Classifications

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

Definitions

• the present invention relates to a polyamide composition and a molded article, and in particular, a polyamide composition containing a specific diamine unit having a branched chain and a dicarboxylic acid unit, a polyamide composition containing a polyolefin, and a molded article made of the polyamide composition Regarding.
• 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, toughness, etc. are required.
• a material that takes a short time to cool and solidify from a molten state in other words, a material that has a high crystallization rate. Having a high crystallization rate improves moldability, can shorten the time required for molding one part, and can improve production efficiency. Therefore, it is required to have good other properties such as heat resistance while having high moldability.
• Patent Document 1 discloses a polyamide obtained by polymerizing a diamine containing at least 50 mol% of a diamine having a branched structure and a dicarboxylic acid containing at least 50 mol% of an aliphatic dicarboxylic acid, and a polyamide composition containing titanium oxide particles. things are disclosed. Patent Document 1 describes that the above polyamide composition is excellent in fluidity, toughness, resistance to heat discoloration, and processability. Further, Patent Document 2 discloses a method for producing a polyamide composition containing constitutional units derived from diamines having methyl or ethyl branches. Furthermore, in 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 as optional structural 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 mention a methyl group, an ethyl group, an n-propyl group, and the like as substituents branched from the main chain of the structural unit derived from the diamine that forms the polyamide.
• diamines with methyl groups as branched chains are specifically exemplified.
• None of the documents has a specific disclosure of a polyamide containing a structural unit derived from a branched diamine, which has a substituent longer than a methyl group as a branched chain, in other words, a substituent having more carbon atoms than a methyl group.
• an object of the present invention is to provide a polyamide composition having high moldability, excellent heat resistance and toughness, and a molded article made of the polyamide composition.
• the present invention is as follows.
• 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,
• a polyamide composition, wherein the content of the polyolefin (B) in the polyamide composition is 2% by mass or more and less than 40% by mass.
• the diamine unit (X1) is 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 [ 5], the polyamide composition.
• 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) comprises a structural unit derived from at least one selected from the group consisting of terephthalic acid, cyclohexanedicarboxylic acid, and naphthalenedicarboxylic acid.
• the polyolefin (B) is a polymer modified with an unsaturated compound having at least one selected from the group consisting of a carboxyl group and an acid anhydride group.
• Polyamide composition according to. [13] A molded article made of the polyamide composition according to any one of [1] to [12] above.
• the present invention it is possible to provide a polyamide composition having high moldability, excellent heat resistance and toughness, and a molded article made of the polyamide composition.
• 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 composition of the present embodiment contains a polyamide (A) containing diamine units (X) and dicarboxylic acid units (Y). Then, 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 0.1 mol % or more and less than 36 mol % of the diamine unit (X1), which is a structural unit derived from an aliphatic diamine to which 3 alkyl groups are bonded.
• the polyamide composition has high moldability, excellent heat resistance, and toughness.
• a component such as a branched chain having a large excluded volume is contained in the polymer skeleton, it becomes difficult for the molecular chains to arrange regularly, so the polymer tends to exhibit a low crystallization rate.
• a polyamide (A) containing a specific amount of structural units derived from a diamine having an alkyl group having 2 or 3 carbon atoms as a branched chain such as an ethyl group or a propyl group is used. Therefore, it unexpectedly exhibits a high crystallization rate.
• the polyamide (A) contained in the polyamide composition has a relatively bulky substituent having 2 or 3 carbon atoms such as an ethyl group or a propyl group as a branched chain. , the lowering of the melting point is small, and excellent heat resistance can be expressed.
• the glass transition temperature is a property that becomes higher as the molecular mobility of the amorphous portion becomes lower. Therefore, when a component with high molecular mobility such as a branched chain is contained, the glass transition temperature generally tends to be low.
• the polyamide (A) contained in the polyamide composition of the present embodiment unexpectedly shows little decrease in glass transition temperature.
• One of the reasons why the polyamide (A) expresses the above properties is that the number of carbon atoms in the branched chain, the position of the branched chain, and the amount of the branched chain in the diamine unit (X) contained in the polyamide (A) are , it is thought that it affects the improvement of the crystallization speed while suppressing the heat resistance from greatly decreasing.
• the detailed reason is unknown.
• the polyamide composition of the present embodiment contains a polyolefin (B), thereby maintaining the excellent physical properties of the polyamide (A) while maintaining high moldability and excellent It has toughness.
• polyamide (A) The polyamide (A) contained in the polyamide composition contains diamine units (X) and dicarboxylic acid units (Y). The configuration of the polyamide (A) will be described below.
• 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.
• branched aliphatic diamine unit 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.
• 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 bonded to the carbon atom at the 2-position is selected from the group consisting of an ethyl group, a propyl group, and an isopropyl group. It is preferably at least one selected, more preferably at least one selected from the group consisting of ethyl groups and propyl groups. If the number of carbon atoms in the alkyl group bonded to the carbon atom at the 2-position is 1 or 4 or more, the crystallization speed will not be improved and the heat resistance may be lowered.
• branched aliphatic diamine used to form the diamine unit (X1)
• a branched chain such as a methyl group
• the number of other branched chains is preferably one or less, and more preferably the diamine unit (X1) does not contain other branched chains.
• diamine unit (X1) examples 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. Among them, the diamine unit (X) is 2-ethyl-1,7- A structural unit derived from at least one selected from the group consisting of heptanediamine and 2-propyl-1,6-hexanediamine is preferred.
• 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%.
• 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, still more preferably 5 mol % or more.
• the diamine unit (X1) in the diamine unit is preferably 35 mol% or less, more preferably 30 mol% or less, still more preferably 25 mol% or less, still more preferably 20 mol% or less, and even more preferably 20 mol% or less. It is preferably 18 mol % or less, more preferably 15 mol % or less, and even more preferably 10 mol % or less.
• 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 More preferably 1 to 25 mol %, still more preferably 1 to 20 mol %, still more preferably 1 to 18 mol %, still more preferably 1 to 15 mol %, particularly preferably 1 to 10 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.
• a structural unit derived from diamine is included, 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.
• the content is preferably 20 mol% or less, more preferably 16 mol% or less, even more preferably 15 mol% or less, and even more preferably 12 mol% or less. , 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. preferable.
• the content is preferably 5 mol% or less, more preferably 3 mol% or less, even more preferably 2 mol% or less, and more preferably 1.5 mol% or less. More preferred.
• 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 diamine units other than the diamine unit (X1) (hereinafter also referred to as "diamine unit (X2)") as the diamine unit (X).
• the diamine unit (X2) is contained in more than 64 mol% and 99.9 mol% or less in the diamine unit (X). When the content of the diamine unit (X2) is more than 64 mol%, deterioration of heat resistance can be suppressed, and when it is 99.9 mol% or less, the crystallization rate can be improved.
• the diamine unit (X2) in the diamine unit (X) is preferably 99.5 mol% or less, more preferably 99 mol% or less, More preferably 97 mol % or less, still more preferably 95 mol % or less.
• the diamine unit (X2) in the diamine unit is preferably 65 mol% or more, more preferably 70 mol% or more, still more preferably 75 mol% or more, still more preferably 80 mol% or more, and still more It is preferably 82 mol % or more, still more preferably 85 mol % or more, and even more preferably 90 mol % or more.
• the diamine unit (X) is preferably 65 to 99.5 mol%, more preferably 75 to 99 mol%, even more preferably 80 to 99 mol%, more preferably 80 to 99 mol%, more preferably More preferably 82 to 99 mol %, still more preferably 85 to 99 mol %, particularly preferably 90 to 99 mol %.
• 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 facilitating 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 species 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.
• the 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. From the viewpoint that the effects of the present invention are likely to be exhibited more remarkably, 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) 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 (Y) derived from the above 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. and more 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 dicarboxylic acid unit more preferably contains a structural unit derived from terephthalic acid, from the viewpoint of further improving the crystallization rate and heat resistance and being excellent in hydrolysis resistance.
• 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, and even more preferably 95 mol% or more. , or even 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 other structural units in addition to the diamine units (X) and the dicarboxylic acid units (Y). For example, it may further contain an aminocarboxylic acid unit, a polyvalent carboxylic acid unit, and a terminal blocker unit.
• aminocarboxylic acid unit examples 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.
• 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.
• a method for determining the content of the terminal blocker unit in the polyamide (A) for example, as shown in JP-A-7-228690, the inherent 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; are mentioned.
• the content of the polyamide (A) contained in the total amount of the polyamide composition of the present embodiment is preferably more than 60% by mass and 98% by mass or less from the viewpoint of easily ensuring good moldability, heat resistance, and toughness. Yes, more preferably 65 to 97% by mass, still more preferably 70 to 96% by mass, still more preferably 75 to 95% by mass.
• the polyamide (A) preferably has an inherent viscosity of 0.5 dl/g or more, more preferably 0.7 dl/g or more. Also, it is preferably 2.0 dl/g or less, more preferably 1.5 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, it becomes easier to obtain a polyamide (A) having 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.
• Polyamide (A) preferably has a terminal amino group content ([NH 2 ]) in its molecular chain of 5 to 100 ⁇ 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. If the amount of terminal amino groups is 100 ⁇ mol/g or less, even better heat resistance is exhibited. From the viewpoint of crystallization rate and hydrolysis resistance, the terminal amino group content is more preferably 8 ⁇ mol/g or more, still more preferably 10 ⁇ mol/g or more, still more preferably 12 ⁇ mol/g or more, and even more preferably 15 ⁇ mol/g. g or more.
• the terminal amino group content is more preferably 80 ⁇ mol/g or less, still more preferably 70 ⁇ mol/g or less, even more preferably 50 ⁇ mol/g or less, and even more preferably 35 ⁇ mol/g or less.
• the amount of terminal amino groups in polyamide (A) refers to the amount (unit: ⁇ mol) of terminal amino groups contained in 1 g of polyamide (A).
• the amount of terminal amino groups of polyamide (A) can be obtained by a neutralization titration method using an indicator. More specifically, it can be determined by the method described in Examples.
• Polyamide (A) preferably has a terminal carboxyl group content ([COOH]) of 10 to 100 ⁇ mol/g.
• a terminal carboxyl group content [COOH]
• the amount of terminal carboxyl groups is 10 ⁇ mol/g or more, a much more excellent crystallization rate is exhibited, and excellent heat resistance is likely to be exhibited. If the amount of terminal carboxyl groups is 100 ⁇ mol/g or less, good hydrolysis resistance can be exhibited.
• the terminal carboxyl group content is more preferably 15 ⁇ mol/g or more, still more preferably 20 ⁇ mol/g or more, and still more preferably 25 ⁇ mol/g or more.
• the terminal carboxyl group content is more preferably 70 ⁇ mol/g or less, and still more preferably 50 ⁇ mol/g or less.
• the amount of terminal carboxyl groups in polyamide (A) refers to the amount (unit: ⁇ mol) of terminal carboxyl groups contained in 1 g of polyamide (A).
• the terminal carboxyl group content of the polyamide (A) can be determined by a neutralization titration method using an indicator. More specifically, it can be determined by the method described in Examples.
• the ratio [NH 2 ]/[COOH] of the terminal amino group amount [NH 2 ] to the terminal carboxyl group amount [COOH] in the polyamide (A) is preferably 0.1 to 30, preferably 0.1 to 20 is more preferable, and 0.3 to 10 is even more preferable. If [NH 2 ]/[COOH] is 0.1 or more, a much more excellent crystallization rate can be exhibited, and good hydrolysis resistance can be exhibited. When [NH 2 ]/[COOH] is 30 or less, even better heat resistance is likely to be exhibited.
• 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, the polyamide composition can be made more excellent in heat resistance.
• 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 280-330°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, the polyamide composition can have even better heat resistance.
• 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 0.020° C. ⁇ 1 or more, more preferably 0.040° C. ⁇ 1 or more.
• the crystallization temperature of the polyamide (A) is preferably 200° C. or higher, more preferably 210° C. or higher, still more preferably 220° C. or higher, and preferably 310° C. or lower. It is preferably 300° C. or lower, more preferably 290° C. or lower. In other words, the crystallization temperature of polyamide (A) is preferably between 200 and 310°C.
• the crystallization temperature of the polyamide (A) can be obtained as the peak temperature of the exothermic peak that appears when the temperature is raised to a predetermined temperature at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) device, and the temperature is lowered. More specifically, it can be determined by the method described in the Examples.
• 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.
• a nylon salt is produced by first adding a diamine, a dicarboxylic acid, and optionally a catalyst and a terminal blocking agent all at once. At this time, the amount of terminal amino groups and the amount of terminal carboxyl groups can be easily controlled by adjusting the number of moles of all carboxyl groups and the number of moles of all amino groups contained in the reaction raw materials. After the nylon salt is produced, it can be produced by thermally polymerizing at a temperature of 200 to 250° C. to form a prepolymer, and further solid-phase polymerizing it or polymerizing it using a melt extruder.
• 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.
• the polymerization temperature is preferably 370° C. or lower. 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. If the content is not more than the above upper limit, catalyst-derived impurities are less likely to occur, and for example, when the polyamide composition is made into a film, problems caused by the above impurities can be prevented.
• the polyamide composition of the present embodiment further contains polyolefin (B). Further containing a polyolefin in the polyamide composition can improve the toughness of the polyamide composition.
• the above polyolefin (B) is not particularly limited as long as the effects of the present invention can be suitably obtained, but it is preferably at least one selected from the group consisting of the following (1) to (5).
• ⁇ -olefin copolymer (2) at least one selected from the group consisting of ethylene, propylene and ⁇ -olefins having 4 or more carbon atoms, ⁇ , ⁇ -unsaturated carboxylic acid, ⁇ , ⁇ -unsaturated A copolymer with at least one selected from the group consisting of saturated carboxylic acid esters and ⁇ , ⁇ -unsaturated carboxylic acid anhydrides (3) the ionomer of (2) above (4) an aromatic vinyl compound and a conjugated diene compound A copolymer (5) wherein at least one selected from the group consisting of the above (1) to (4) is modified with an unsaturated compound having at least one selected from the group consisting of a carboxyl group and an acid anhydride group polymer
• ⁇ -olefin copolymers include copolymers of ethylene and ⁇ -olefins having 3 or more carbon atoms, and propylene and ⁇ -olefins having 4 or more carbon atoms. and copolymers with.
• ⁇ -olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene.
• ⁇ -olefin copolymers include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5 -isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornen
• the copolymer comprises at least one selected from the group consisting of ethylene, propylene and ⁇ -olefins having 4 or more carbon atoms, ⁇ , ⁇ -unsaturated carboxylic acid, ⁇ , ⁇ - It is a copolymer with at least one selected from the group consisting of unsaturated carboxylic acid esters and ⁇ , ⁇ -unsaturated carboxylic acid anhydrides.
• ⁇ -olefin having 4 or more carbon atoms those having 4 or more carbon atoms among those described in (1) ⁇ -olefin copolymer can be used.
• One of these ethylene, propylene and ⁇ -olefins having 4 or more carbon atoms may be used alone, or two or more thereof may be used in combination.
• Examples of the ⁇ , ⁇ -unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.
• One of these ⁇ , ⁇ -unsaturated carboxylic acids may be used alone. You may use 2 or more types together.
• Examples of ⁇ , ⁇ -unsaturated carboxylic acid esters include methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, octyl esters, nonyl esters and decyl esters of the above ⁇ , ⁇ -unsaturated carboxylic acids. These ⁇ , ⁇ -unsaturated carboxylic acid esters may be used singly or in combination of two or more.
• Examples of ⁇ , ⁇ -unsaturated carboxylic anhydrides include maleic anhydride and itaconic anhydride.
• ⁇ , ⁇ -unsaturated carboxylic anhydrides may be used singly or in combination of two or more. may be used together. At least one selected from the group consisting of the above ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated carboxylic acid esters and ⁇ , ⁇ -unsaturated carboxylic acid anhydrides is an ⁇ , ⁇ -unsaturated carboxylic acid Anhydrides are preferred, and maleic anhydride is more preferred.
• Ionomers (3) Ionomers include those in which at least part of the carboxyl groups of the copolymer (2) are ionized by neutralization with metal ions.
• metal ions include alkali metals and alkaline earth metals such as Li, Na, K, Mg, Ca, Sr, and Ba, as well as Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, Cd etc. are mentioned.
• metal ions may be used alone, or two or more thereof may be used in combination.
• the copolymer is a copolymer of an aromatic vinyl compound and a conjugated diene compound, preferably a block copolymer.
• the block copolymer include block copolymers (aromatic vinyl compound/conjugated diene compound block copolymers) composed of an aromatic vinyl compound polymer block and a conjugated diene compound polymer block.
• a block copolymer having at least one polymer block and at least one conjugated diene compound polymer block is preferred. Further, in the above block copolymer, some or all of the unsaturated bonds in the conjugated diene compound polymer block may be hydrogenated.
• the aromatic vinyl compound polymer block is a polymer block mainly composed of constitutional units derived from an aromatic vinyl compound.
• the aromatic vinyl compound include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene and the like, and these may be used singly or in combination of two or more.
• a conjugated diene compound polymer block is a polymer block mainly composed of structural units derived from a conjugated diene compound.
• the conjugated diene compound include 1,3-butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3 -hexadiene, etc., and these may be used singly or in combination of two or more.
• the hydrogenated aromatic vinyl compound/conjugated diene compound block copolymer typically, part or all of the unsaturated bond portions in the conjugated diene compound polymer block are hydrogenated to single bonds. .
• the molecular structure of the aromatic vinyl compound/conjugated diene compound block copolymer may be linear, branched, radial, or any combination thereof.
• the aromatic vinyl compound/conjugated diene compound block copolymer which may be a hydrogenated product
• one aromatic vinyl compound polymer block and one conjugated diene compound polymer block are A linearly bonded diblock copolymer, in which three polymer blocks are linearly bonded in the order of aromatic vinyl compound polymer block - conjugated diene compound polymer block - aromatic vinyl compound polymer block.
• One or more triblock copolymers are preferably used.
• aromatic vinyl compound/conjugated diene compound block copolymers (which may be hydrogenated products) include unhydrogenated or hydrogenated styrene/butadiene block copolymers, and unhydrogenated or hydrogenated styrene/isoprene block copolymers.
• Copolymer, unhydrogenated or hydrogenated styrene/isoprene/styrene block copolymer, unhydrogenated or hydrogenated styrene/butadiene/styrene block copolymer, unhydrogenated or hydrogenated styrene/isoprene/butadiene/styrene block A copolymer etc. are mentioned.
• Modified polymer (5) contains at least one selected from the group consisting of (1) to (4) above, and at least one selected from the group consisting of carboxyl groups and acid anhydride groups. It is a polymer modified with an unsaturated compound having
• Examples of unsaturated compounds having a carboxyl group include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid.
• Examples of the unsaturated compound having an acid anhydride group include dicarboxylic acid anhydrides having an ⁇ , ⁇ -unsaturated bond such as maleic anhydride and itaconic anhydride.
• the unsaturated compound having at least one selected from the group consisting of a carboxyl group and an acid anhydride group is preferably a dicarboxylic acid anhydride having an ⁇ , ⁇ -unsaturated bond, more preferably maleic anhydride.
• the total content of carboxyl groups and acid anhydride groups in the modified polymer (5) is preferably in the range of 25 to 200 ⁇ mol/g, more preferably in the range of 50 to 100 ⁇ mol/g. preferable. When the content is 25 ⁇ mol/g or more, the effect of improving the mechanical properties is sufficient, and when it is 200 ⁇ mol/g or less, the moldability of the resin composition is improved.
• base resin As a modification method with an unsaturated compound, at least one selected from the group consisting of the above (1) to (4) (hereinafter also referred to as "base resin") is produced by addition polymerization.
• a method of polymerizing and a method of grafting the unsaturated compound to the base resin can be exemplified, and the latter is preferred.
• Polyolefin (B) may be used alone or in combination of two or more.
• the polyolefin (B) is preferably (5) a modified polymer, and at least one ⁇ -olefin copolymer selected from the group consisting of a carboxyl group and an acid anhydride group. It is more preferably a polymer modified with an unsaturated compound having seeds, and more preferably a maleic anhydride-modified ethylene-propylene copolymer.
• the modified polymer (5) When the modified polymer (5) is used as the polyolefin (B), the terminal amino groups of the polyamide (A) react with the carboxyl groups and/or acid anhydride groups of the modified polymer (5), The interface affinity between the polyamide (A) and the polyolefin (B) is strengthened, and mechanical properties such as impact resistance and elongation are further improved.
• the modified polymer commercially available products can be used.
• the content of the polyolefin (B) contained in the total amount of the polyamide composition of the present embodiment is 2% by mass or more and less than 40% by mass, and good moldability, heat resistance, and toughness. It is preferably 3 to 35% by mass, more preferably 4 to 30% by mass, and even more preferably 5 to 25% by mass.
• the resin composition preferably contains 2 parts by mass or more and 67 parts by mass or less of polyolefin (B) with respect to 100 parts by mass of polyamide (A).
• the content of the polyolefin (B) is more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, relative to 100 parts by mass of the polyamide (A).
• the content of the polyolefin (B) is more preferably 45 parts by mass or less, still more preferably 35 parts by mass or less, relative to 100 parts by mass of the polyamide (A).
• the resin composition tends to exhibit better toughness, and defects such as cracks are less likely to occur in molded articles molded from the resin composition. Further, when the content of the polyolefin (B) is 67 parts by mass or less, the toughness and the melt viscosity are low, so that the resin composition has good fillability into a mold when the resin composition is injection molded. can do.
• the polyamide composition may optionally contain other additives in addition to the above polyamide (A) and polyolefin (B).
• additives include, for example, antioxidant; colorant; ultraviolet absorber; light stabilizer; antistatic agent; flame retardant; oxygen absorber; hydrogen sulfide adsorbent; crystallization retardant;
• the content of the other additives is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0.02 to 100 parts by mass, preferably 0.1 to 50 parts by mass, relative to 100 parts by mass of the polyamide (A). Parts by mass are more preferred.
• the method for producing the polyamide composition is not particularly limited, and a method capable of uniformly mixing the polyamide (A) and the polyolefin (B) 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 range about 10 to 50° C. higher than the melting point of the polyamide (A) can be mentioned.
• the polyamide composition preferably has a notched Charpy impact strength in bending of 8 KJ/m 2 or more, more preferably 10 KJ/m 2 or more.
• the notched Charpy impact strength of the polyamide composition can be determined by performing an impact test after injection molding the polyamide composition into a test piece having a thickness of 4 mm, and more specifically, it can be determined by the method described in the Examples. can be done.
• a molded article made of the polyamide composition can be used.
• 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 during molding, and further, treatment such as heat treatment or electron beam cross-linking may be performed after molding.
• the molded article of this embodiment can be used as electrical and electronic parts, automobile parts, industrial parts, faucet parts, fibers, films, sheets, household goods, leisure goods, and various other molded articles of any shape and purpose. can.
• 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, Engine 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, conveyor roller bearings, railway sleeper spring holders, outboard engine covers, generator engine covers, wind power generators blades, irrigation valves, and large switches.
• 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.
• 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, fishing nets, tire cords, artificial grass, 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 valve/pump housings for tea and coffee makers, valve/pump housings for cooking appliances (rice cookers, steamers, etc.), steam-resistant parts for cooking appliances (rice cookers, steamers, etc.) (top lids for rice cookers, etc.) ), sliding parts (gears, etc.) of cooking appliances (rice cookers, steamers, etc.), sliding parts (gears for gear pumps, etc.) of commercial cooking utensils, steam-resistant parts of commercial cooking utensils (pipes of commercial rice cookers etc.).
• Portable goods include inner soles and outsoles of sports shoes, racket frames and grommets, golf club heads and sleeves, fishing reels and rods, boat screws, bicycle suspensions, gears, saddles, and bottle cages. are mentioned.
• 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).
• ⁇ Melting point (heat resistance), crystallization temperature, glass transition temperature The melting point, crystallization temperature, and glass transition temperature of the polyamides obtained in Examples and Comparative Examples were obtained using a differential scanning calorimeter "DSC7020" manufactured by Hitachi High-Tech Science Co., Ltd. ” was used to measure. The melting point and crystallization temperature were measured according to ISO 11357-3 (2nd edition, 2011). Specifically, in a nitrogen atmosphere, the sample (polyamide) was heated from 30 ° C. to 340 ° C. at a rate of 10 ° C./min, held at 340 ° C. for 5 minutes to completely melt the sample, and then heated to 10 ° C. After cooling to 50° C.
• the peak temperature of the exothermic peak that appeared when the temperature was lowered was defined as the crystallization temperature
• the peak temperature of the endothermic peak that appeared when the temperature was increased again was defined as the melting point (°C).
• 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.
• Amount of terminal amino group ([NH 2 ]) The amount of terminal amino groups of the polyamides obtained in Examples and Comparative Examples was obtained by adding thymol blue as an indicator to a solution of 1 g of polyamide dissolved in 30 mL of phenol, and titrating with a 0.01 mol/L hydrochloric acid aqueous solution. Calculated. In Tables 1 to 3, the terminal amino group content of polyamide is represented by [NH 2 ].
• 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. Calculated by titration with a 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 was set to 30 ° C. higher, and the polyamide compositions of Examples 1 to 13, 15, 16 and Comparative Examples 1 to 5, 7, 8 were molded at a mold temperature of 140 ° C.
• the polyamide composition was molded using a T-runner mold under conditions of a mold temperature of 170 ° C., and a multi-purpose test piece type A1 (dumbbell-shaped test piece described in JIS K7139; 4 mm thick, full length 170 mm, parallel portion length 80 mm, parallel portion width 10 mm).
• Molecular weight change rate (%) ((Molecular weight after heat treatment - Molecular weight before heat treatment) / (Molecular weight before heat treatment)) ⁇ 100 (Formula 2) ⁇ Evaluation criteria> ⁇ A: Molecular weight change rate is within ⁇ 10% ⁇ B: Molecular weight change rate is more than ⁇ 10% and within ⁇ 20% ⁇ C: Molecular weight change rate is more than ⁇ 20%
• the multi-purpose test piece type A1 prepared by the above method is immersed in an antifreeze solution (an aqueous solution obtained by diluting twice the "super long life coolant" (pink) manufactured by Toyota Motor Corporation) in a pressure container, The pressure-resistant container was placed in a constant temperature bath set at 130° C. for 100 hours. The molecular weights of the removed test piece and the test piece not subjected to the immersion treatment were measured, and the molecular weight change rate was calculated from the following formula (Formula 3). Based on the calculated molecular weight change rate, hydrolysis resistance was evaluated according to the following criteria. "A” and "B” were rated as passing, and "C” was rated as failing.
• Molecular weight change rate (%) ((molecular weight after immersion treatment - molecular weight before immersion treatment) / (molecular weight before immersion treatment)) ⁇ 100 (Formula 3) ⁇ Evaluation criteria> ⁇ A: Molecular weight change rate is within ⁇ 10% ⁇ B: Molecular weight change rate is more than ⁇ 10% and within ⁇ 20% ⁇ C: Molecular weight change rate is more 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
• ⁇ Other additives Components used to prepare polyamide compositions in Examples and Comparative Examples are shown. ⁇ Antioxidant "KG HS01-P” (manufactured by PolyAd Services) ⁇ Lubricant “LICOWAX OP” (manufactured by Clariant Chemicals) ⁇ Crystal nucleating agent “TALC ML112” (manufactured by Fuji Talc Industry Co., Ltd.) ⁇ Colorant carbon black “#980B” (manufactured by Mitsubishi Chemical Corporation)
• Example 1 5,400 g of terephthalic acid, a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine and 2-methyl-1,8-octanediamine [4/1/95 (molar ratio) ] 5,260 g, 121 g of benzoic acid, 10 g of sodium hypophosphite monohydrate (0.1% by mass based on the total mass of the raw materials) and 4.8 liters of distilled water are placed in an autoclave having an internal volume of 40 liters, Nitrogen was substituted. After stirring at 150°C for 30 minutes, the temperature inside the autoclave was raised to 220°C over 2 hours.
• 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 further 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 state polymerization at 230°C and 13 Pa (0.1 mmHg) for 10 hours to obtain polyamide (A) having a melting point of 282°C.
• polyamide (A) and polyolefin (B) (polyolefin B-1, Tafmer (registered trademark) MH7020, manufactured by Mitsui Chemicals, Inc.) and other additives in the proportions shown in Table 1 were extruded by a twin-screw extruder (Toshiba Machinery Co., Ltd.).
• a pellet-shaped polyamide composition was obtained by feeding from an upstream hopper of "TEM-26SS" manufactured by Co., Ltd., melt-kneading, extruding, cooling and cutting.
• Example 2 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 )], a polyamide (A) was prepared in the same manner as in Example 1, and a polyamide composition was obtained in the same manner as in Example 1 except that the polyamide (A) thus obtained was used.
• Example 3 diamine units as a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine and 2-methyl-1,8-octanediamine [12/3/85 (molar ratio)]
• a polyamide (A) was produced in the same manner as in Example 1 except that the above was performed, and a polyamide composition was obtained in the same manner as in Example 1 except that the polyamide (A) thus obtained was used.
• the diamine unit is a mixture of 2-ethyl-1,7-heptanediamine, 2-propyl-1,6-hexanediamine and 2-methyl-1,8-octanediamine [16/4/80 (molar ratio)]
• a polyamide (A) was produced in the same manner as in Example 1 except that the above was performed, and a polyamide composition was obtained in the same manner as in Example 1 except that the polyamide (A) thus obtained was used.
• 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)] was prepared in the same manner as in Example 1, and the polyamide composition was prepared in the same manner as in Example 1 except that the polyamide (A) thus obtained was used. got stuff
• Example 6 to 8, 11, Comparative Examples 2 and 3 Polyamide (A) was produced in the same manner as in Example 5, except that the blending amounts of polyolefin and other additives were set to the ratios shown in Tables 1 and 2, and the polyamide (A) thus obtained was used. A polyamide composition was obtained in the same manner as in Example 5 except for the above.
• Example 9 A polyamide (A) was prepared in the same manner as in Example 8 except that polyolefin B-1 was polyolefin B-2 (Tafmer (registered trademark) MH7010, manufactured by Mitsui Chemicals, Inc.), and the polyamide (A ) was used in the same manner as in Example 8 to obtain a polyamide composition.
• Example 10 A polyamide (A) was produced in the same manner as in Example 8 except that polyolefin B-1 was polyolefin B-3 (Tafmer (registered trademark) MP0620, manufactured by Mitsui Chemicals, Inc.), and the polyamide (A ) was used in the same manner as in Example 8 to obtain a polyamide composition.
• polyolefin B-1 was polyolefin B-3 (Tafmer (registered trademark) MP0620, manufactured by Mitsui Chemicals, Inc.)
• MP0620 Tefmer (registered trademark) MP0620, manufactured by Mitsui Chemicals, Inc.
• Example 12 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)]
• Polyamide (A) was produced in the same manner as in Example 5 except that the terminal amino group content and the terminal carboxyl group content were set to the contents shown in Table 2 by using 5,400 g.
• a polyamide composition was obtained in the same manner as in Example 5, except that the polyamide (A) thus obtained was used.
• Example 13 By blending the polyamide used in Example 5 and the polyamide used in Example 12 at 7: 3, the terminal amino group content and the terminal carboxyl group content were set to the contents shown in Table 2.
• Example 5 A polyamide composition was obtained in the same manner as in Example 5 except that a polyamide (A) was prepared in the same manner as in Example 5 and the polyamide (A) thus obtained was used.
• Example 14 The diamine unit was a mixture of 2-ethyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine and 1,9-nonanediamine [0.5/14.5/85 (molar ratio)].
• a polyamide (A) was produced in the same manner as in Example 1, except that the polyamide (A) thus obtained was used, and a polyamide composition was obtained in the same manner as in Example 1.
• Example 1 A polyamide (A) was produced in the same manner as in Example 5 except that no polyolefin was blended, and a polyamide composition was obtained in the same manner as in Example 5 except that the polyamide (A) thus obtained was used. rice field.
• Polyamide (A) was prepared in the same manner as in Example 1 except that the diamine unit was only 2-methyl-1,8-octanediamine unit, and the polyamide (A) thus obtained was used.
• a polyamide composition was obtained in the same manner as in Example 1.
• Polyamide (A) was 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)].
• a polyamide composition was obtained in the same manner as in Example 1, except that the polyamide (A) thus obtained was used.
• Example 15 A polyamide (A) was prepared in the same manner as in Example 5 except that the dicarboxylic acid unit was 7,027 g of 2,6-naphthalene dicarboxylic acid, and the polyamide (A) thus obtained was used. A polyamide composition was obtained in the same manner as in Example 5.
• Polyamide (A) was prepared in the same manner as in Example 15 except that the diamine unit was a mixture of 2-methyl-1,8-octanediamine and 1,9-nonanediamine [15/85 (molar ratio)].
• a polyamide composition was obtained in the same manner as in Example 15, except that the polyamide (A) thus obtained was used.
• Polyamide (A) was produced in the same manner as in Example 16 except that the diamine unit was a mixture of 2-methyl-1,8-octanediamine and 1,9-nonanediamine [15/85 (molar ratio)].
• a polyamide composition was obtained in the same manner as in Example 16, except that the polyamide (A) thus obtained was used.
• 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/ Polyamide (A) was prepared in the same manner as in Example 5 except that the polyamide (A) was used in the same manner as in Example 5 except that the polyamide (A) thus obtained was used. A composition was obtained.
• Polyamide (A) was produced in the same manner as in Example 17 except that the diamine unit was a mixture of 2-methyl-1,8-octanediamine and 1,10-decanediamine [20/80 (molar ratio)].
• a polyamide composition was obtained in the same manner as in Example 17, except that the polyamide (A) thus obtained was used.
• the Example has 2-ethyl-1,7- Even when heptanediamine and 2-propyl-1,6-hexanediamine are contained, the melting point and glass transition temperature are less lowered, indicating excellent heat resistance. Therefore, from Tables 1 to 3, it can be seen that the polyamide compositions of Examples have an improved crystallization rate while maintaining excellent heat resistance, and are excellent in both moldability and heat resistance. Furthermore, the toughness is also excellent due to the inclusion of polyolefin. Further, from Tables 1 to 3, by optimizing the terminal amino group amount and dicarboxylic acid unit of the polyamide, it is possible to express excellent heat aging resistance and hydrolysis resistance by the polyamide composition. I understand.
• the polyamide composition of the present invention has high moldability, excellent heat resistance, and toughness. Therefore, the polyamide of the present invention is very useful because it can be used as various molded articles that require heat resistance and toughness, and can improve the productivity in manufacturing molded articles.

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