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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

• Crystalline polyamides such as nylon 6 and nylon 66 are widely used for industrial parts because of their excellent heat resistance, mechanical properties, moldability, and the like.
• metal parts are being made of resin, and crystalline polyamides, which are excellent in the above properties, are often used.
• the performance required of plastic materials is becoming stricter from the viewpoint of improving fuel efficiency and responding to environmental regulations, and materials with better performance from the viewpoint of heat resistance are in demand.
• a material with a high crystallization rate which is the time required for the material to cool and solidify from a molten state.
• a high crystallization rate can shorten the time required for molding one part, and can improve production efficiency.
• Patent Document 1 discloses that a polyamide that simultaneously satisfies fluidity, toughness, rigidity, etc. can be obtained by including at least 50 mol% of a diamine unit with a branched structure in the main chain of the polyamide.
• US Pat. No. 6,200,008 discloses a method for producing polyamide compositions containing diamine units with methyl or ethyl branches.
• Patent Document 3 60 mol % or more and 100 mol % or less of the diamine units are branched aliphatic diamine units and linear aliphatic diamine units of arbitrary constitutional units, a polyamide composition containing a polyamide. disclosed.
• JP 2011-80055 A Japanese Patent Publication No. 2017-517594 WO2020/040282
• Patent Documents 1 to 3 a methyl group, an ethyl group, an n-propyl group, etc. are described as substituents branched from the main chain of the structural unit derived from the diamine forming the polyamide.
• diamines having methyl groups as branched chains are specifically exemplified. None of the documents specifically disclose a branched diamine having a substituent with more carbon atoms than a methyl group as a branched chain, and the effect of having a branched chain with 2 or more carbon atoms has not been clarified. .
• the present invention provides a polyamide composition with excellent heat resistance, mechanical properties, and moldability.
• the present invention is as follows.
• a polyamide composition comprising a polyamide (A) and a fibrous filler (B),
• the polyamide (A) contains diamine units (X) and dicarboxylic acid units (Y),
• the diamine unit (X) contains 0.1 mol% or more and less than 36 mol% of the diamine unit (X1),
• the diamine unit (X1) has 6 to 10 carbon atoms, and when the carbon atom to which any one amino group is bonded is the 1st position, the carbon atom at the 2nd position has 2 carbon atoms or A structural unit derived from an aliphatic diamine to which 3 alkyl groups are bonded, Polyamide composition.
• the diamine unit (X1) contains a structural unit derived from at least one selected from the group consisting of 2-ethyl-1,7-heptanediamine and 2-propyl-1,6-hexanediamine.
• the diamine unit (X) further includes a diamine unit (X2) which is a diamine unit other than the diamine unit (X1), and the diamine unit (X2) is a linear aliphatic diamine, the diamine unit A structural unit derived from at least one selected from the group consisting of branched aliphatic diamines other than the aliphatic diamines constituting (X1), alicyclic diamines, and aromatic diamines, above [1] to The polyamide composition according to any one of [4]. [6] The above [ 1] The polyamide composition according to any one of [5].
• the diamine unit (X2) is 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 2-methyl-1,5-pentanediamine, and 2-methyl-1,8 -
• the dicarboxylic acid unit (Y) contains a structural unit derived from at least one selected from the group consisting of terephthalic acid, cyclohexanedicarboxylic acid, and naphthalenedicarboxylic acid.
• a polyamide composition according to any one of the preceding claims. [12] Any one of [1] to [11] above, wherein the fibrous filler (B) is contained in an amount of 1 part by mass or more and 200 parts by mass or less relative to 100 parts by mass of the polyamide (A). of the polyamide composition.
• fibrous filler (B) is at least one selected from the group consisting of carbon fiber, glass fiber, and aramid fiber.
• Polyamide composition [14] A molded article made of the polyamide composition according to any one of [1] to [13] above.
• this embodiment an embodiment of the present invention (hereinafter sometimes referred to as "this embodiment") will be described based on an example.
• the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following description.
• preferred forms of embodiments are indicated herein, and combinations of two or more of the individual preferred forms are also preferred forms.
• the lower and upper limits thereof can be selectively combined to form a preferred form.
• a numerical range is described as "XX to YY"
• unit means "a structural unit derived from”
• dicarboxylic acid unit means "to a dicarboxylic acid.
• a "structural unit derived from a diamine” means a “structural unit derived from a diamine”.
• the polyamide (A) used in the present invention contains diamine units (X) and dicarboxylic acid units (Y).
• the diamine unit (X) has 6 to 10 carbon atoms, and when the carbon atom to which any one amino group is bonded is the 1st position, the carbon atom at the 2nd position has 2 carbon atoms or It is characterized by containing a specific amount of a diamine unit (X1) derived from an aliphatic diamine to which three alkyl groups are bonded.
• the polyamide (A) contains a specific amount of the diamine unit (X1) having an alkyl group having 2 or 3 carbon atoms, such as an ethyl group or a propyl group, as a branched chain. increased speed.
• a polyamide has a bulky substituent such as a branched chain, it becomes difficult to take a crystal structure, and the melting point tends to be lowered.
• the polyamide (A) even if the polyamide (A) has a relatively bulky substituent group having 2 or 3 carbon atoms such as an ethyl group or a propyl group as a branched chain, the decrease in the melting point is small. , can exhibit excellent heat resistance. Furthermore, the lower the molecular mobility of the amorphous portion, the higher the glass transition temperature. Therefore, the glass transition temperature generally tends to be low when a component with high molecular mobility such as a branched chain is contained. However, in the present embodiment, the polyamide (A) unexpectedly shows little decrease in the glass transition temperature and exhibits excellent heat resistance.
• the polyamide composition of the present embodiment has excellent mechanical properties while maintaining the excellent physical properties of the polyamide (A) by containing the polyamide (A) and the fibrous filler (B). .
• the diamine unit (X) has 6 to 10 carbon atoms, and when the carbon atom to which any one of the amino groups is bonded is the 1st position, the carbon atom at the 2nd position has 2 or 3 carbon atoms. contains a diamine unit (X1) derived from an aliphatic diamine to which an alkyl group of is bonded.
• the diamine unit (X1) is assumed to be a linear aliphatic chain with the carbon atoms to which two amino groups are respectively bonded as the carbon atoms at both ends, and any one amino group is bonded to 1 It is derived from an aliphatic diamine having a structure in which one of the hydrogen atoms on the 2-position carbon atom adjacent to the 2-position carbon atom is substituted with an alkyl group having 2 or 3 carbon atoms.
• a structural unit derived from an aliphatic diamine having a structure in which one of the hydrogen atoms on the carbon atom at the 2-position is substituted with an alkyl group having 2 or 3 carbon atoms is also referred to as a "branched aliphatic diamine unit". If the number of carbon atoms in the alkyl group is 1 or 4 or more, the crystallization rate may not be improved and the heat resistance may be lowered.
• the branched aliphatic diamine unit forming the diamine unit (X1) preferably has 8 to 10 carbon atoms, more preferably 9 carbon atoms.
• the number of carbon atoms is within the above range, the polymerization reaction between the dicarboxylic acid and the diamine proceeds favorably, and the physical properties of the polyamide composition are likely to be improved.
• the alkyl group having 2 or 3 carbon atoms is preferably at least one selected from the group consisting of an ethyl group, a propyl group, and an isopropyl group, More preferably, it is at least one selected from the group consisting of ethyl and propyl groups.
• the branched aliphatic diamine that forms the diamine unit (X1) has a branched chain such as a methyl group (referred to as "another branched chain”) at a carbon other than the 2-position as long as the effect of the present invention is not impaired. may have The number of other branched chains is preferably one or less, and more preferably the diamine unit (X1) does not contain other branched chains.
• the diamine unit (X1) is contained in the diamine unit (X) in an amount of 0.1 mol% or more and less than 36 mol%. By making it 0.1 mol % or more, it becomes possible to improve the crystallization speed. By making it less than 36 mol %, the risk of deterioration in heat resistance can be reduced. From the viewpoint of obtaining a polyamide composition having an excellent balance between heat resistance and crystallization speed, the content of the diamine unit (X1) in the diamine unit (X) is preferably 0.5 mol% or more, more preferably 1 mol. % or more, more preferably 3 mol % or more, and even more preferably 5 mol % or more.
• the content of the diamine unit (X1) in the diamine unit (X) is preferably 35 mol% or less, more preferably 30 mol% or less, even more preferably 25 mol% or less, and even more preferably 20 mol% or less.
• mol % or less more preferably 18 mol % or less, even more preferably 15 mol % or less, and even more preferably 10 mol % or less.
• the content of structural units derived from 2-ethyl-1,7-heptanediamine in the diamine units (X) is preferably 0.5 mol % or more and 20 mol % or less.
• the content of structural units derived from 2-propyl-1,6-hexanediamine in the diamine unit (X) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. preferable.
• the content is preferably 5 mol % or less, more preferably 2 mol % or less. That is, the content of structural units derived from 2-propyl-1,6-hexanediamine in diamine units (X) is preferably 0.1 mol % or more and 5 mol % or less.
• Polyamide (A) contains diamine units (hereinafter also referred to as "diamine units (X2)") other than diamine units (X1) as diamine units (X).
• the diamine unit (X2) is preferably a structural unit derived from a diamine having 6 to 10 carbon atoms, more preferably derived from a diamine having 8 to 10 carbon atoms, from the viewpoint of good progress of the polymerization reaction between the dicarboxylic acid and the diamine. more preferably a structural unit derived from a diamine having 9 carbon atoms.
• Linear aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8 - octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15- pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine.
• Examples of branched aliphatic diamines other than the aliphatic diamines constituting the diamine unit (X1) include 1,2-propanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-Butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4- butanediamine, 2-methyl-1,3-propanediamine, 2-methyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3 -methyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine , 3,3-dimethyl-1,6-hexanedia
• Alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, norbornanedimethylamine, tricyclodecanedimethyldiamine, bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino-3-ethyl-5- methylcyclohexyl)methane.
• aromatic diamines examples include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4' -diaminodiphenyl ether, 4,4'-methylenedi-2,6-diethylaniline. Only one type of structural unit derived from the diamine may be used, or two or more types thereof may be used.
• diamine units (X2) structural units derived from at least one selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines having a methyl group are more preferred.
• the other diamine units include 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, and 2-methyl-1,5-pentane.
• Structural units derived from at least one selected from the group consisting of diamines and 2-methyl-1,8-octanediamine are more preferred.
• dicarboxylic acid unit (Y) Any dicarboxylic acid unit can be included as the dicarboxylic acid unit (Y).
• the dicarboxylic acid unit (Y) can contain a structural unit derived from, for example, at least one selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.
• aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, dimethylmalonic acid, 2, 2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid.
• aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, diphenic acid, 4,4′-biphenyldicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 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, 2,7-naphthalenedicarboxylic acid, 2,3-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,5-furandicarboxylic acid
• alicyclic dicarboxylic acids examples include 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclodecanedicarboxylic acid. mentioned. Only one kind of structural unit derived from the dicarboxylic acid may be contained, or two or more kinds thereof may be contained.
• the dicarboxylic acid unit (Y) may contain a structural unit derived from at least one selected from the group consisting of aromatic dicarboxylic acids and alicyclic dicarboxylic acids. More preferably, it contains a structural unit derived from at least one selected from the group consisting of terephthalic acid, cyclohexanedicarboxylic acid, and naphthalenedicarboxylic acid.
• the dicarboxylic acid unit (Y) more preferably contains a structural unit derived from terephthalic acid, from the viewpoint of further improving the crystallization speed and heat resistance and being excellent in hydrolysis resistance.
• the molar ratio [diamine unit (X)/dicarboxylic acid unit (Y)] of the diamine unit (X) and the dicarboxylic acid unit (Y) in the polyamide (A) is preferably 45/55 to 55/45.
• the molar ratio between the diamine units (X) and the dicarboxylic acid units (Y) can be adjusted according to the compounding ratio (molar ratio) between the raw material diamine and the raw material dicarboxylic acid.
• Total ratio of diamine units (X) and dicarboxylic acid units (Y) in polyamide (A) is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more. , or even 100 mol %. Further, the total proportion of the diamine units (X) and the dicarboxylic acid units (Y) in the polyamide (A) may be 100 mol% or less, or 99.5 mol% or less.
• the total proportion of diamine units (X) and dicarboxylic acid units (Y) in polyamide (A) is preferably 70 mol % or more and 100 mol % or less.
• the total ratio of the diamine units (X) and the dicarboxylic acid units (Y) is within the above range, it is possible to obtain a polyamide composition having more excellent physical properties than desired.
• the polyamide (A) may further contain aminocarboxylic acid units in addition to the diamine units (X) and the dicarboxylic acid units (Y).
• aminocarboxylic acid units include structural units derived from lactams such as caprolactam and lauryllactam; aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid.
• the content of aminocarboxylic acid units in the polyamide (A) is 40 mol% or less with respect to the total 100 mol% of the diamine units (X) and the dicarboxylic acid units (Y) constituting the polyamide (A). Preferably, it is 20 mol % or less.
• the polyamide (A) may contain structural units derived from a terminal blocker (terminal blocker units).
• the content of the terminal blocker unit is preferably 1.0 mol % or more, more preferably 2.0 mol % or more, relative to 100 mol % of the diamine unit (X).
• the content of the terminal blocker unit is preferably 10 mol % or less, more preferably 5.0 mol % or less, relative to 100 mol % of the diamine unit (X). That is, the content of the terminal blocker unit is preferably 1.0 mol % or more and 10 mol % or less with respect to 100 mol % of the diamine unit (X).
• the content of the terminal blocker unit is within the above range, it is easy to obtain a polyamide (A) having desired excellent physical properties.
• the content of the terminal blocking agent unit can be set within the above desired range by appropriately adjusting the amount of the terminal blocking agent when charging the polymerization raw material. Considering volatilization of the monomer components during polymerization, the charging amount of the terminal blocker should be finely adjusted so that the desired amount of terminal blocker units are introduced into the resulting polyamide (A). is desirable.
• a method for determining the content of terminal blocker units in the polyamide (A) for example, as shown in JP-A-7-228690, the solution viscosity is measured, and the number average molecular weight is calculated.
• a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group can be used as the terminal blocking agent.
• Specific examples include monocarboxylic acids, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and monoamines. From the viewpoint of reactivity and stability of the terminal to be blocked, monocarboxylic acid is preferable as the terminal blocking agent for the terminal amino group, and monoamine is preferable as the terminal blocking agent for the terminal carboxyl group. From the standpoint of ease of handling, etc., monocarboxylic acids are more preferable as terminal blocking agents.
• the monocarboxylic acid used as a terminal blocking agent is not particularly limited as long as it is reactive with amino groups, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, and laurin.
• acids tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, aliphatic monocarboxylic acids such as isobutyric acid; alicyclic monocarboxylic acids such as cyclopentanecarboxylic acid and cyclohexanecarboxylic acid; benzoic acid, toluic acid, aromatic monocarboxylic acids such as ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid; and any mixture thereof.
• acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, and stearic acid are preferred in terms of reactivity, stability of blocked ends, and price.
• benzoic acid are preferred.
• the monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with carboxyl groups. Examples include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, and stearyl. Aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine and dibutylamine; Alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; is mentioned.
• the content of the polyamide (A) contained in the total amount of the polyamide composition of the present embodiment is preferably 30 to 95% by mass, more preferably 30 to 95% by mass, from the viewpoint of easily ensuring good heat resistance, mechanical properties, and moldability. is 40 to 90% by mass, more preferably 45 to 85% by mass, more preferably 45 to 80% by mass.
• the terminal amino group content is more preferably 70 ⁇ mol/g or less, still more preferably 50 ⁇ mol/g or less, and even more preferably 35 ⁇ mol/g or less.
• the amount of terminal amino groups refers to the amount (unit: ⁇ mol) of terminal amino groups contained in 1 g of polyamide (A).
• the amount of terminal amino groups can be determined by a neutralization titration method using an indicator. More specifically, the terminal amino group content can be determined by the method described in Examples.
• the crystallization rate of polyamide (A) is preferably 0.020° C. ⁇ 1 or higher, more preferably 0.040° C. ⁇ 1 or higher. When the crystallization speed is within the above range, a polyamide composition having excellent productivity can be obtained.
• Polyamide (A) can be produced using any known method for producing polyamides. For example, it can be produced by a method such as a melt polymerization method, a solid phase polymerization method, or a melt extrusion polymerization method using a dicarboxylic acid and a diamine as raw materials. Among these, the solid-phase polymerization method is preferable from the viewpoint of being able to better suppress thermal deterioration during polymerization.
• faucet parts include housings for transporting tap water, housings for storing tap water, housings for filter casings, housings for faucets, housings for pipes, bathroom faucets (hot water switching valve, water volume switching valve etc.) housings, sanitary parts housings, kitchen faucet housings, water heater housings, valve parts (shut-off balls, slides, cylinders) and valve part housings, toilet faucet housings, housings in shower heads, Valve housings for water heaters, joints for residential plumbing (underfloor piping, etc.), joints for bathroom faucets, joints for water pipes, pipe joints, water meter housings, water meter parts (bearings, propellers, pins) and water meters, Gas meter housings, distributor housings, valve/pump housings for household equipment, steam-resistant parts of steam irons, inner containers of electric kettles, parts of dishwashers (washing tanks, washing nozzles, baskets), housings of pumps, pumps Components (e.g.
• the polyamide composition of the present embodiment is excellent in crystallization speed, heat resistance, and mechanical properties, so it can be suitably used for automobile parts that have strict cost requirements and require high heat resistance and mechanical properties. Specifically, it can be suitably used for radiator tanks, intercooler tanks, engine mount brackets, and the like.
• Molecular weight change rate (%) (molecular weight after immersion treatment - molecular weight before immersion treatment) / (molecular weight before immersion treatment) x 100 (Formula 3) ⁇ Evaluation Criteria> A: Molecular weight change rate within ⁇ 10%, B: Molecular weight change rate greater than ⁇ 10% and within ⁇ 20%, C: Molecular weight change rate greater than ⁇ 20%
• the molecular weight of the multi-purpose test piece type A1 was obtained as a standard polymethyl methacrylate equivalent molecular weight by gel permeation chromatography (GPC). Specifically, 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) was dissolved at a rate of 0.85 g with respect to 1 kg of HFIP solution, and the sample was 1.5 mg (in terms of resin) of (the multipurpose test piece type A1) was weighed and dissolved in 3 mL of the eluent. The solution was passed through a 0.2 ⁇ m membrane filter to prepare a measurement sample, and measurement was performed under the following conditions.
• GPC gel permeation chromatography
• the pressure inside the autoclave increased to 2 MPa. Heating was continued for 5 hours while maintaining the pressure at 2 MPa, and water vapor was gradually removed to allow the reaction to proceed. Next, the pressure was lowered to 1.3 MPa over 30 minutes, and the reaction was continued for 1 hour to obtain a prepolymer.
• the resulting prepolymer was dried at 100° C. under reduced pressure for 12 hours and pulverized to a particle size of 2 mm or less. This was subjected to solid phase polymerization at 230°C and 13 Pa (0.1 mmHg) for 10 hours to obtain a polyamide having a melting point of 282°C.
• the obtained polyamide and other additives are fed from the upstream hopper of a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd. "TEM-26SS") at the ratio shown in Table 1, and glass fibers ("ECS 03 T-262H ”, manufactured by Nippon Electric Glass Co., Ltd., catalog value: fiber diameter 10.5 ⁇ m, fiber length 3 mm) is fed from the side feed port on the downstream side of the extruder at the ratio shown in Table 1, melt-kneaded and extruded, A polyamide composition in the form of pellets was obtained by cooling and cutting.
• TEM-26SS twin-screw extruder
• the diamine unit is a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine and 2-methyl-1,8-octanediamine [5.6/0.4/94 (molar ratio )], in the same manner as in Example 1, to obtain a polyamide and a polyamide composition.
• the diamine unit is a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine and 1,9-nonanediamine [4/1/20 /75 (molar ratio)] in the same manner as in Example 1 to obtain a polyamide and a polyamide composition.
• Example 8 As diamine units, a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine and 1,9-nonanediamine [4/1/20 / 75 (molar ratio)] 5400 g, a polyamide and a polyamide composition were obtained in the same manner as in Example 1, except that the terminal amino group content and the terminal carboxyl group content were set to the contents shown in Table 1. rice field.
• Example 9 By blending the polyamide of Example 5 and the polyamide of Example 8 at a ratio of 7:3 (mass ratio), the terminal amino group content and the terminal carboxyl group content were set to the contents shown in Table 1.
• Example 5 Polyamides and polyamide compositions were obtained in the same manner as above.
• Example 3 A polyamide and a polyamide composition were prepared in the same manner as in Example 1 except that the diamine unit was a mixture of 2-methyl-1,8-octanediamine and 1,9-nonanediamine [15/85 (molar ratio)]. Obtained.
• Example 11 A polyamide and a polyamide composition were obtained in the same manner as in Example 5 except that the dicarboxylic acid unit was 7027 g of 2,6-naphthalenedicarboxylic acid.
• Example 4 A polyamide and a polyamide composition were prepared in the same manner as in Example 11 except that the diamine unit was a mixture of 2-methyl-1,8-octanediamine and 1,9-nonanediamine [15/85 (molar ratio)]. Obtained.
• Example 5 A polyamide and a polyamide composition were prepared in the same manner as in Example 13 except that the diamine unit was a mixture of 2-methyl-1,8-octanediamine and 1,9-nonanediamine [15/85 (molar ratio)]. Obtained.
• the diamine unit is a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine and 1,10-decanediamine [4/1/ 20/75 (molar ratio)] in the same manner as in Example 1 to obtain a polyamide and a polyamide composition.
• compositions of Examples and Comparative Examples and their measurement results are shown in Table 1 or Table 2.
• Examples have 2-ethyl-1, By containing a specific amount of 7-heptanediamine units and/or 2-propyl-1,6-hexanediamine units, it is found that the melting point and glass transition temperature are less lowered and the heat resistance is excellent. Therefore, from Tables 1 and 2, the polyamide compositions of Examples have improved moldability while maintaining excellent heat resistance, and are excellent in both moldability and heat resistance. It can be seen that the inclusion exhibits high flexural strength and flexural modulus, and is also excellent in mechanical properties. Moreover, from Tables 1 and 2, it can be seen that by optimizing the amount of terminal amino groups and the dicarboxylic acid unit of the polyamide, the polyamide composition can exhibit even better hydrolysis resistance.
• the polyamide composition of the present invention can simultaneously achieve excellent heat resistance, mechanical properties, and moldability, which have hitherto been difficult. Therefore, the polyamide composition of the present invention can be used as various molded articles that require heat resistance and mechanical properties, and it is possible to improve productivity when manufacturing molded articles, which is very useful. is.
• This application is based on a Japanese patent application (Japanese Patent Application No. 2021-206181) filed on December 20, 2021, the entirety of which is incorporated by reference.

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