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
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2231—Oxides; Hydroxides of metals of tin
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2296—Oxides; Hydroxides of metals of zinc
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K3/2279—Oxides; Hydroxides of metals of antimony
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

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, and materials with better performance in terms of heat resistance, hydrolysis resistance, etc. are required.
• there is a demand for 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 having 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.
• the present invention provides a polyamide composition that is excellent in heat resistance, flame retardancy, moldability, and hydrolysis resistance.
• the present inventors have conceived the following invention and found that the problems can be solved. That is, the present invention is as follows.
• 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 polyamide composition which is a structural unit derived from an aliphatic diamine to which 3 alkyl groups are bonded.
• the diamine unit (X1) is a structural unit derived from at least one diamine selected from the group consisting of 2-ethyl-1,7-heptanediamine and 2-propyl-1,6-hexanediamine.
• the diamine unit (X2) is a structural unit derived from at least one diamine selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines having a methyl group as a branched chain.
• 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 dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.
• the dicarboxylic acid unit (Y) contains a structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, cyclohexanedicarboxylic acid, and naphthalene dicarboxylic acid, above [1] to [ 9], the polyamide composition according to any one of the above.
• B1 brominated flame retardant
• 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 this embodiment 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 melting point is less lowered.
• the melting point is less lowered.
• the melting point is less lowered.
• the melting point is less lowered.
• the glass transition temperature 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.
• the polyamide (A) unexpectedly shows little decrease in the glass transition temperature and exhibits excellent heat resistance.
• 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) which is a structural unit 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 a structural unit 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".
• the branched aliphatic diamine unit constituting 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. 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.
• branched aliphatic diamine used to form the diamine unit (X1) as long as the effects of the present invention are not impaired, a branched chain such as a methyl group ("other branched chain” ).
• the number of other branched chains is preferably one or less, and more preferably the diamine unit (X1) does not contain other branched chains.
• Examples of the diamine unit (X1) include 2-ethyl-1,4-butanediamine, 2-ethyl-1,5-pentanediamine, 2-ethyl-1,6-hexanediamine, 2-ethyl-1,7 -heptanediamine, 2-ethyl-1,8-octanediamine, 2-propyl-1,5-pentanediamine, 2-propyl-1,6-hexanediamine, 2-propyl-1,7-heptanediamine, and 2 ,4-diethyl-1,6-hexanediamine. Only one type of these structural units may be contained, or two or more types may be contained.
• the diamine unit (X1) is a 2-ethyl-1,7- It is preferably a structural unit derived from at least one diamine selected from the group consisting of heptanediamine and 2-propyl-1,6-hexanediamine.
• the diamine unit (X) contains 0.1 mol % or more and less than 36 mol % of the diamine unit (X1). 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 rate, the diamine unit (X) is preferably 0.5 mol% or more, more preferably 1 mol% or more, of the diamine unit (X1).
• the diamine unit (X) is preferably 0.5 to 35 mol%, more preferably 0.5 to 30 mol%, still more preferably 1 to 30 mol%, more preferably 0.5 to 30 mol%, more preferably 0.5 to 30 mol%, more preferably More preferably 3 to 25 mol %, still more preferably 5 to 20 mol %.
• the diamine unit (X1) is at least one selected from the group consisting of 2-ethyl-1,7-heptanediamine and 2-propyl-1,6-hexanediamine.
• structural units derived from diamine an example of the content of each structural unit is as follows.
• the content of structural units derived from 2-ethyl-1,7-heptanediamine in the diamine unit (X) is preferably 0.5 mol% or more, more preferably 2 mol% or more, Also, it is preferably 20 mol % or less, more preferably 16 mol % or less, and even more preferably 10 mol % or less.
• the content of structural units derived from 2-ethyl-1,7-heptanediamine in diamine units (X) is preferably 0.5 to 20 mol %.
• 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. It is preferably 5 mol % or less, more preferably 3 mol % or less, and even more preferably 2 mol % or less.
• the content of structural units derived from 2-propyl-1,6-hexanediamine in diamine units (X) is preferably 0.1 to 5 mol %.
• the polyamide (A) contains, as the diamine unit (X), a diamine unit other than the diamine unit (X1) (hereinafter also referred to as "diamine unit (X2)").
• the diamine unit (X2) is preferably derived from a diamine having 6 to 10 carbon atoms, more preferably 8 to 10 carbon atoms, and still more preferably 9 carbon atoms, from the viewpoint of good progress of the polymerization reaction between the dicarboxylic acid and the diamine.
• the diamine unit (X2) is selected from the group consisting of linear aliphatic diamines, branched aliphatic diamines other than the aliphatic diamines constituting the diamine unit (X1), alicyclic diamines, and aromatic diamines. Structural units derived from at least one diamine are included.
• 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.
• Branched aliphatic diamines such as 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-hexanediamine , 2,2-dimethyl-1,6-hexanediamine, 2,2,
• 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 diamine selected from the group consisting of linear aliphatic diamines and branched aliphatic diamines having a methyl group are more preferred.
• the diamine unit (X2) is 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 2-methyl-1,5- Structural units derived from at least one diamine selected from the group consisting of pentanediamine and 2-methyl-1,8-octanediamine are more preferred.
• the dicarboxylic acid unit (Y) may contain, for example, a structural unit derived from at least one dicarboxylic acid 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) is a structural unit derived from at least one dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acids and alicyclic dicarboxylic acids. It preferably contains a structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, cyclohexanedicarboxylic acid, and naphthalenedicarboxylic acid.
• the total content of structural units derived from an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an alicyclic dicarboxylic acid in the dicarboxylic acid unit (Y) is from the viewpoint of making it easier to exhibit the effects of the present invention more remarkably. , preferably 80 mol % or more, more preferably 90 mol %, still more preferably 95 mol % or more, and may be 100 mol %. In other words, the total content of structural units derived from an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an alicyclic dicarboxylic acid in the dicarboxylic acid unit (Y) is preferably 80 to 100 mol%.
• the total content of structural units derived from terephthalic acid, cyclohexanedicarboxylic acid, and naphthalenedicarboxylic acid in the dicarboxylic acid unit (Y) is preferably 80 mol% or more, more preferably 90 mol. %, more preferably 95 mol % or more, and may be 100 mol %.
• the total content of structural units derived from terephthalic acid, cyclohexanedicarboxylic acid and naphthalenedicarboxylic acid in the dicarboxylic acid unit (Y) is preferably 80 to 100 mol%.
• 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, still more preferably 90 mol% or more, even more preferably 95 mol% or more, and It may be 100 mol %.
• the polyamide (A) can have more excellent physical properties than desired. In other words, the total proportion of diamine units (X) and dicarboxylic acid units (Y) in polyamide (A) is preferably 70-100 mol %.
• 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 the aminocarboxylic acid unit in the polyamide (A) is 40 mol% or less with respect to the total 100 mol% of the diamine unit (X) and the dicarboxylic acid unit (Y) constituting the polyamide (A). Preferably, it is 20 mol % or less. In other words, the content of aminocarboxylic acid units in the polyamide (A) is preferably 0 to 40 mol %.
• Polyvalent carboxylic acid unit Polyamide (A) is a range that does not impair the effects of the present invention, trimellitic acid, trimesic acid, pyromellitic acid, etc. Polyvalent carboxylic acid with a valence of 3 or more, a structural unit derived from, melt molding is possible can also contain
• the polyamide (A) may contain structural units derived from a terminal blocker (terminal blocker units).
• the terminal blocker unit is preferably 1.0 mol% or more, more preferably 2.0 mol% or more, and 10 mol% or less with respect to 100 mol% of the diamine unit (X). preferably 5.0 mol % or less.
• the terminal blocker unit is preferably 1.0 to 10 mol% with respect to 100 mol% of the diamine unit (X).
• 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.
• the inherent viscosity is measured, and this and the number
• JP-A-7-228690 the inherent viscosity (intrinsic viscosity) is measured, and this and the number
• JP-A-7-228690 the inherent viscosity (intrinsic viscosity) is measured, and this and the number
• a monofunctional compound having reactivity with a terminal amino group or a terminal carboxy 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 blocked terminal, 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 carboxy 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 is reactive with the carboxyl group. 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 20 to 60% by mass from the viewpoint of making it easy to ensure good moldability, heat resistance, mechanical strength and chemical resistance. , more preferably 25 to 55% by mass, still more preferably 30 to 50% by mass.
• Polyamide (A) preferably has an inherent viscosity of 0.5 dl/g or more, more preferably 0.7 dl/g or more, and preferably 2.0 dl/g or less. It is more preferably 5 dl/g or less. In other words, the inherent viscosity of polyamide (A) is preferably between 0.5 and 2.0 dl/g. When the inherent viscosity is within the above range, the polyamide (A) can have more excellent physical properties than desired.
• the inherent viscosity of the polyamide (A) can be determined by measuring the flowing time of a solution using concentrated sulfuric acid at a concentration of 0.2 g / dl and a temperature of 30 ° C. as a solvent, and more specifically described in the Examples. method.
• the polyamide (A) preferably has a melting point of 250° C. or higher, more preferably 280° C. or higher. When the melting point is within the above range, a polyamide composition having excellent heat resistance can be obtained.
• the upper limit of the melting point of the polyamide (A) is not particularly limited, it is preferably 330° C. or less in consideration of moldability. In other words, the melting point of polyamide (A) is preferably 250-330°C.
• the melting point of the polyamide (A) can be obtained as the peak temperature of the endothermic peak that appears when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) device. It can be obtained by the method described.
• the polyamide (A) preferably has a glass transition temperature of 110° C. or higher, more preferably 120° C. or higher. When the glass transition temperature is within the above range, a polyamide composition having excellent heat resistance can be obtained.
• the upper limit of the glass transition temperature of the polyamide (A) is not particularly limited, it is preferably 180° C. or less, more preferably 160° C. or less from the viewpoint of handleability, and even if it is 150° C. or less. good. In other words, the glass transition temperature of polyamide (A) is preferably 110-180°C.
• the glass transition temperature of the polyamide (A) can be obtained as the temperature of the inflection point that appears when the temperature is raised at a rate of 20 ° C./min using a differential scanning calorimetry (DSC) device. It can be obtained by the method described in the example.
• DSC differential scanning calorimetry
• Polyamide (A) preferably has a crystallization rate of 0.02° C. ⁇ 1 or more, more preferably 0.04° C. ⁇ 1 or more.
• Polyamide (A) preferably has a terminal amino group content ([NH 2 ]) in its molecular chain of 5 ⁇ mol/g or more, more preferably 10 ⁇ mol/g or more, and 160 ⁇ mol/g or less. is preferably 100 ⁇ mol/g or less, and even more preferably 80 ⁇ mol/g or less. In other words, the terminal amino group content is preferably 5 to 160 ⁇ mol/g. If the amount of terminal amino groups is 5 ⁇ mol/g or more, a much more excellent crystallization rate can be exhibited, and good hydrolysis resistance can be exhibited.
• a terminal amino group content [NH 2 ]
• the polyamide composition of the present embodiment contains a fibrous filler (C1) as the filler (C), the adhesion with the fibrous filler (C1) is improved, and the mechanical properties are improved. can be done. If the amount of terminal amino groups is 160 ⁇ mol/g or less, further excellent heat resistance is exhibited, and the melt viscosity during processing of the polyamide composition is improved. In the present invention, the amount of terminal amino groups refers to the amount (unit: ⁇ mol) of terminal amino groups contained in 1 g of polyamide.
• the amount of terminal amino groups of the polyamide (A) can be determined by titrating a phenol solution in which the polyamide (A) is dissolved with an aqueous hydrochloric acid solution, and more specifically determined by the method described in Examples. be able to.
• the polyamide (A) preferably has a terminal carboxy group content ([COOH]) of the molecular chain of 2 ⁇ mol/g or more, more preferably 5 ⁇ mol/g or more, and further preferably 10 ⁇ mol/g or more. It is preferably 100 ⁇ mol/g or less, more preferably 80 ⁇ mol/g or less. In other words, the terminal carboxy group content is preferably 2 to 100 ⁇ mol/g. When the amount of terminal carboxy groups is 2 ⁇ mol/g or more, a further excellent crystallization rate is exhibited, and excellent heat resistance is likely to be exhibited.
• the polyamide composition of the present embodiment contains a fibrous filler (C1) as the filler (C), the adhesion with the fibrous filler (C1) is improved, and the mechanical properties are improved. can be done.
• the amount of terminal carboxy groups is 100 ⁇ mol/g or less, good hydrolysis resistance can be exhibited. Furthermore, hydrolysis in an acidic environment is suppressed, improving chemical resistance.
• the amount of terminal carboxy groups refers to the amount (unit: ⁇ mol) of terminal carboxy groups contained in 1 g of polyamide.
• the amount of terminal carboxyl groups of the polyamide (A) can be obtained by titrating a cresol solution in which the polyamide (A) is dissolved with a potassium hydroxide solution, more specifically the method described in the Examples. can be obtained by
• Polyamide (A) has a ratio ([NH 2 ]/[COOH]) of a terminal amino group amount ([NH 2 ]) to a terminal carboxy group amount ([COOH]) of the molecular chain of 0.1 or more. more preferably 0.3 or more, preferably 50 or less, more preferably 10 or less, and even more preferably 6 or less.
• the ratio ([NH 2 ]/[COOH]) is preferably between 0.1 and 50. If the ratio ([NH 2 ]/[COOH]) is 0.1 or more, a much more excellent crystallization rate can be exhibited, and good hydrolysis resistance can be exhibited. If the ratio ([NH 2 ]/[COOH]) is 50 or less, even better heat resistance is exhibited.
• 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.
• polyamide (A) for example, a diamine, a dicarboxylic acid, and, if necessary, a catalyst and a terminal blocking agent are added all at once to produce a nylon salt, and then heat polymerized at a temperature of 200 to 250 ° C. It can be produced by preparing a prepolymer by heating and then solid-phase polymerizing it, or by polymerizing it using a melt extruder. When the final stage of polymerization is carried out by solid phase polymerization, it is preferably carried out under reduced pressure or under inert gas flow. Coloring and gelation can be effectively suppressed. When the final stage of polymerization is carried out using a melt extruder, the polymerization temperature is preferably 370° C. or less. Polymerization under such conditions yields a polyamide (A) with little degradation and little decomposition.
• Examples of catalysts that can be used when producing polyamide (A) include phosphoric acid, phosphorous acid, hypophosphorous acid, or salts or esters thereof.
• Examples of the above salts or esters include phosphoric acid, phosphorous acid, or hypophosphorous acid and potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony, and the like.
• Salt with metal Ammonium salt of phosphoric acid, phosphorous acid or hypophosphite; Ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester of phosphoric acid, phosphorous acid or hypophosphorous acid , decyl ester, stearyl ester, phenyl ester, and the like.
• the amount of the catalyst used is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 1.0% by mass or less with respect to 100% by mass of the total mass of the raw materials. and more preferably 0.5% by mass or less. In other words, the amount of the catalyst used is preferably 0.01 to 1.0% by mass with respect to 100% by mass of the total mass of the raw materials. If the amount of the catalyst used is at least the above lower limit, the polymerization proceeds satisfactorily. Further, when the amount of the catalyst used is equal to or less than the above upper limit, impurities derived from the catalyst are less likely to be generated, and, for example, when the polyamide composition is made into a film, problems due to the above impurities can be prevented.
• the polyamide composition of this embodiment contains a halogen flame retardant (B).
• a halogen flame retardant (B) By containing the halogen-based flame retardant (B), a polyamide composition having improved flame retardancy is obtained.
• the halogen-based flame retardant (B) contained in the polyamide composition of the present embodiment is not particularly limited, and compounds known as flame retardants containing a halogen element can be used, for example, brominated flame retardants (B1), Chlorine-based flame retardants (B2) and the like can be mentioned, and brominated flame retardants (B1) are preferred. These may be used individually by 1 type, and may use 2 or more types together.
• brominated flame retardant (B1) examples include hexabromocyclododecane, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, bis(tribromophenoxy)ethane, bis(pentabromophenoxy)ethane, tetrabromo Bisphenol A epoxy resin, tetrabromobisphenol A carbonate, ethylene (bistetrabromophthal)imide, ethylenebispentabromodiphenyl, tris(tribromophenoxy)triazine, bis(dibromopropyl)tetrabromobisphenol A, bis(dibromopropyl)tetra Bromobisphenol S, brominated polyphenylene ethers such as poly(di)bromophenylene ether, brominated polystyrenes such as polydibromostyrene
• brominated flame retardant (B1) from the viewpoint of reducing the amount of corrosive gas generated during melt processing such as extrusion and molding and improving the flame retardancy and mechanical properties of electrical or electronic parts, brominated Polyphenylene ether and brominated polystyrene are preferred, and brominated polystyrene is more preferred.
• Brominated polystyrene is produced by, for example, polymerizing styrene monomers to produce polystyrene, then brominated the benzene ring of polystyrene, and polymerizing brominated styrene monomers such as bromostyrene, dibromostyrene, and tribromostyrene. It can be manufactured by a method.
• the bromine content in the brominated polystyrene is preferably 55-75% by mass, more preferably 55-70% by mass.
• the bromine content is preferably 55-75% by mass, more preferably 55-70% by mass.
• the amount of bromine required for flame retardancy can be satisfied with a small brominated polystyrene content, and the deterioration of the mechanical properties of the polyamide (A) is also suppressed.
• a polyamide composition having excellent mechanical properties and heat resistance can be obtained.
• by setting the bromine content to 75% by mass or less it is difficult to cause thermal decomposition during melt processing such as extrusion and molding, it is possible to suppress gas generation, etc., and a polyamide composition having excellent heat discoloration resistance can be obtained. be able to.
• Chlorine flame retardant (B2) examples include chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene (“Dechloran Plus 25” manufactured by Occidental Chemical Co.), het acid anhydride, and the like. mentioned.
• the polyamide composition of this embodiment preferably contains 5 parts by mass or more and 100 parts by mass or less of the halogen-based flame retardant (B) described above with respect to 100 parts by mass of the polyamide (A), and 10 parts by mass or more and 75 parts by mass. It is more preferably contained in an amount of 30 to 70 parts by mass, and even more preferably 40 to 60 parts by mass.
• the content of the halogen-based flame retardant (B) is set to 100 parts by mass or less, generation of decomposition gas during melt-kneading, deterioration of fluidity during molding (especially thin-wall fluidity) and molding die Adhesion of contaminants to the surface can be suppressed, and deterioration of mechanical properties and external appearance of molded products can also be suppressed.
• the total amount thereof should be within the above range.
• the polyamide composition of this embodiment may further contain a filler (C).
• a filler (C) By using the filler (C), it is possible to obtain a thin polyamide composition having excellent flame retardancy, heat resistance, moldability, and mechanical strength.
• filler (C) those having various forms such as fibrous, tabular, needle-like, powdery and cloth-like can be used.
• inorganic or organic fibrous fillers such as glass fiber, carbon fiber, wholly aromatic polyamide fiber (aramid fiber), liquid crystal polymer (LCP) fiber, gypsum fiber, brass fiber, ceramic fiber, boron whisker fiber, etc.
• C1 flat fillers such as glass flakes and mica; needle fillers such as potassium titanate whiskers, aluminum borate whiskers, calcium carbonate whiskers, magnesium sulfate whiskers, wollastonite, sepiolite, xonotlite, and zinc oxide whiskers (C2); aluminum nitride, boron nitride, potassium titanate, aluminum silicate (kaolin, clay, pyrophyllite, bentonite), calcium silicate, magnesium silicate (attapulgite), aluminum borate, calcium sulfate, barium sulfate, Magnesium sulfate, asbestos, glass beads, carbon black, graphene, graphite, carbon nanotubes, silicon carbide, sericite, hydrotalcite, montmorillonite, molybdenum disulfide, ultra-high molecular weight polyethylene particles, phenol resin particles, crosslinked styrene resin particles, powder fillers such as crosslinked acrylic resin particles; cloth fillers such as glass cloth; These may be
• the surface of the filler (C) is coated with polymer compounds such as silane coupling agents, titanium coupling agents, acrylic resins, urethane resins, and epoxy resins for the purpose of enhancing dispersibility and adhesion in the polyamide (A).
• polymer compounds such as silane coupling agents, titanium coupling agents, acrylic resins, urethane resins, and epoxy resins for the purpose of enhancing dispersibility and adhesion in the polyamide (A).
• it may be surface-treated with other low-molecular-weight compounds.
• the fillers (C) at least one selected from the group consisting of fibrous fillers (C1) and acicular fillers (C2) because it is low in cost and gives molded articles with high mechanical strength. is preferred. From the viewpoint of high strength and low cost, the fibrous filler (C1) is preferable, and glass fiber is more preferable.
• the acicular filler (C2) is preferable from the viewpoint of obtaining a molded article with high surface smoothness.
• the fibrous filler (C1) and the needle-like filler (C2) are preferably at least one selected from the group consisting of glass fibers, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, and aluminum borate whiskers. , glass fiber and wollastonite are more preferable, and glass fiber is more preferable.
• the fibrous filler (C1) preferably has an average fiber length of 1 to 10 mm, more preferably 1 to 7 mm, still more preferably 2 to 4 mm. Also, the average fiber diameter of the fibrous filler (C1) is preferably 6 to 20 ⁇ m, more preferably 6 to 15 ⁇ m, from the viewpoint of obtaining mechanical strength.
• the average fiber length and average fiber diameter of the fibrous filler (C1) are obtained by measuring the fiber length and fiber diameter of 400 arbitrarily selected fibrous fillers (C1) by image analysis using an electron microscope. , can be obtained by calculating the respective average values.
• the average fiber length and average fiber diameter of the fibrous filler (C1) in the polyamide composition or in the molded article formed by molding the polyamide composition are, for example, the polyamide composition or the molded article in an organic solvent is dissolved, the fibrous filler (C1) is extracted, and it can be determined by image analysis using an electron microscope in the same manner as described above.
• the cross-sectional shape of the fibrous filler (C1) and the needle-like filler (C2) includes, for example, a circular shape, a rectangular shape, an oval shape close to a rectangle, an elliptical shape, a cocoon shape, and a cocoon shape with a constricted central portion in the longitudinal direction. mentioned. Among them, the cross-sectional shape of the fibrous filler (C1) and the needle-like filler (C2) is preferably circular, rectangular, oval nearly rectangular, elliptical, or cocoon-shaped.
• the fibrous filler (C1) is glass fiber
• specific compositions include an E glass composition, a C glass composition, an S glass composition, an alkali-resistant glass composition, and the like.
• the tensile strength of the glass fiber is arbitrary, but usually 290 kg/mm 2 or more.
• E glass is preferable from the viewpoint of easy availability.
• These glass fibers are preferably surface-treated with a silane coupling agent such as ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane.
• the adhered amount is usually 0.01% by mass or more based on the mass of the glass fiber (the total amount of the glass fiber and the surface treatment agent).
• the polyamide composition of the present embodiment contains a filler (C)
• its content is preferably 0.1 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyamide (A), and more It is preferably 1 part by mass or more and 180 parts by mass or less, more preferably 5 parts by mass or more and 150 parts by mass or less.
• the polyamide composition of this embodiment may further contain a flame retardant aid (D).
• a flame retardant aid D
• the auxiliary flame retardant (D) together with the halogen-based flame retardant (B)
• the polyamide composition of the present embodiment and the molded article made thereof can exhibit even better flame retardancy.
• Examples of the flame retardant aid (D) include antimony oxides such as diantimony trioxide, diantimony tetroxide and diantimony pentoxide; antimony compounds such as antimonates such as sodium antimonate; melamine orthophosphate, pyrophosphate.
• Melamine compounds such as melamine, melamine borate, and melamine polyphosphate; Tin oxides such as tin monoxide and tin dioxide; Iron oxides such as ferric oxide and ⁇ -iron oxide; Aluminum oxide, silicon oxide (silica), titanium oxide , zirconium oxide, manganese oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, nickel oxide, copper oxide, tungsten oxide and other metal oxides; metal hydroxides such as aluminum hydroxide; aluminum, iron, Metal powders such as titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, and tungsten; Metal carbonates such as zinc carbonate, magnesium carbonate, and barium carbonate; Zinc borate, calcium borate, etc. metal borates; zinc stannates such as zinc trioxide; and silicones. However, those corresponding to the filler (C) are excluded. These may
• At least one selected from the group consisting of antimony-based compounds, melamine-based compounds, metal oxides, metal hydroxides, metal borates, and zinc stannate is preferable.
• At least one selected from the group consisting of antimony, diantimony pentoxide, sodium antimonate, melamine orthophosphate, melamine pyrophosphate, melamine borate, melamine polyphosphate, aluminum oxide, aluminum hydroxide, zinc borate, and zinc tin trioxide 1 type is more preferable.
• the flame retardant aid (D) is preferably contained in the polyamide composition of the present embodiment in the form of powder.
• the upper limit of the average particle size is preferably 30 ⁇ m, more preferably 15 ⁇ m, still more preferably 10 ⁇ m, and particularly preferably 7 ⁇ m.
• the lower limit of the average particle size of the auxiliary flame retardant (D) is preferably 0.01 ⁇ m.
• the average particle size is 0.01 to 30 ⁇ m, the resulting polyamide composition has improved flame retardancy.
• the "average particle size” means the volume average particle size, and the particle size at which the cumulative volume is 50% (50 % particle diameter D50).
• the content is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyamide (A), 1 part by mass 25 mass parts or less is more preferable, 3 mass parts or more and 20 mass parts or less is still more preferable, and 3 mass parts or more and 15 mass parts or less is even more preferable.
• the polyamide composition of this embodiment includes the above-described polyamide (A) and halogen-based flame retardant (B), and optionally used filler (C) and flame retardant aid (D) other additives may be included as needed.
• additives include, for example, stabilizers such as copper compounds; antioxidants such as hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and thio-based antioxidants; colorants; UV absorber; light stabilizer; antistatic agent; heat stabilizer; crystal nucleating agent; plasticizer; lubricant; impact modifiers such as copolymers and rubbers; anti-drip agents such as fluororesins;
• the content of the other additives is not particularly limited as long as it does not impair the effects of the present invention.
• 03 to 100 parts by mass is more preferable, 0.05 to 50 parts by mass is more preferable, and 0.1 to 20 parts by mass is even more preferable.
• the total content of the polyamide (A) and the halogen-based flame retardant (B) in the total amount of the polyamide composition of the present embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably is 60% by mass or more.
• the polyamide composition of the present embodiment maintains the excellent physical properties of the polyamide (A) and has excellent flame retardancy, moldability and It has hydrolysis resistance.
• Method for producing polyamide composition There are no particular restrictions on the method for producing the polyamide composition, and the polyamide (A), the halogen-based flame retardant (B), the filler (C) used as necessary, the flame retardant auxiliary (D) and the above additives are uniformly mixed. can be preferably employed.
• a method of melt-kneading using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, or the like is preferably adopted.
• the melt-kneading conditions are not particularly limited, for example, a method of melt-kneading for about 1 to 30 minutes at a temperature in the range of about 10 to 50° C. higher than the melting point of the polyamide can be mentioned.
• the polyamide composition preferably has a bending strength of 100 MPa or more, more preferably 150 MPa or more. Also, the bending elastic modulus is preferably 2 GPa or more, more preferably 5 GPa or more. When the bending strength and bending elastic modulus are within the above ranges, a polyamide composition having excellent mechanical properties can be obtained.
• the flexural strength and flexural modulus of the polyamide composition can be determined by performing a bending test after injection molding the polyamide composition into a test piece having a thickness of 4 mm, and more specifically determined by the method described in the Examples. be able to.
• a molded article made of the above polyamide composition can be provided.
• the method for producing the molded article is not particularly limited, and known methods can be used. Additives such as a chain extender may be added at the time of molding, and further, treatment such as heat treatment or electron beam cross-linking may be performed after molding.
• the molded article of the present embodiment can be used as various molded articles of any shape and purpose such as electric parts, electronic parts, automobile parts, industrial parts, faucet parts, fibers, films, sheets, household goods, leisure goods, etc. be able to.
• Examples of electrical and electronic components include connectors such as FPC connectors, BtoB connectors, card connectors, SMT connectors (coaxial connectors, etc.), memory card connectors; SMT relays; SMT bobbins; sockets such as memory sockets and CPU sockets; , switches such as SMT switches; optical components such as optical fiber components and optical sensors; LED application components such as LED reflectors; .
• connectors such as FPC connectors, BtoB connectors, card connectors, SMT connectors (coaxial connectors, etc.), memory card connectors; SMT relays; SMT bobbins; sockets such as memory sockets and CPU sockets; , switches such as SMT switches; optical components such as optical fiber components and optical sensors; LED application components such as LED reflectors; .
• Automotive parts include cooling parts such as thermostat housings, coolant control valve housings, thermal management module housings, radiator tanks, radiator hoses, water outlets, water inlets, water pump housings, rear joints; intercooler tanks, intercooler cases, Intake and exhaust system parts such as turbo duct pipes, EGR cooler cases, resonators, throttle bodies, intake manifolds, tail pipes; fuel delivery pipes, gasoline tanks, quick connectors, canisters, pump modules, fuel pipes, oil strainers, lock nuts, seals Fuel system parts such as lumber; Structural parts such as mount brackets, torque rods, and cylinder head covers; Drive system parts such as bearing retainers, gear tensioners, headlamp actuator gears, throttle valve gears, slide door rollers, and clutch peripheral parts; Air brake tubes Brake system parts such as; wire harness connectors in the engine room, motor parts, sensors, ABS bobbins, combination switches, automotive electrical parts such as in-vehicle switches; sliding door dampers, door mirror stays, door mirror brackets, inner mirror stays, roof rails, engines Mount
• Examples of industrial parts include gas pipes, oil field mining pipes, hoses, anti-termite cables (communication cables, pass cables, etc.), powder coating parts (inner coating of water pipes, etc.), submarine oil field pipes, pressure hoses, Hydraulic tubes, paint tubes, fuel pump housings and impellers, separators, supercharge ducts, butterfly valves, carrier roller bearings, railway sleeper spring holders, outboard engine covers, generator engine covers, wind power generators blades, irrigation valves, large switches, and monofilaments such as fishing nets (extruded threads).
• 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 component housings, kitchen faucet housings, water heater housings, valve components (shut-off balls, slides, cylinders) and valve component 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.
• turbine wheels, impellers housings for water supply systems (hot water tanks, etc.), housings for heating systems, housings for cooling systems, water control valves, pressure reducing valves, relief valves, solenoid valves, three-way valves, thermo valves, Hot water temperature sensor, water volume sensor, bathtub adapter, etc.
• fibers include airbag base fabrics, heat-resistant filters, reinforcing fibers, bristles for brushes, fishing lines, tire cords, artificial turf, carpets, and fibers for seat sheets.
• Films and sheets include, for example, heat-resistant masking tapes, heat-resistant adhesive tapes such as industrial tapes; cassette tapes, magnetic tapes for data storage for digital data storage, materials for magnetic tapes such as video tapes; food packaging materials such as individual packaging and packaging of processed meat products; and electronic component packaging materials such as packaging for semiconductor packages.
• Household goods include, for example, valve/pump housings for tea and coffee makers; valve/pump housings for cooking appliances such as rice cookers and steamers; Sliding parts (gears, etc.) of cooking appliances such as rice cookers and steamers; sliding parts of commercial cooking utensils (gears for gear pumps, etc.); steam-resistant parts of commercial cooking utensils (pipes of commercial rice cookers, etc.), etc. is mentioned.
• Portable goods include, for example, inner soles of sports shoes, frames and grommets of rackets, heads and sleeves of golf clubs, reels and rods of fishing gear, boat screws, bicycle suspensions, gears, saddles, bottle cages, and the like. .
• the polyamide composition of the present embodiment has excellent heat resistance, flame retardancy and moldability, and excellent hydrolysis resistance, so it is required to produce a large number of parts in a short time.
• Electric parts and electronic parts It can be suitably used for Specifically, electrical and electronic components including SMT processes, more specifically connectors compatible with SMT, SMT relays, SMT bobbins, sockets, command switches, SMT switches, camera modules, power supply components, sensors, and capacitor base plates. , hard disk parts, resistors, fuse holders, coil bobbins, IC housings and other surface mount parts.
• the inherent viscosity (dl/g) at a concentration of 0.2 g/dl and a temperature of 30° C. using concentrated sulfuric acid as a solvent was obtained from the following formula.
• ⁇ [ln(t 1 /t 0 )]/c
• ⁇ represents the inherent viscosity (dl / g)
• t 0 represents the flow time (seconds) of the solvent (concentrated sulfuric acid)
• t 1 represents the flow time (seconds) of the sample solution
• c is the sample Represents the concentration (g/dl) of the sample in solution (ie 0.2 g/dl).
• the glass transition temperature (° C.) was measured according to ISO 11357-2 (2nd edition, 2013). Specifically, in a nitrogen atmosphere, the sample (polyamide) was heated from 30 ° C. to 340 ° C. at a rate of 20 ° C./min, held at 340 ° C. for 5 minutes to completely melt the sample, and then heated to 20 ° C. /min to 50°C and held at 50°C for 5 minutes. The temperature at the inflection point when the temperature was again raised to 200°C at a rate of 20°C/min was taken as the glass transition temperature (°C).
• Terminal carboxy group amount ([COOH])
• the amount of terminal carboxyl groups of the polyamides obtained in Examples and Comparative Examples was obtained by dissolving a solution of 0.5 g of polyamide in 40 mL of cresol with a potentiometric titrator manufactured by Kyoto Electronics Industry Co., Ltd., and adding 0.01 mol/L hydroxylation. It was calculated by titration with an aqueous potassium solution.
• the amount of terminal carboxyl groups of polyamide is represented by [COOH].
• ⁇ Polyamide composition> ⁇ Preparation of test piece>> Using an injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. (clamping force: 100 tons, screw diameter: ⁇ 32 mm), using the polyamide compositions obtained in Examples and Comparative Examples, the melting point of the polyamide was 20 The cylinder temperature is set to 30 ° C. higher, and the polyamide compositions of Examples 1 to 8, 11 and Comparative Examples 1, 2, 4, 5 are obtained under the conditions of a mold temperature of 140 ° C., Examples 9, 10 and Comparative Example 3.
• Table 1 shows the compositions of Examples and Comparative Examples and their measurement results.

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