resin (A) used in this embodiment is mainly composed of diamine units and dicarboxylic acid units, but this does not exclude the inclusion of other monomer units, and it goes without saying that it may contain 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 (A), 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 (A) preferably accounts for 90.0% by mass or more of the total monomer units, and more preferably accounts for 95.0% by mass or more.
• the polyamide resin (A) used in the present embodiment has a number average molecular weight (Mn) of preferably 5,000 or more, more preferably 10,000 or more.
• Mn number average molecular weight
• the upper limit of Mn is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.
• the Mn of the polyamide resins is the Mn of the mixture.
• (B) polyamide resins The same applies to (B) polyamide resins.
• the polyamide resin (A) used in the present embodiment has a melting point of preferably 210° C. or higher, more preferably 240° C. or higher, even more preferably 250° C. or higher, and even more preferably 260° C. or higher. There is no particular upper limit to the melting point, but a practical upper limit is 290° C. or lower.
• the melting point of the resin is the melting point of the highest polyamide.
• the glass transition temperature of the (A) polyamide resin is preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 105° C. or higher.
• the glass transition temperature is that of the polyamide having the highest glass transition temperature.
• the melting point and glass transition temperature of the polyamide resin (A) are measured according to the description in the Examples section described later.
• the resin composition of the present embodiment includes a polyamide resin (B) that contains diamine-derived structural units and dicarboxylic acid-derived structural units, in which 70 mol % or more of the diamine-derived structural units are derived from an aliphatic diamine having 4 to 20 carbon atoms, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from terephthalic acid.
• the total of the diamine-derived structural units is 100 mol %
• the total of the dicarboxylic acid-derived structural units is also 100 mol %.
• (B) polyamide resin it is preferable that 80 mol% or more of the diamine-derived structural units are derived from aliphatic diamines having 4 to 20 carbon atoms (preferably linear aliphatic diamines having 4 to 20 carbon atoms), more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 99 mol% or more are derived from aliphatic diamines having 4 to 20 carbon atoms (preferably linear aliphatic diamines having 4 to 20 carbon atoms).
• the aliphatic diamine having 4 to 20 carbon atoms is preferably a straight-chain aliphatic diamine having 5 to 12 carbon atoms, more preferably at least one selected from the group consisting of 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine, even more preferably 1,6-hexanediamine, 1,9-nonanediamine, or 1,10-decanediamine, even more preferably 1,9-nonanediamine or 1,10-decanediamine, and even more preferably 1,10-decanediamine.
• diamines other than aliphatic diamines having 4 to 20 carbon atoms include alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decalin, and bis(aminomethyl)tricyclodecane, as well as diamines having aromatic rings such as bis(4-aminophenyl)ether, paraphenylenediamine, and bis(aminomethyl)naphthalene, and these can be used alone or in combination of two or more.
• alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(amino
• polyamide resin 70 mol% or more of the dicarboxylic acid-derived structural units are derived from terephthalic acid, and preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 99 mol% or more are derived from aliphatic diamines having 4 to 20 carbon atoms.
• dicarboxylic acids other than terephthalic acid include linear aliphatic dicarboxylic acids such as pimelic acid, suberic acid, adipic acid, sebacic acid, and azelaic acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, phthalic acid compounds such as isophthalic acid and orthophthalic acid, and naphthalene dicarboxylic acids such as 1,2-naphthalene dicarboxylic acid, 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic
• 70 mol% or more (preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 99 mol% or more) of the diamine-derived structural units are derived from a straight-chain aliphatic diamine having 5 to 12 carbon atoms (preferably at least one selected from 1,6-hexanediamine, 1,9-nonanediamine, and 1,10-decanediamine, more preferably at least one selected from 1,9-nonanediamine and 1,10-decanediamine, and even more preferably 1,10-decanediamine), and 70 mol% or more (preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 99 mol% or more) of the dicarboxylic acid-derived structural units are derived from terephthalic acid.
• a part of the dicarboxylic acid-derived structural units may be structural units derived from cyclohexanedicarboxylic acid.
• the proportion of the structural units derived from cyclohexanedicarboxylic acid is preferably 5 mol% or more, more preferably 20 mol% or less, and even more preferably 15 mol% or less.
• the polyamide resin (B) used in this embodiment is mainly composed of diamine units and dicarboxylic acid units, but this does not exclude the inclusion of other monomer units, and it goes without saying that it may contain 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 (B), 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 (B) preferably accounts for 90.0% by mass or more of the total monomer units, and more preferably accounts for 95.0% by mass or more.
• the polyamide resin (B) used in this embodiment preferably has a lower limit of number average molecular weight (Mn) of 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 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 (B) used in the present embodiment has a melting point of preferably 290° C. or higher, more preferably 300° C. or higher, and even more preferably 310° C. or higher. There is no particular upper limit to the melting point, but a practical upper limit is 330° C. or lower.
• the glass transition temperature of the polyamide resin (B) is preferably 120° C. or higher, more preferably 130° C. or higher, and even more preferably 140° C. or higher.
• the upper limit of the glass transition temperature is not particularly limited, but a practical upper limit is 170° C. or lower.
• the melting point and glass transition temperature of the polyamide resin (B) are measured according to the description in the Examples section described later.
• the resin composition of this embodiment contains 75 to 99 parts by mass of (A) polyamide resin and 25 to 1 part by mass of (B) polyamide resin.
• the total of (A) polyamide resin and (B) polyamide resin is 100 parts by mass, it is preferable to contain 75 to 99 parts by mass of (A) polyamide resin and 25 to 1 part by mass of (B) polyamide resin, more preferably 75 to 95 parts by mass of (A) polyamide resin and 25 to 5 parts by mass of (B) polyamide resin, and even more preferably 80 to 95 parts by mass of (A) polyamide resin and 20 to 5 parts by mass of (B) polyamide resin.
• the sum of the (A) polyamide resin and the (B) polyamide resin preferably accounts for 90 mass% or more of the resin composition, more preferably 95 mass% or more, and even more preferably 97 mass% or more. Furthermore, when the resin composition of this embodiment contains a reinforcing filler, the sum of the (A) polyamide resin and the (B) polyamide resin preferably accounts for 90 mass % or more of the components of the resin composition excluding the reinforcing filler, more preferably 95 mass % or more, and even more preferably 97 mass % or more.
• the polyamide resin (A) and the polyamide resin (B) may each be contained alone or in combination of two or more. When two or more types are contained, the total amount is preferably within the above range.
• the resin composition of the present embodiment may or may not contain a polyamide resin other than the polyamide resin (A) and the polyamide resin (B).
• the other polyamide resin may be an aliphatic polyamide resin or a semi-aromatic polyamide resin.
• aliphatic polyamide resins examples 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 total of the (A) polyamide resin and (B) contained in the resin composition of the present 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.
• the resin composition of this embodiment can be configured to be substantially free of other polyamide resins than the polyamide resin (A) and (B).
• “Substantially free” means that the content of other polyamide resins is less than 5 parts by mass per 100 parts by mass of the total of the polyamide resin (A) and (B), preferably 1 part by mass or less, more preferably 0.1 part by mass or less, and even more preferably 0.01 part by mass or less.
• 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 reinforcing filler When the reinforcing filler is short fiber, filler, beads, or the like, examples of the resin composition of this embodiment include pellets, powdered pellets, and films formed from the pellets.
• the reinforcing filler When the reinforcing filler is a long fiber, 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.
• UD materials Uni-Directional
• 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 body 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 body 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, which can increase the crystallization rate.
• 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 0.9 parts by mass or more, per 100 parts by mass of the total amount of polyamide resin ((A) polyamide resin, (B) polyamide resin, and other polyamide resins). 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 3 parts by mass or less, per 100 parts by mass of the total amount of polyamide resin.
• 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 may contain other components in addition to those described above.
• other components include thermoplastic resins other than polyamide resins and resin additives.
• thermoplastic resins other than polyamide resins include polyphenylene ether resins and polyester resins.
• resin additives include flame retardants, stabilizers, release agents, elastomers, titanium oxide, hydrolysis resistance improvers, matting agents, plasticizers, dispersants, antistatic agents, coloring inhibitors, antigelling agents, colorants, etc.
• 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 resin composition of the present embodiment preferably has a glass transition temperature (Tg) according to differential scanning calorimetry (DSC) of 100° C. or higher, more preferably 105° C. or higher, and even more preferably 108° C. or higher.
• Tg glass transition temperature
• the upper limit of the glass transition temperature (Tg) is, for example, 200° C. or lower, and even if it is 150° C. or lower, or 130° C. or lower, 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 200°C or more, more preferably 215°C or more, even more preferably 220°C or more, even more preferably 240°C or more, even more preferably 250°C or more, and preferably 350°C or less, more preferably 330°C or less, even more preferably 300°C or less, and may be 290°C or less.
• 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 190°C or higher, more preferably 200°C or higher, and may even be 210°C or higher or 220°C or higher, and is preferably 250°C or lower, more preferably 245°C or lower.
• Tcc crystallization temperature
• the resin composition of this embodiment preferably has a difference (Tm-Tg) between the melting point (Tm) and the glass transition temperature (Tg) according to differential scanning calorimetry (DSC) of 175°C or less, more preferably 170°C or less, even more preferably 165°C or less, even more preferably 162°C or less, and even more preferably 158°C or less. If the difference between the melting point (Tm) and the glass transition temperature (Tg) is small, the retention stability due to heating during molding is excellent.
• DSC differential scanning calorimetry
• the lower limit of the difference (Tm-Tg) between the melting point (Tm) and the glass transition temperature (Tg) is not particularly set, but may be, for example, 120°C or more, or even 130°C or more, 140°C or more, or 150°C or more.
• the difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature (Tcc) during cooling according to differential scanning calorimetry (DSC) is preferably 43 ° C. or less, more preferably 400 ° C. or less, even more preferably 35 ° C. or less, even more preferably 32 ° C. or less, and even more preferably 29 ° C. or less. If the difference between the melting point (Tm) and the crystallization temperature during cooling (Tcc) is small, there is an advantage that the crystallization rate is fast and the dimensions of the molded product are less likely to change.
• the lower limit of the difference (Tm-Tcc) between the melting point (Tm) and the crystallization temperature during cooling (Tcc) is not particularly specified, 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 upon cooling (Tcc) are measured according to the description in the examples described later.
• 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. Furthermore, 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 the present embodiment is formed from the resin composition or pellets of the present 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.
• the dropping of 8434.5g (59.29mol) of 1,4-bisaminomethylcyclohexane stored in the dropping tank was started to the molten raw material in the reaction vessel, and the temperature in the reaction vessel was continuously raised to 290°C while removing the generated condensed water from the system while maintaining the vessel at 0.4MPa.
• the pressure inside the reaction vessel was gradually returned to normal pressure, and then the pressure inside the reaction vessel was reduced to 80 kPa using an aspirator to remove the condensed water.
• the dropping of 8243.6 g (57.95 mol) of 1,4-bisaminomethylcyclohexane stored in the dropping tank was started to the molten raw material in the reaction vessel, and the temperature in the reaction vessel was continuously raised to 290° C. while removing the generated condensed water from the system while maintaining the vessel at 0.4 MPa.
• the pressure inside the reaction vessel was gradually returned to normal pressure, and then the pressure inside the reaction vessel was reduced to 80 kPa using an aspirator to remove the condensed water.
• the stirring torque of the stirrer was observed during the reduction in pressure, and when a predetermined torque was reached, the stirring was stopped, the reaction vessel was pressurized with nitrogen, the bottom discharge valve was opened, and the polymer was extracted from the strand die and formed into strands, which were then cooled and pelletized with a pelletizer to obtain 1,4-BAC6C (BAC trans isomer ratio 40 mol%).
• the dripping of 10,373.1 g (72.93 mol) of 1,3-bisaminomethylcyclohexane stored in the dripping tank was started to the molten raw material in the reaction vessel, and the temperature in the reaction vessel was continuously raised to 255°C while removing the generated condensed water outside the system while maintaining the pressure in the vessel at 0.4 MPa.
• the pressure in the reaction vessel was gradually returned to normal pressure, and then the pressure in the reaction vessel was reduced to 80 kPa using an aspirator to remove the condensed water.
• the stirring torque of the stirrer was observed during the pressure reduction, and when a predetermined torque was reached, stirring was stopped, the inside of the reaction vessel was pressurized with nitrogen, the bottom discharge valve was opened, and the polymer was discharged through the strand die and formed into strands. The polymer was then cooled and pelletized with a pelletizer to obtain 1,3-BAC6 (proportion of trans isomer of BAC: 26 mol %).
• the dropping of 84.35 kg (592.94 mol) of 1,4-bisaminomethylcyclohexane stored in the dropping tank was started to the molten raw material in the reaction vessel, and the temperature in the reaction vessel was continuously raised to 290 ° C. while removing the condensed water generated outside the system while maintaining the vessel at 0.4 MPa.
• the pressure inside the reaction vessel was gradually returned to normal pressure, and then the pressure inside the reaction vessel was reduced to 80 kPa using an aspirator to remove the condensed water.
• PA10T Polyamide resin mainly composed of 1,10-decanediamine and terephthalic acid, Manufacturer: Unitika Ltd., Product number: XecoT XN400
• PA6T Polyamide resin whose main components are 1,6-hexanediamine and terephthalic acid, Manufacturer: Mitsui Chemicals, Inc., Product number: Arlen AE4200
• PA9T Polyamide resin mainly composed of 1,9-nonanediamine and terephthalic acid, Manufacturer: Kuraray Co., Ltd., Product number: Genestar N1000A
• Glass fiber Manufacturer: Nippon Electric Glass Co., Ltd., Product number: T-296GH Nucleating agent: talc, Micron White #5000A, manufactured by Hayashi Kasei Co., Ltd.
• the obtained resin composition (pellets) was crushed and placed in the measurement pan of the differential scanning calorimeter, and heated to the melting point + 20 ° C. shown in Tables 1 to 3 at a heating rate of 10 ° C./min under a nitrogen atmosphere. Immediately after the heating was completed, the measurement pan was removed and pressed against dry ice to rapidly cool. Then, the measurement was performed.
• the measurement conditions were as follows: the temperature was raised to a temperature above the melting point at a rate of 10° C./min, held for 5 minutes, and then the temperature was lowered at a rate of ⁇ 5° C./min down to 100° C. to determine each thermal property value.
• Tm-Tcc unit: ° C.
• Tm-Tg unit: ° C.
• the t ratio (mol %) of BAC indicates the proportion of trans isomers in the BAC.
• a small Tm-Tcc indicates a high crystallization rate
• a small Tm-Tg indicates excellent retention stability due to heating during molding.
• the resin composition of the present invention has a significantly increased crystallization rate by blending a predetermined amount of polyamide resin (B) with polyamide resin (A). This is particularly valuable in that the crystallization rate can be increased without lowering the glass transition temperature of the resin composition.
• the resin compositions of Examples 1 to 11 were injection molded, good injection molded articles were obtained.

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• 2023
  • 2023-12-25 JP JP2024570131A patent/JPWO2024150652A1/ja active Pending
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