CN110964315B

CN110964315B - Polyamide composition, method for producing same, and molded article

Info

Publication number: CN110964315B
Application number: CN201910903204.9A
Authority: CN
Inventors: 渡边将史; 永濑康一; 家田真次; 荒木祥文
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2018-09-28
Filing date: 2019-09-24
Publication date: 2023-10-13
Anticipated expiration: 2039-09-24
Also published as: CN116285337A; DE102019214712A1; JP2020056003A; CN110964315A; JP7280146B2

Abstract

The present invention relates to a polyamide composition, a method for producing the same, and a molded article. The present invention provides a polyamide composition which does not contain halogen, but has excellent flame retardance and good long-term heat resistance when being made into a molded article. A polyamide composition comprising: (a) an aliphatic polyamide; (B) A semiaromatic polyamide containing diamine units and dicarboxylic acid units; (C) At least one phosphinate selected from the group consisting of phosphinates represented by the following general formula (1), diphosphinates represented by the following general formula (2), and condensates thereof; and (D) a polymer having an oxygen index of 27% or more and an aromatic group in the main chain, wherein the content of the (D) polymer is 0.1% by mass or more and 8% by mass or less relative to the total mass of the (A) aliphatic polyamide, the (B) semiaromatic polyamide, the (C) phosphinate, and the (D) polymer.

Description

Polyamide composition, method for producing same, and molded article

Technical Field

The present invention relates to a polyamide composition, a method for producing the same, and a molded article

Background

Compositions based on aliphatic polyamides have excellent property properties and are therefore used in a great variety of applications for the manufacture of molded articles. In particular, polyamide compositions having flame retardant properties are necessary for the components in the electrical and electronic industry in order to ensure adequate fire resistance.

Polyamides are often flame retardant treated by the addition of halogen compounds. However, recently, various regulations have been made such that products containing halogen compounds are not used in electric and electronic parts according to regulations of harmful substances such as RoHS (restriction of harmful substances) and PoHS (disabling of specific harmful substances in consumer products). Accordingly, various halogen-free flame retardants for polyamides have been developed.

Examples of the halogen-free flame retardant include phosphorus compounds. Patent document 1 discloses the use of calcium and aluminum salts of phosphinic acid or diphosphinic acid as flame retardants for polyamides. A test piece having a sample thickness of 1.2mm, which was produced from a polyamide composition containing these halogen-free flame retardants and reinforced with glass fibers in an amount of 30 mass% relative to the total mass of the composition, reached a flammability classification V-0 based on UL 94.

In order to achieve the flammability classification V-0 of UL94, patent document 2 discloses: in a glass fiber reinforced polyamide composition containing polyamide 6 as a main component, aluminum phosphinate in an amount of much more than 20 mass% is required with respect to the total mass of the composition; in the glass fiber reinforced polyamide composition having polyamide 66 as a main component, more than 30 mass% of aluminum phosphinate is required. It can be seen that in order to achieve flammability classification V-0 using phosphinic flame retardants, a large amount of addition is necessary, and thus, there is a problem in that the mechanical properties are adversely affected.

Accordingly, patent document 3 discloses a polyamide composition based on a mixture of an aliphatic polyamide and a semiaromatic polyamide, which contains a phosphinate as a flame retardant. It is reported that the addition of the semiaromatic polyamide can reduce the amount of the flame retardant used and improve the tensile elongation.

In addition, patent document 4 discloses a polyamide composition using phosphinate as a flame retardant and based on a mixture of polyamide containing aromatic polyamide and polyphenylene sulfide. It is reported that by adding polyphenylene sulfide excellent in flame retardancy to a polyamide containing an aromatic polyamide, the amount of the flame retardant used can be reduced and the amount of outgas emissions from the flame retardant can be reduced.

Prior art literature

Patent literature

Patent document 1: japanese patent No. 3947261

Patent document 2: japanese patent No. 4698789

Patent document 3: japanese patent No. 4614959

Patent document 4: japanese patent laid-open No. 2009-270107

Patent document 5: japanese patent laid-open publication No. 2005-179362

Patent document 6: european patent application publication No. 699708 specification

Patent document 7: japanese patent laid-open No. 08-073720

Disclosure of Invention

Problems to be solved by the invention

However, the polyamide composition described in patent document 3 has room for improvement in flexural modulus under the atmospheric equilibrium moisture absorption, long-term heat resistance, and the like required for automobiles and various electric parts, although the tensile elongation at break is improved by reducing the amount of the flame retardant used.

In addition, the polyamide composition described in patent document 4 has the following problems, although the amount of flame retardant used is reduced and outgas is reduced by adding polyphenylene sulfide: when the proportion of the aliphatic polyamide relative to the aromatic polyamide is increased, it is difficult to maintain the flammability classification V-0 based on UL 94. In addition, there is a concern that CTI (relative tracking index) required for an electrical component is degraded.

Therefore, a polyamide composition which does not contain halogen, is excellent in flame retardancy, and has excellent tensile strength, flexural modulus upon water absorption, and long-term heat resistance has not been known in the prior art.

The present invention has been made in view of the above circumstances, and provides a polyamide composition which is excellent in flame retardancy and good in long-term heat resistance when formed into a molded article, although it does not contain halogen, a method for producing the same, and a molded article comprising the polyamide composition.

Means for solving the problems

That is, the present invention includes the following modes.

The polyamide composition according to the invention according to the 1 st aspect comprises:

(A) Aliphatic polyamides;

(B) A semiaromatic polyamide containing diamine units and dicarboxylic acid units;

(C) At least one phosphinate selected from the group consisting of phosphinates represented by the following general formula (1), diphosphinates represented by the following general formula (2), and condensates thereof; and

(D) A polymer having an oxygen index of 27% or more and an aromatic group in the main chain, wherein,

the content of the polymer (D) is 0.1 to 8 mass% inclusive relative to the total mass of the aliphatic polyamide (A), the semiaromatic polyamide (B), the phosphinate (C) and the polymer (D),

(in the general formula (1), R ¹¹ And R is ¹² Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. M is M ⁿ¹¹⁺ Is a metal ion of valence n 11. M is an element belonging to group 2 or group 15 of the periodic Table, a transition element, zinc or aluminum. n11 is 2 or 3. In the case where n11 is 2 or 3, a plurality of R's are present ¹¹ And R is ¹² Each of which may be the same or different.

In the general formula (2), R ²¹ And R is ²² Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Y is Y ²¹ An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M's' ^m21+ A metal ion having a valence of m 21. M' is an element belonging to group 2 or group 15 of the periodic Table, a transition element, zinc or aluminum. n21 is an integer of 1 to 3. In the case where n21 is 2 or 3, a plurality of R's are present ²¹ 、R ²² And Y ²¹ Each of which may be the same or different. m21 is 2 or 3.x is 1 or 2. In the case where x is 2, a plurality of M's may be the same or different. n21, x, and m21 are integers satisfying a relation of 2×n21=m21×x. )

The (D) polymer may be polyphenylene sulfide, polyphenylene ether or maleic anhydride-modified polyphenylene ether.

The aliphatic polyamide (A) may contain a diamine unit and a dicarboxylic acid unit.

The (a) aliphatic polyamide may be polyamide 66.

The content of the (C) phosphinates may be 0.1 mass% or more and 30 mass% or less with respect to the total mass of the (a) aliphatic polyamide, the (B) semiaromatic polyamide, the (C) phosphinates and the (D) polymer.

The polyamide composition may have a tan delta peak temperature of 90 ℃ or higher.

The (B) semiaromatic polyamide may contain 50 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

The (B) semiaromatic polyamide may contain 75 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

The (B) semiaromatic polyamide may contain 100 mol% of isophthalic acid units among all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

The weight average molecular weight of the polyamide composition may be 10000 or more and 50000 or less.

The polyamide composition according to the above-mentioned item 1 may further contain at least one filler (E).

The molded article according to claim 2 of the present invention is obtained by molding the polyamide composition according to claim 1.

The method for producing a polyamide composition according to claim 3 of the present invention is a method for producing the polyamide composition according to claim 1, wherein the raw material components including the (a) aliphatic polyamide, the (B) semiaromatic polyamide, the (C) phosphinate, and the (D) polymer are melt kneaded.

Effects of the invention

According to the polyamide composition and the method for producing the same, a molded article having excellent flame retardancy and good long-term heat resistance can be obtained, although the polyamide composition does not contain halogen. The molded article of the above embodiment does not contain halogen, but is excellent in flame retardancy and good in long-term heat resistance.

Detailed Description

Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following, but the present invention may be implemented by appropriately modifying the present invention within the scope of the gist thereof.

In the present specification, "polyamide" means a polymer having an amide group (-NHCO-) in the main chain.

Polyamide composition

The polyamide composition of the present embodiment contains the following components (a) to (D).

(A) Aliphatic polyamides;

(C) Phosphinates;

(D) A polymer having an oxygen index of 27% or more and an aromatic group in the main chain (hereinafter, may be simply referred to as "(D polymer").

In the polyamide composition of the present embodiment, the content of the component (D) is 0.1 mass% or more and 8.0 mass% or less relative to the total mass of the components (a) to (D).

The phosphinates (C) are at least one kind of phosphinates selected from the group consisting of phosphinates represented by the following general formula (1) (hereinafter, sometimes simply referred to as "phosphinates (1)"), diphosphinates represented by the following general formula (2) (hereinafter, sometimes simply referred to as "diphosphinates (2)") and condensates thereof.

In the general formula (2), R ²¹ And R is ²² Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Y is Y ²¹ An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M's' ^m21+ A metal ion having a valence of m 21. M' is an element belonging to group 2 or group 15 of the periodic Table, a transition element, zinc or aluminum. n21 is an integer of 1 to 3. In the case where n21 is 2 or 3, a plurality of R's are present ²¹ 、R ²² And Y ²¹ Each of which may be the same or different. m21 is 2 or 3.x is 1 or 2. In the case where x is 2, a plurality of M's may be the same or different. n21, x, and m21 are integers satisfying the relationship of 2×n21=m21×x).

The polyamide composition of the present embodiment has the above-described constitution, and thus can provide a molded article which does not contain halogen, is excellent in flame retardancy, has a tensile strength, a flexural modulus at the time of water absorption, and has good long-term heat resistance.

< Properties of Polyamide composition >

The molecular weight and tan δ peak temperature of the polyamide composition of the present embodiment may be set to the following structures, and specifically, may be measured by the method described in examples below.

[ weight average molecular weight (Mw) of Polyamide composition ]

As an index of the molecular weight of the polyamide composition, a weight average molecular weight (Mw) can be utilized.

The weight average molecular weight (Mw) of the polyamide composition is preferably 10000 or more and 50000 or less, more preferably 17000 or more and 45000 or less, still more preferably 20000 or more and 45000 or less, still more preferably 25000 or more and 45000 or less, particularly preferably 30000 or more and 42000 or less, and most preferably 35000 or more and 40000 or less.

When the weight average molecular weight (Mw) of the polyamide composition is within the above range, a polyamide composition having more excellent mechanical properties, particularly, water absorption rigidity, thermal rigidity, fluidity and the like can be obtained. Further, molded articles obtained from the polyamide composition containing the component represented by the filler (E) have more excellent tensile strength, flexural modulus at the time of water absorption and long-term heat resistance.

Examples of the method for controlling the Mw of the polyamide composition within the above range include (A) aliphatic polyamide, (B) semiaromatic polyamide, and (D) polymer, wherein the Mw is within the range described below.

The measurement of Mw (weight average molecular weight) may be performed by GPC (gel permeation chromatography) as described in examples described below.

[ tan delta peak temperature of Polyamide composition ]

The lower limit of the tan delta peak temperature of the polyamide composition is preferably 90 ℃, more preferably 105 ℃, and even more preferably 110 ℃.

On the other hand, the upper limit of the tan δ peak temperature of the polyamide composition is preferably 150 ℃, more preferably 140 ℃, and even more preferably 130 ℃.

That is, the tan δ peak temperature of the polyamide composition is 90 ℃ or higher, preferably 105 ℃ or higher and 150 ℃ or lower, more preferably 110 ℃ or higher and 140 ℃ or lower, and still more preferably 110 ℃ or higher and 130 ℃ or lower.

When the tan delta peak temperature of the polyamide composition is equal to or higher than the lower limit, a polyamide composition having more excellent water absorption rigidity and thermal rigidity tends to be obtained. On the other hand, when the tan δ peak temperature of the polyamide composition is equal to or lower than the upper limit, a molded article obtained from the polyamide composition containing the component represented by the filler (E) tends to be a molded article having more excellent tensile strength, flexural modulus upon water absorption, and long-term heat resistance.

Examples of the method for controlling the tan delta peak temperature of the polyamide composition within the above range include a method for controlling the content of (a) an aliphatic polyamide and (B) a semiaromatic polyamide within the below-described range.

Hereinafter, each constituent component of the polyamide composition of the present embodiment will be described in detail.

(A) aliphatic Polyamide

The constituent unit of the (a) aliphatic polyamide contained in the polyamide composition of the present embodiment preferably satisfies at least one of the following conditions (1) and (2).

(1) Contains (A-a) aliphatic dicarboxylic acid units and (A-b) aliphatic diamine units.

(2) Contains (A-c) at least one selected from the group consisting of lactam units and aminocarboxylic acid units.

The polyamide composition of the present embodiment may contain, as the aliphatic polyamide (a), one or two or more kinds of polyamides satisfying at least one of the conditions (1) and (2) described above. Among them, the constituent unit of the aliphatic polyamide (a) contained in the polyamide composition of the present embodiment particularly preferably satisfies the above (1).

[ (A-a) aliphatic dicarboxylic acid units ]

Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit (a-a) include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms.

The linear saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms is not limited to the following, and examples thereof include: malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, icosanedioic acid, diglycolic acid, and the like.

The branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms is not limited to the following, and examples thereof include: dimethyl malonic acid, 2-dimethyl succinic acid, 2, 3-dimethyl glutaric acid, 2-diethyl succinic acid, 2, 3-diethyl glutaric acid, 2-dimethyl glutaric acid, 2-methyl adipic acid, trimethyl adipic acid, and the like.

The aliphatic dicarboxylic acids constituting the aliphatic dicarboxylic acid unit (A-a) may be used alone or in combination of two or more.

Among them, the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit (a-a) is preferably a linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms, because of the tendency of the polyamide composition to be more excellent in heat resistance, flowability, toughness, low water absorption, rigidity, and the like.

Specific examples of the linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms include: adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and the like.

Among them, adipic acid, sebacic acid, or dodecanedioic acid is preferable as the linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms from the viewpoint of heat resistance of the polyamide composition.

The aliphatic polyamide (a) may further contain a unit derived from a polycarboxylic acid having three or more members as needed within a range that does not impair the effect of the polyamide composition of the present embodiment. Examples of the polycarboxylic acid having three or more members include: trimellitic acid, trimesic acid, pyromellitic acid, and the like. These three or more polycarboxylic acids may be used alone or in combination of two or more.

[ (A-b) aliphatic diamine units ]

Examples of the aliphatic diamine constituting the aliphatic diamine unit (a-b) include: a linear saturated aliphatic diamine having 2 to 20 carbon atoms, or a branched saturated aliphatic diamine having 3 to 20 carbon atoms.

The linear saturated aliphatic diamine having 2 to 20 carbon atoms is not limited to the following, and examples thereof include: ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, and the like.

The branched saturated aliphatic diamine having 3 to 20 carbon atoms is not limited to the following, and examples thereof include: 2-methylpentamethylenediamine (also referred to as 2-methyl-1, 5-diaminopentane), 2, 4-trimethylhexamethylenediamine, 2, 4-trimethylhexamethylenediamine, 2-methyl-1, 8-octanediamine (also referred to as 2-methylpentamethylenediamine), 2, 4-dimethyloctamethylenediamine, and the like.

The aliphatic diamine constituting the aliphatic diamine unit (A-b) may be used alone or in combination of two or more.

Among them, the aliphatic diamine constituting the aliphatic diamine unit (a-b) has preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aliphatic diamine constituting the aliphatic diamine unit (A-b) has at least the lower limit of the number of carbon atoms, and the obtained molded article has more excellent heat resistance. On the other hand, when the number of carbon atoms is not more than the upper limit, the molded article obtained is more excellent in crystallinity and releasability.

Specific examples of the linear or branched saturated aliphatic diamine having 6 to 12 carbon atoms may include: hexamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-1, 8-octanediamine, and the like.

Among them, hexamethylenediamine or 2-methylpentamethylenediamine is preferable as a linear or branched saturated aliphatic diamine having 6 to 12 carbon atoms. By containing such (a-b) aliphatic diamine units, the molded article obtained from the polyamide composition is more excellent in heat resistance, rigidity, and the like.

The aliphatic polyamide (a) may contain a unit derived from an aliphatic polyamine of three or more, as needed, within a range that does not impair the effect of the polyamide composition of the present embodiment. Examples of the aliphatic polyamine having three or more members include bis (hexamethylene) triamine.

[ (A-c) at least one constituent unit selected from the group consisting of lactam units and aminocarboxylic acid units ]

(A) The aliphatic polyamide may contain (a-c) at least one constituent unit selected from the group consisting of a lactam unit and an aminocarboxylic acid unit. By containing such units, polyamide having excellent toughness tends to be obtained.

Here, "lactam unit" and "aminocarboxylic acid unit" refer to a polymerized (condensed) lactam and aminocarboxylic acid.

The lactam constituting the lactam unit is not limited to the following, and examples thereof include: butyrolactam, valerolactam, epsilon-caprolactam, caprylolactam, enantholactam, undecanolactam, laurolactam (laurolactam) and the like.

Among them, epsilon-caprolactam or laurolactam is preferable as the lactam constituting the lactam unit, and epsilon-caprolactam is more preferable. By containing such a lactam, the molded article obtained from the polyamide composition tends to have more excellent toughness.

The aminocarboxylic acid constituting the aminocarboxylic acid unit is not limited to the following, and examples thereof include: omega-aminocarboxylic acids, alpha, omega-amino acids, and the like, which are compounds obtained by ring opening of lactams.

As the aminocarboxylic acid constituting the aminocarboxylic acid unit, a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms in which ω -position is substituted with an amino group is preferable. Examples of such aminocarboxylic acids include, but are not limited to, the following: 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. In addition, as the aminocarboxylic acid, p-aminomethylbenzoic acid and the like can be mentioned.

The lactam and the aminocarboxylic acid each having at least one constituent unit selected from the group consisting of a lactam unit and an aminocarboxylic acid unit may be used alone or in combination of two or more.

Among them, the aliphatic polyamide (a) contained in the polyamide composition of the present embodiment is preferably a polyamide containing a dicarboxylic acid unit and a diamine unit, and more preferably polyamide 66 (PA 66) from the viewpoints of mechanical properties, heat resistance, moldability and toughness. PA66 is considered to be a material suitable for automobile parts because of its excellent mechanical properties, heat resistance, moldability and toughness.

The content of the (a) aliphatic polyamide in the polyamide composition of the present embodiment may be set to, for example, 10 mass% or more and 100 mass% or less, for example, 50 mass% or more and 100 mass% or less, and for example, 55 mass% or more and 100 mass% or less, with respect to the total mass of the polyamide in the polyamide composition.

[ (A) weight average molecular weight Mw (A) ] of aliphatic polyamide

As an index of the molecular weight of the aliphatic polyamide (a), a weight average molecular weight Mw (a) can be used. The weight average molecular weight Mw (a) of the aliphatic polyamide is preferably 10000 or more and 50000 or less, more preferably 17000 or more and 45000 or less, still more preferably 20000 or more and 45000 or less, still more preferably 25000 or more and 45000 or less, particularly preferably 30000 or more and 45000 or less, and most preferably 35000 or more and 40000 or less.

When the weight average molecular weight Mw (A) is within the above range, a polyamide composition having more excellent mechanical properties, particularly, water absorption rigidity, thermal rigidity, fluidity, tensile strength when formed into a molded article, flexural modulus when absorbing water, long-term heat resistance, and the like can be obtained.

The weight average molecular weight Mw (a) may be measured by GPC as described in examples below.

(B) semi-aromatic Polyamide ]

The (B) semiaromatic polyamide contained in the polyamide composition of the present embodiment is a polyamide containing a diamine unit and a dicarboxylic acid unit.

The (B) semiaromatic polyamide preferably contains 20 to 80 mol% of an aromatic constituent unit, more preferably 30 to 70 mol% of an aromatic constituent unit, and still more preferably 40 to 60 mol% of an aromatic constituent unit, based on the total constituent units of the (B) semiaromatic polyamide. The term "aromatic constituent unit" as used herein means an aromatic diamine unit and an aromatic dicarboxylic acid unit.

The (B) semiaromatic polyamide preferably contains (B-a) dicarboxylic acid units containing 50 mol% or more of isophthalic acid units relative to the total dicarboxylic acid units of the (B) semiaromatic polyamide, and (B-B) diamine units containing diamine units having 4 to 10 carbon atoms.

In this case, the total content of the isophthalic acid unit and the diamine unit having 4 to 10 carbon atoms in the (B) semiaromatic polyamide is preferably 50 mol% or more, more preferably 80 mol% or more and 100 mol% or less, still more preferably 90 mol% or more and 100 mol% or less, and particularly preferably 100 mol% relative to the total constituent units of the (B) semiaromatic polyamide.

The proportion of the predetermined monomer units constituting the (B) semiaromatic polyamide may be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.

[ (B-a) dicarboxylic acid units ]

The dicarboxylic acid unit (B-a) is not particularly limited, and examples thereof include: aromatic dicarboxylic acid units, aliphatic dicarboxylic acid units, alicyclic dicarboxylic acid units, and the like.

Among them, the dicarboxylic acid unit (B-a) preferably contains 50 mol% or more of isophthalic acid unit, more preferably 65 mol% or more and 100 mol% or less of isophthalic acid unit, still more preferably 75 mol% or more and 100 mol% or less of isophthalic acid unit, particularly preferably 80 mol% or more and 100 mol% or less of isophthalic acid unit, and most preferably 100 mol% or less of isophthalic acid unit, based on the total mole number of the dicarboxylic acid unit (B-a).

When the ratio of the isophthalic acid unit in the dicarboxylic acid unit (B-a) is not less than the lower limit, a polyamide composition which can satisfy mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity and the like, tends to be obtained. Further, molded articles obtained from the polyamide composition tend to be more excellent in tensile strength, flexural modulus upon water absorption, and long-term heat resistance.

(aromatic dicarboxylic acid unit)

The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit other than the isophthalic acid unit is not limited to the following, and examples thereof include dicarboxylic acids having an aromatic group such as a phenyl group and a naphthyl group. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or substituted.

The substituent is not particularly limited, and examples thereof include: an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkylaryl group having 7 to 10 carbon atoms, a halogen group, a silyl group having 1 to 6 carbon atoms, a sulfonic acid group, a salt thereof (sodium salt, etc.), and the like.

Examples of the alkyl group having 1 to 4 carbon atoms include, but are not limited to, the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like.

Examples of the aryl group having 6 to 10 carbon atoms include, but are not limited to, the following groups: phenyl, naphthyl, and the like.

Examples of the aralkyl group having 7 to 10 carbon atoms include, but are not limited to, the following groups: benzyl, and the like.

The alkylaryl group having 7 to 10 carbon atoms is not limited to the following groups, and examples thereof include: tolyl, xylyl, and the like.

The halogen group is not limited to the following groups, and examples thereof include: fluoro, chloro, bromo, iodo, and the like.

The silyl group having 1 to 6 carbon atoms is not limited to the following groups, and examples thereof include: trimethylsilyl, t-butyldimethylsilyl, and the like.

Among them, as the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit other than the isophthalic acid unit, an unsubstituted aromatic dicarboxylic acid having 8 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms substituted with a predetermined substituent is preferable.

The unsubstituted aromatic dicarboxylic acid having 8 to 20 carbon atoms or the aromatic dicarboxylic acid having 8 to 20 carbon atoms substituted with a predetermined substituent is not particularly limited, and examples thereof include: terephthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methyltetraphthalic acid, isophthalic acid-5-sodium sulfonate, and the like.

The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit may be used alone or in combination of two or more.

(aliphatic dicarboxylic acid unit)

Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms.

(alicyclic dicarboxylic acid unit)

The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit (hereinafter, sometimes referred to as "alicyclic dicarboxylic acid unit") is not limited to the following, and examples thereof include: alicyclic dicarboxylic acids having 3 to 10 carbon atoms in the alicyclic structure, and the like. Among them, preferred as the alicyclic dicarboxylic acid is an alicyclic dicarboxylic acid having an alicyclic structure having 5 to 10 carbon atoms.

Examples of such alicyclic dicarboxylic acids include, but are not limited to, the following: 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, and the like. Among them, 1, 4-cyclohexanedicarboxylic acid is preferable as the alicyclic dicarboxylic acid.

The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit may be used alone or in combination of two or more.

The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or substituted. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the same groups as those exemplified for the "aromatic dicarboxylic acid unit".

The dicarboxylic acid unit other than the isophthalic acid unit preferably contains an aromatic dicarboxylic acid unit, and more preferably contains an aromatic dicarboxylic acid having 6 or more carbon atoms.

By using such dicarboxylic acid, a polyamide composition which can satisfy mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, and the like, tends to be obtained. Further, molded articles obtained from the polyamide composition tend to be more excellent in tensile strength, flexural modulus upon water absorption, and long-term heat resistance.

(B) The dicarboxylic acid constituting the dicarboxylic acid unit (B-a) in the semiaromatic polyamide is not limited to the compounds described as the dicarboxylic acid, and may be compounds equivalent to the dicarboxylic acid.

The term "compound equivalent to a dicarboxylic acid" as used herein means a compound which can give a dicarboxylic acid structure identical to that of a dicarboxylic acid derived from the above dicarboxylic acid. Examples of such a compound include, but are not limited to, the following: anhydrides of dicarboxylic acids, acid halides of dicarboxylic acids, and the like.

The semiaromatic polyamide (B) may further contain a unit derived from a polycarboxylic acid having three or more members, as needed, within a range that does not impair the effects of the polyamide composition of the present embodiment.

Examples of the polycarboxylic acid having three or more members include: trimellitic acid, trimesic acid, pyromellitic acid, and the like. These three or more polycarboxylic acids may be used alone or in combination of two or more.

[ (B-B) diamine units ]

The diamine unit (B-B) constituting the semiaromatic polyamide (B) is not particularly limited, and examples thereof include: aromatic diamine units, aliphatic diamine units, alicyclic diamine units, and the like. Among them, (B-B) diamine units constituting (B) semi-aromatic polyamide preferably contain diamine units having 4 to 10 carbon atoms, more preferably contain diamine units having 6 to 10 carbon atoms.

(aliphatic diamine unit)

Examples of the aliphatic diamine constituting the aliphatic diamine unit include: and linear saturated aliphatic diamines having 4 to 20 carbon atoms.

The linear saturated aliphatic diamine having 4 to 20 carbon atoms is not limited to the following, and examples thereof include: ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, and the like.

(alicyclic diamine unit)

The alicyclic diamine (hereinafter, sometimes referred to as "alicyclic diamine") constituting the alicyclic diamine unit is not limited to the following, and examples thereof include: 1, 4-cyclohexanediamine, 1, 3-cyclopentanediamine, and the like.

(aromatic diamine unit)

The aromatic diamine constituting the aromatic diamine unit is not limited to the following as long as it is a diamine containing an aromatic group. Specific examples of the aromatic diamine include m-xylylenediamine and the like.

These diamines constituting each diamine unit may be used alone or in combination of two or more.

Among them, the (B-B) diamine unit is preferably an aliphatic diamine unit, more preferably a linear saturated aliphatic diamine unit having 4 to 10 carbon atoms, still more preferably a linear saturated aliphatic diamine unit having 6 to 10 carbon atoms, and particularly preferably a hexamethylenediamine unit.

By using such a diamine, a polyamide composition which can satisfy mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, and the like, tends to be obtained. Further, molded articles obtained from the polyamide composition tend to be more excellent in tensile strength, flexural modulus upon water absorption, and long-term heat resistance.

The (B) semiaromatic polyamide contained in the polyamide composition of the present embodiment is preferably polyamide 6I (polymetaphthaloyl hexamethylenediamine), polyamide 9I or polyamide 10I, more preferably polyamide 6I. Polyamide 6I is considered to be a material suitable for automobile parts because of its excellent heat resistance, molding processability and flame retardancy.

The content of the (B) semiaromatic polyamide in the polyamide composition of the present embodiment may be set to 5 mass% or more and 90 mass% or less, preferably 10 mass% or more and 50 mass% or less, more preferably 15.0 mass% or more and 40 mass% or less, and still more preferably 20 mass% or more and 45 mass% or less, relative to the total mass of the polyamide in the polyamide composition.

By setting the content of the (B) semiaromatic polyamide in the above range, the mechanical properties of a molded article obtained from the polyamide composition are more excellent. Further, the polyamide composition tends to give a molded article having more excellent tensile strength, flexural modulus at the time of water absorption and long-term heat resistance by containing the component represented by the filler (E).

[ (B) weight average molecular weight Mw (B) of semi-aromatic Polyamide ]

As an index of the molecular weight of the (B) semiaromatic polyamide, the weight average molecular weight Mw (B) can be used. The weight average molecular weight Mw (B) of the semiaromatic polyamide is preferably 10000 or more and 50000 or less, more preferably 15000 or more and 45000 or less, still more preferably 15000 or more and 40000 or less, still more preferably 17000 or more and 30000 or less, particularly preferably 17000 or more and 25000 or less, and most preferably 18000 or more and 22000 or less.

When the weight average molecular weight Mw (B) is within the above range, a polyamide composition having more excellent mechanical properties, particularly, water absorption rigidity, thermal rigidity, fluidity, tensile strength when formed into a molded article, flexural modulus when absorbing water, long-term heat resistance, and the like can be obtained.

The weight average molecular weight Mw (B) may be measured by GPC as described in examples below.

< blocking agent >

The terminal ends of the polyamide ((a) aliphatic polyamide and (B) semiaromatic polyamide) contained in the polyamide composition of the present embodiment may be blocked with a known blocking agent.

Such a blocking agent may be added as a molecular weight regulator in the case of producing a polyamide from the dicarboxylic acid and the diamine, or producing a polyamide from at least one selected from the group consisting of the lactam and the aminocarboxylic acid.

Examples of the blocking agent include, but are not limited to, the following: monocarboxylic acids, monoamines, anhydrides (phthalic anhydride, etc.), monoisocyanates, monoesters, monoalcohols, etc. The blocking agent may be used alone or in combination of two or more.

Among them, monocarboxylic acids or monoamines are preferable as the blocking agent. By capping the ends of the polyamide with the capping agent, the molded article obtained from the polyamide composition tends to be more excellent in heat stability.

The monocarboxylic acid that can be used as the blocking agent may be any one that has reactivity with an amino group that may be present at the terminal of the polyamide. Examples of monocarboxylic acids include, but are not limited to, the following: aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, aromatic monocarboxylic acids, and the like.

Examples of the aliphatic monocarboxylic acid include: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, and the like.

Examples of the alicyclic monocarboxylic acid include: cyclohexane carboxylic acid, and the like.

Examples of the aromatic monocarboxylic acid include: benzoic acid, toluic acid, alpha-naphthoic acid, beta-naphthoic acid, methylnaphthoic acid, phenylacetic acid, and the like.

These monocarboxylic acids may be used alone or in combination of two or more.

In particular, from the viewpoints of fluidity and mechanical strength, the terminal ends of the (B) semiaromatic polyamide are preferably end-capped with acetic acid.

The monoamine that can be used as the blocking agent may be any one having reactivity with carboxyl groups that may be present at the terminal ends of the polyamide. The monoamine is not limited to the following, and examples thereof include: aliphatic monoamines, alicyclic monoamines, aromatic monoamines, and the like.

Examples of the aliphatic monoamine include: methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and the like.

Examples of the alicyclic monoamine include: cyclohexylamine, dicyclohexylamine, and the like.

Examples of the aromatic monoamine include: aniline, toluidine, diphenylamine, naphthylamine, and the like.

These monoamines may be used alone or in combination of two or more.

Polyamide compositions containing a polyamide blocked with a blocking agent tend to be more excellent in heat resistance, flowability, toughness, low water absorption and rigidity.

Process for producing (A) aliphatic polyamide and (B) semiaromatic polyamide

In the production of the polyamide ((a) aliphatic polyamide and (B) semiaromatic polyamide) contained in the polyamide composition of the present embodiment, the amount of the dicarboxylic acid to be added and the amount of the diamine to be added are preferably about the same molar amount. In terms of the molar ratio, the molar amount of the entire diamine is preferably 0.9 to 1.2, more preferably 0.95 to 1.1, still more preferably 0.98 to 1.05, based on the molar amount 1 of the entire diamine, in view of the portion of the diamine escaping to the outside of the reaction system during the polymerization reaction.

The method for producing polyamide is not limited to the following method, and includes, for example, the following polymerization step (1) or (2).

(1) And polymerizing a combination of a dicarboxylic acid constituting a dicarboxylic acid unit and a diamine constituting a diamine unit to obtain a polymer.

(2) And polymerizing at least one selected from the group consisting of lactams constituting the lactam unit and aminocarboxylic acids constituting the aminocarboxylic acid unit to obtain a polymer.

In addition, as the method for producing polyamide, it is preferable that the method further comprises a step of raising the polymerization degree of polyamide after the polymerization step. The polymerization step and the raising step may be followed by a capping step of capping the end of the obtained polymer with a capping agent, if necessary.

Specific methods for producing polyamides include, for example, the various methods described in 1) to 4) below.

1) A method of polymerizing one or more aqueous solutions or aqueous suspensions selected from the group consisting of dicarboxylic acid-diamine salts, mixtures of dicarboxylic acids and diamines, lactams and aminocarboxylic acids while maintaining the molten state (hereinafter, sometimes referred to as "hot melt polymerization method").

2) A method of increasing the polymerization degree of a polyamide obtained by a hot melt polymerization method while maintaining the solid state at a temperature of not more than the melting point (hereinafter, sometimes referred to as "hot melt polymerization/solid phase polymerization method").

3) A method of polymerizing one or more selected from the group consisting of dicarboxylic acid-diamine salts, a mixture of dicarboxylic acid and diamine, lactam and aminocarboxylic acid while maintaining the solid state (hereinafter, sometimes referred to as "solid-phase polymerization method").

4) A method of polymerizing a dicarboxylic acid halide component and a diamine component equivalent to dicarboxylic acids (hereinafter, sometimes referred to as "solution method") by using them.

Among them, a specific method for producing polyamide is preferably a method comprising a hot melt polymerization method. In addition, in the production of polyamide by the hot melt polymerization method, it is preferable to keep the molten state until the polymerization is completed. In order to maintain the molten state, it is necessary to carry out the production under polymerization conditions suitable for the polyamide composition. Examples of the polymerization conditions include the following conditions. First, the polymerization pressure in the hot melt polymerization method was controlled to 14kg/cm ² Above and 25kg/cm ² Heating was continued as follows (gauge pressure). Then, the pressure was reduced for 30 minutes or longer until the pressure in the tank reached the atmospheric pressure (gauge pressure: 0 kg/cm) ² )。

In the method for producing polyamide, the polymerization method is not particularly limited, and may be either a batch method or a continuous method.

The polymerization apparatus used for producing polyamide is not particularly limited, and a known apparatus can be used. Specific examples of the polymerization apparatus include: autoclave type reactors, roll type reactors, extruder type reactors (kneaders, etc.), and the like.

Hereinafter, a method for producing polyamide by a batch hot melt polymerization method is specifically described as a method for producing polyamide, but the method for producing polyamide is not limited thereto.

First, an aqueous solution containing about 40 mass% or more and about 60 mass% or less of a raw material component (a combination of a dicarboxylic acid and a diamine, and if necessary, at least one selected from the group consisting of a lactam and an aminocarboxylic acid) of a polyamide is prepared. Next, the aqueous solution is concentrated to about 65 mass% or more and about 90 mass% or less in a concentration tank operated at a temperature of 110 ℃ or more and 180 ℃ or less and a pressure of about 0.035MPa or more and about 0.6MPa or less (gauge pressure), thereby obtaining a concentrated solution.

The resulting concentrated solution was then transferred to an autoclave and heating was continued until the pressure in the autoclave reached about 1.2MPa or more and about 2.2MPa or less (gauge pressure).

Next, in the autoclave, the pressure was maintained at about 1.2MPa or more and about 2.2MPa or less (gauge pressure) while at least any one of water and gas components was removed. Then, the pressure is reduced to atmospheric pressure (gauge pressure: 0 MPa) at a time when the temperature reaches about 220 ℃ or higher and about 260 ℃ or lower. The pressure in the autoclave is reduced to atmospheric pressure, and then reduced as necessary, whereby by-product water can be effectively removed.

Next, the autoclave is pressurized with an inert gas such as nitrogen, and the polyamide melt is extruded from the autoclave in the form of strands. The extruded strands were cooled and cut, thereby obtaining pellets of polyamide.

< Polymer end of Polyamide >

The polymer terminals of the polyamide ((a) aliphatic polyamide and (B) semiaromatic polyamide) contained in the polyamide composition of the present embodiment are not particularly limited, and may be classified and defined as 1) to 4) below.

I.e., 1) amino-terminal, 2) carboxyl-terminal, 3) terminal formed by the capping agent, 4) other terminal.

1) The amino end is provided with amino (-NH) ₂ Radical) is derived from a diamine.

2) The carboxyl terminus is the polymer terminus with carboxyl (-COOH group) derived from dicarboxylic acids.

3) The terminal end formed by the blocking agent is a terminal end formed in the case where the blocking agent is added at the time of polymerization. The blocking agent may be the blocking agent described above.

4) The other ends are polymer ends which are not classified as 1) to 3) above. As the other end, specifically, there may be mentioned: a terminal produced by deamination of the amino terminus, a terminal produced by decarboxylation of the carboxyl terminus, and the like.

(C) phosphinates ]

The (C) phosphinate contained in the polyamide composition according to the present embodiment is at least one kind of phosphinate selected from the group consisting of phosphinate represented by the following general formula (1) (phosphinate (1)), diphosphinate represented by the following general formula (2) (diphosphinate (2)), and a condensate thereof.

In the general formula (2), R ²¹ And R is ²² Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Y is Y ²¹ An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M's' ^m21+ A metal ion having a valence of m 21. M' is an element belonging to group 2 or group 15 of the periodic Table, a transition element, zinc or aluminum. n21 is an integer of 1 to 3. At n21 is 2 or 3In the case of (a) a plurality of R's are present ²¹ 、R ²² And Y ²¹ Each of which may be the same or different. m21 is 2 or 3.x is 1 or 2. In the case where x is 2, a plurality of M's may be the same or different. n21, x, and m21 are integers satisfying the relationship of 2×n21=m21×x).

[R ¹¹ 、R ¹² 、R ²¹ And R is ²² ]

R ¹¹ 、R ¹² 、R ²¹ And R is ²² Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. In the case where n11 is 2 or 3, a plurality of R's are present ¹¹ And R is ¹² The two may be the same or different, but from the viewpoint of easy production, the same is preferable. In addition, when n21 is 2 or 3, a plurality of R's are present ²¹ And R is ²² The two may be the same or different, but from the viewpoint of easy production, the same is preferable.

The alkyl group may be chain-shaped or cyclic, but is preferably chain-shaped. The chain alkyl group may be a straight chain alkyl group or a branched alkyl group. Examples of the linear alkyl group include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and the like. Examples of the branched alkyl group include: 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, 1-methylbutyl, 2-methylbutyl 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, and the like.

Examples of the aryl group include: phenyl, naphthyl, and the like.

The alkyl group and the aryl group may have a substituent. Examples of the substituent on the alkyl group include aryl groups having 6 to 10 carbon atoms. Examples of the substituent on the aryl group include an alkyl group having 1 to 6 carbon atoms.

Specific examples of the alkyl group having a substituent include: benzyl, and the like.

Specific examples of the aryl group having a substituent include: tolyl, xylyl, and the like.

Wherein R is as R ¹¹ 、R ¹² 、R ²¹ And R is ²² Alkyl groups having 1 to 6 carbon atoms are preferable, and methyl or ethyl groups are more preferable.

[Y ²¹ ]

Y ²¹ An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. In the case where n21 is 2 or 3, a plurality of Y's are present ²¹ The two may be the same or different, but from the viewpoint of easy production, the same is preferable.

The alkylene group may be chain-shaped or cyclic, but is preferably chain-shaped. The chain alkylene group may be a straight chain alkylene group or a branched chain alkylene group. Examples of the linear alkylene group include: methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and the like. Examples of the branched alkylene group include: 1-methylethylene, 1-methylpropylene, and the like.

Examples of the arylene group include: phenylene, naphthylene, and the like.

The alkylene group and arylene group may have a substituent. Examples of the substituent on the alkylene group include aryl groups having 6 to 10 carbon atoms. Examples of the substituent on the arylene group include an alkyl group having 1 to 6 carbon atoms.

Specific examples of the alkylene group having a substituent include: phenylmethylene, phenylethylene, phenyltrimethylene, phenyltetramethylene, and the like.

Specific examples of the arylene group having a substituent include: methylphenyl, ethylphenyl, t-butylphenyl, methylnaphthylene, ethylnaphthylene, t-butylnaphthylene, and the like.

Wherein as Y ²¹ An alkylene group having 1 to 10 carbon atoms is preferable, and a methylene group or an ethylene group is more preferable.

[ M and M' ]

M and M' are each independently an ion of an element belonging to group 2 or group 15 of the periodic table, an ion of a transition element, a zinc ion or an aluminum ion. Examples of the ions of the element belonging to group 2 of the periodic table include calcium ions and magnesium ions. Examples of the ions of the element belonging to group 15 of the periodic table include bismuth ions.

In the case where x is 2, the plurality of M's may be the same or different, but are preferably the same from the viewpoint of ease of production.

Among them, as M and M', calcium, zinc or aluminum is preferable, and calcium or aluminum is more preferable.

[x]

x represents the number of M' and is 1 or 2.x may be appropriately selected according to the kind of M' and the amount of the diphosphinic acid.

[ n11 and n21]

n11 represents the number of phosphinic acids and the valence of M, and n11 is 2 or 3. n11 may be appropriately selected according to the kind and valence of M.

n21 represents the number of the diphosphinic acids, and n21 is an integer of 1 to 3. n21 may be appropriately selected according to the kind and the number of M'.

[m21]

M21 represents the valence of M', and M21 is 2 or 3.

n21, x, and m21 are integers satisfying a relation of 2×n21=m21×x.

Specific examples of the preferable phosphinate (1) include: calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium methylethylphosphinate, magnesium methylethylphosphinate, aluminum methylethylphosphinate, zinc methylethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methylphosphinate, magnesium methylphosphinate, aluminum methylphosphinate, zinc methylphosphinate, calcium methane bis (methylphosphinate), magnesium methane bis (methylphosphinate), aluminum methane bis (methylphosphinate), zinc methane bis (methylphosphinate), calcium benzene-1, 4- (dimethylphosphinate), magnesium benzene-1, 4- (dimethylphosphinate), aluminum benzene-1, 4- (dimethylphosphinate), zinc methylphosphinate, calcium methylphosphinate, magnesium methylphosphinate, zinc phenylphosphinate, and the like. Among these, calcium dimethylphosphinate or aluminum dimethylphosphinate is particularly preferable as the phosphinate (1) from the viewpoint of excellent flame retardancy.

Specific examples of the preferable bisphosphonate (2) include: calcium methane di (methylphosphinate), magnesium methane di (methylphosphinate), aluminum methane di (methylphosphinate), zinc methane di (methylphosphinate), calcium benzene-1, 4-di (methylphosphinate), magnesium benzene-1, 4-di (methylphosphinate), aluminum benzene-1, 4-di (methylphosphinate), zinc benzene-1, 4-di (methylphosphinate), and the like.

The method for producing the phosphinates is not particularly limited, and examples thereof include the methods described in patent document 5, patent document 6, patent document 7, and the like. Specifically, the production is carried out in an aqueous solution using phosphinic acid and a metal carbonate, metal hydroxide or metal oxide. Although these phosphinates are essentially monomeric compounds, depending on the reaction conditions, polymeric phosphinates may be included as condensates having a degree of condensation of 1 to 3 depending on the circumstances.

The content of the (C) phosphinates is preferably 0.1 mass% or more and 30 mass% or less, more preferably 5 mass% or more and 30 mass% or less, still more preferably 5 mass% or more and 28 mass% or less, particularly preferably 8 mass% or more and 25 mass% or less, relative to the total mass of the (a) aliphatic polyamide, (B) semiaromatic polyamide, (C) phosphinates and (D) polymer.

By setting the content of the phosphinate (C) to the above lower limit or more, a polyamide composition having more excellent flame retardancy can be obtained. On the other hand, by setting the content of the phosphinate (C) to the above upper limit or less, a polyamide composition having more excellent flame retardancy without impairing the properties of the polyamide copolymer can be obtained.

A polymer having an oxygen index of 27% or more and an aromatic group in the main chain

The polymer (D) contained in the polyamide composition of the present embodiment is not particularly limited as long as the oxygen index is 27% or more. Specific examples of the polymer (D) include: polyphenylene sulfide, polyphenylene oxide, maleic anhydride modified polyphenylene oxide, polysulfone, polyetheretherketone, polyetherimide, polyamideimide, polyethersulfone, and the like. Among them, polyphenylene sulfide, polyphenylene ether, maleic anhydride-modified polyphenylene ether, or polysulfone is preferable as the polymer (D), and polyphenylene sulfide, polyphenylene ether, or maleic anhydride-modified polyphenylene ether is particularly preferable.

The "oxygen index" is generally an index of flammability of a material, and is represented by the minimum oxygen concentration (volume%) required for continuous combustion of the material. The oxygen index can be determined according to ISO 4589-2.

The content of the polymer (D) is 0.1 mass% or more and 8.0 mass% or less, preferably 1.0 mass% or more and 8.0 mass% or less, more preferably 2.5 mass% or more and 8.0 mass% or less, still more preferably 2.5 mass% or more and 6.5 mass% or less, relative to the total mass of the aliphatic polyamide (a), the semiaromatic polyamide (B), the phosphinate salt (C) and the polymer (D).

By setting the content of the polymer (D) to the above lower limit or more, a polyamide composition having more excellent flame retardancy can be obtained. On the other hand, by setting the content of the polymer (D) to the above upper limit or less, a polyamide composition having more excellent long-term heat resistance can be obtained.

In addition, by setting the content of the polymer (D) in the above range, a polyamide composition having more excellent flexural modulus and long-term heat resistance at the time of water absorption can be obtained.

[ (D) weight average molecular weight Mw (D) of Polymer ]

As an index of the molecular weight of the (D) polymer, a weight average molecular weight Mw (D) can be used. (D) The weight average molecular weight Mw (D) of the polymer is preferably 10000 or more and 70000 or less, more preferably 15000 or more and 60000 or less, still more preferably 20000 or more and 60000 or less, still more preferably 25000 or more and 60000 or less, particularly preferably 25000 or more and 55000 or less, and most preferably 30000 or more and 55000 or less.

When the weight average molecular weight Mw (D) is within the above range, a polyamide composition having more excellent mechanical properties, particularly, water absorption rigidity, thermal rigidity, fluidity, tensile strength when formed into a molded article, flexural modulus when absorbing water, long-term heat resistance, and the like can be obtained.

The weight average molecular weight Mw (D) may be measured by GPC as described in examples below.

Filling material (E)

The polyamide composition of the present embodiment may further contain (E) a filler in addition to the components (a) to (D). By containing the filler (E), a polyamide composition having more excellent mechanical properties such as toughness and rigidity can be obtained.

The filler (E) contained in the polyamide composition of the present embodiment is not particularly limited, and examples thereof include: glass fibers, carbon fibers, calcium silicate fibers, potassium titanate fibers, aluminum borate fibers, flake glass, talc, kaolin, mica, hydrotalcite, zinc carbonate, monocalcium phosphate, wollastonite, zeolite, boehmite, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluoromica, apatite, and the like.

These (E) fillers may be used alone or in combination of two or more.

Among them, from the viewpoints of rigidity and strength, glass fibers, carbon fibers, scaly glass, talc, kaolin, mica, monocalcium phosphate, wollastonite, carbon nanotubes, graphite, calcium fluoride, montmorillonite, swellable fluoromica, or apatite are preferable as the filler (E). Further, as the filler (E), glass fibers or carbon fibers are more preferable, and glass fibers are further preferable.

When the filler (E) is a glass fiber or a carbon fiber, the number average fiber diameter (D) is preferably 3 μm or more and 30 μm or less. The weight average fiber length (L) is preferably 100 μm or more and 750 μm or less. The aspect ratio ((L)/(D)) of the weight-average fiber length (L) to the number-average fiber diameter (D) is preferably 10 to 100. By using the glass fiber or the carbon fiber having the above-described constitution, higher characteristics can be exhibited.

In the case where the filler (E) is a glass fiber, the number average fiber diameter (D) is more preferably 3 μm or more and 30 μm or less. The weight average fiber length (L) is more preferably 103 μm or more and 500 μm or less. The aspect ratio ((L)/(D)) is more preferably 3 to 100.

(E) The number average fiber diameter and the weight average fiber length of the filler can be measured by the following methods.

First, a polyamide-containing solvent such as formic acid is used to dissolve the molded article of the polyamide composition. Then, for example, 100 or more fillers are arbitrarily selected from the obtained insoluble components. Then, the filling material can be obtained by observing the filling material with an optical microscope, a scanning electron microscope, or the like.

The content of the filler (E) in the polyamide composition is preferably 1% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, still more preferably 15% by mass or more and 60% by mass or less, particularly preferably 20% by mass or more and 50% by mass or less, and most preferably 25% by mass or more and 40% by mass or less, relative to the total mass of the polyamide composition.

When the content of the filler (E) is not less than the lower limit, the mechanical properties such as strength and rigidity of the polyamide composition tend to be further improved. On the other hand, when the content of the filler (E) is not more than the upper limit, a polyamide composition having more excellent moldability tends to be obtained.

In particular, the filler (E) is glass fiber, and the content of the filler (E) is in the above range relative to the total mass of the polyamide composition, whereby the mechanical properties such as strength and rigidity of the polyamide composition tend to be further improved.

(F) other additives ]

In addition to the components (a) to (E), the polyamide composition of the present embodiment may contain other additives (F) commonly used in polyamides within a range that does not impair the effects of the polyamide composition of the present embodiment. Examples of the other additives (F) include: (F1) A moldability improver, (F2) a deterioration inhibitor, (F3) a nucleating agent, (F4) a heat stabilizer, etc.

The content of the other additive (F) in the polyamide composition of the present embodiment varies depending on the kind thereof, the use of the polyamide composition, and the like, and is not particularly limited as long as the effect of the polyamide composition of the present embodiment is not impaired.

[ (F1) moldability improver ]

The moldability improver (F1) contained in the polyamide composition of the present embodiment is not particularly limited, and examples thereof include: higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, and the like. The moldability improver was also used as a "lubricating material".

(higher fatty acid)

Examples of the higher fatty acid include a linear or branched saturated or unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms.

Examples of the linear saturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include: lauric acid, palmitic acid, stearic acid, behenic acid, montanic acid, and the like.

Examples of the branched saturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include: isopalmitic acid, isostearic acid, and the like.

Examples of the linear unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include: oleic acid, erucic acid, and the like.

Examples of the branched unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include: iso-oleic acid, and the like.

Among them, stearic acid or montanic acid is preferable as the higher fatty acid.

(higher fatty acid metal salt)

The higher fatty acid metal salt refers to a metal salt of a higher fatty acid.

Examples of the metal element of the metal salt include: group 1, group 2 and group 3 elements of the periodic table, zinc, aluminum, and the like.

Examples of the group 1 element in the periodic table include: sodium, potassium, and the like.

Examples of the group 2 element in the periodic table include: calcium, magnesium, and the like.

Examples of the group 3 element in the periodic table include: scandium, yttrium, etc.

Among them, group 1 elements and group 2 elements of the periodic table or aluminum are preferable, and sodium, potassium, calcium, magnesium or aluminum is more preferable.

Specific examples of the higher fatty acid metal salt include: calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like.

Among these, as the higher fatty acid metal salt, montanic acid metal salt or stearic acid metal salt is preferable.

(higher fatty acid ester)

The higher fatty acid ester refers to an ester of a higher fatty acid with an alcohol.

The higher fatty acid ester is preferably an ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms.

Examples of the aliphatic alcohol having 8 to 40 carbon atoms include: stearyl alcohol, sorbitol, lauryl alcohol, and the like.

Specific examples of the higher fatty acid ester include: stearyl stearate, behenyl behenate, and the like.

(higher fatty acid amide)

Higher fatty acid amides refer to amide compounds of higher fatty acids.

Examples of the higher fatty acid amide include: stearamide, oleamide, erucamide, ethylene bisstearamide, ethylene bisoleamide, N-stearyl stearamide, N-stearyl erucamide, and the like.

Each of these higher fatty acids, higher fatty acid metal salts, higher fatty acid esters and higher fatty acid amides may be used alone or in combination of two or more.

[ (F2) degradation inhibitor ]

The (F2) deterioration inhibitor contained in the polyamide composition of the present embodiment is used for the purpose of preventing thermal deterioration, thermochromic, and improving thermal aging resistance.

The degradation inhibitor (F2) is not particularly limited, and examples thereof include: copper compounds, phenolic stabilizers, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, benzotriazole stabilizers, benzophenone stabilizers, cyanoacrylate stabilizers, salicylate stabilizers, sulfur-containing stabilizers, and the like.

Examples of the copper compound include: copper acetate, copper iodide, and the like.

Examples of the phenolic stabilizer include: hindered phenol compounds, and the like.

These (F2) degradation inhibitors may be used singly or in combination of two or more.

[ (F3) nucleating agent ]

(F3) The nucleating agent is a substance which can obtain at least any one of the following effects (1) to (3) by adding the nucleating agent.

(1) Effect of increasing the crystallization peak temperature of the polyamide composition.

(2) The effect of reducing the difference between the extrapolated onset temperature and the extrapolated end temperature of the crystallization peak.

(3) The effect of making the spherulites of the obtained molded article finer or the size thereof uniform.

The nucleating agent (F3) is not limited to the following, and examples thereof include: talc, boron nitride, mica, kaolin, silicon nitride, carbon black, potassium titanate, molybdenum disulfide, and the like.

(F3) The nucleating agent may be used alone or in combination of two or more.

Among them, talc or boron nitride is preferable as the (F3) nucleating agent from the viewpoint of the nucleating agent effect.

The number average particle diameter of the (F3) nucleating agent is preferably 0.01 μm or more and 10 μm or less, because the effect of the nucleating agent is high.

The number average particle diameter of the nucleating agent can be measured by the following method. First, the molded article is dissolved by a solvent such as formic acid in which polyamide is soluble. Then, for example, 100 or more nucleating agents are arbitrarily selected from the insoluble components obtained. Then, the particle diameter can be obtained by observing and measuring the particle diameter by an optical microscope, a scanning electron microscope, or the like.

The content of the nucleating agent in the polyamide composition of the present embodiment is preferably 0.001 parts by mass or more and 1 part by mass or less, more preferably 0.001 parts by mass or more and 0.5 parts by mass or less, and still more preferably 0.001 parts by mass or more and 0.09 parts by mass or less, per 100 parts by mass of the polyamide ((a) aliphatic polyamide and (B) semiaromatic polyamide).

When the content of the nucleating agent is set to the above lower limit or more relative to 100 parts by mass of the polyamide, the heat resistance of the polyamide composition tends to be further improved, and when the content of the nucleating agent is set to the above upper limit or less relative to 100 parts by mass of the polyamide, a polyamide composition having more excellent toughness can be obtained.

[ (F4) Heat stabilizer ]

The heat stabilizer (F4) is not limited to the following, and examples thereof include: phenolic heat stabilizers, phosphorus-containing heat stabilizers, amine heat stabilizers, metal salts of elements of groups 3, 4 and 11 to 14 of the periodic table, and the like.

(phenolic heat stabilizer)

The phenolic heat stabilizer is not limited to the following, and examples thereof include hindered phenol compounds. The hindered phenol compound has properties of imparting excellent heat resistance and light resistance to resins such as polyamides or fibers.

The hindered phenol compound is not limited to the following, and examples thereof include: n, N '-hexane-1, 6-diylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl propionamide), pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1,1 dimethylethyl } -2,4,8, 10-tetraoxaspiro [5.5] undecane, diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphonate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, and the like.

These hindered phenol compounds may be used alone or in combination of two or more.

When the phenolic heat stabilizer is used, the content of the phenolic heat stabilizer in the polyamide composition is preferably 0.01 mass% or more and 1 mass% or less, more preferably 0.05 mass% or more and 1 mass% or less, relative to the total mass of the polyamide composition.

When the content of the phenolic heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generation can be further reduced.

(phosphorus-containing Heat stabilizer)

Examples of the phosphorus-containing heat stabilizer include, but are not limited to, the following: pentaerythritol phosphite, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, triisodecyl phosphite, diisodecyl phosphite, ditridecyl phosphite, isooctyl phosphite, diphenyl phosphite, isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (butoxyethyl) phosphite, tris (4, 4' -butylidenebis (3-methyl-6-tert-butylphenyl) phosphite-tetra (tridecyl) phosphite, 4' -isopropylidenediphenyl-tetra (C12-C15 mixed alkyl) phosphite, 4' -isopropylidenebis-di (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (1, 4' -di-tert-butylphenyl) diphenyl phosphite, 1, 4' -di-tert-butylphenyl-1-4-di-tert-butylphenyl) 4-di-tert-butylphenyl phosphite, 1-tert-4-butylidene-4-di-tert-butylphenyl phosphite, tris (mono-, di-mixed nonylphenyl) phosphite, 4 '-isopropylidenebis (2-t-butylphenyl) phosphite-bis (nonylphenyl) ester, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3, 5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4, 4' -isopropylidenediphenyl polyphosphite, bis (4, 4 '-butylidenebis (3-methyl-6-t-butylphenyl)) -1, 6-hexanol bisphosphite, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane bisphosphite hexa (tridecyl) phosphite, tris (4, 4' -isopropylidenebis (2-t-butylphenyl) phosphite, tris (1, 3-stearoyloxyisopropyl) phosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octylphosphite, 2-methylenebis (3-methyl-6-t-butylphenyl) diphenylphosphite, 4 '-di-t-butylphenyl) biphenyl 4,4' -di-t-butylphenyl) 4,4 '-di-butylphenyl 4-4' -biphenylene phosphite and the like.

These phosphorus-containing heat stabilizers may be used alone or in combination of two or more.

The pentaerythritol-type phosphite compound is not limited to the following, and examples thereof include: pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-phenyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-methyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-2-ethylhexyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-isodecyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-lauryl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-isotridecyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-stearyl ester pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-cyclohexyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-benzyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-ethylcellosolve ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-butylcarbitol ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-octylphenyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-nonylphenyl ester, pentaerythritol diphosphite di (2, 6-di-tert-butyl-4-methylphenyl) ester, pentaerythritol diphosphite bis (2, 6-di-tert-butyl-4-ethylphenyl), pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-2, 6-di-tert-butylphenyl, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-2, 4-di-tert-octylphenyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-2-cyclohexylphenyl ester, pentaerythritol diphosphite 2, 6-di-tert-amyl-4-methylphenyl ester, pentaerythritol diphosphite bis (2, 6-di-tert-octyl-4-methylphenyl) ester, and the like.

These pentaerythritol-type phosphite compounds may be used alone or in combination of two or more.

When the phosphorus-containing heat stabilizer is used, the content of the phosphorus-containing heat stabilizer in the polyamide composition is preferably 0.01 mass% or more and 1 mass% or less, more preferably 0.05 mass% or more and 1 mass% or less, relative to the total mass of the polyamide composition.

When the content of the phosphorus-containing heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generation can be further reduced.

(amine Heat stabilizer)

Examples of the amine heat stabilizer include, but are not limited to, the following: 4-Acetyloxy-2, 6-tetramethylpiperidine, 4-stearoyloxy-2, 6-tetramethylpiperidine, 4-acryloyloxy-2, 6-tetramethylpiperidine 4- (Phenylacetoxy) -2, 6-tetramethylpiperidine, 4-benzoyloxy-2, 6-tetramethylpiperidine, 4-methoxy-2, 6-tetramethylpiperidine 4- (Phenylacetoxy) -2, 6-tetramethylpiperidine 4-benzoyloxy-2, 6-tetramethylpiperidine, 4-methoxy-2, 6-tetramethylpiperidine 4- (cyclohexylcarbamoyloxy) -2, 6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2, 6-tetramethylpiperidine bis (2, 6-tetramethyl-4-piperidinyl) carbonate, bis (2, 6-tetramethyl-4-piperidinyl) oxalate, bis (2, 6-tetramethyl-4-piperidinyl) malonate bis (2, 6-tetramethyl-4-piperidinyl) carbonate, bis (2, 6-tetramethyl-4-piperidinyl) oxalate malonic acid bis (2, 6-tetramethyl-4-piperidinyl) ester, benzene-1, 3, 4-tricarboxylic acid tris (2, 6-tetramethyl-4-piperidinyl) ester 1- [2- {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy } butyl ] -4- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] -2, 6-tetramethylpiperidine benzene-1, 3, 4-tricarboxylic acid tris (2, 6-tetramethyl-4-piperidinyl) ester, 1- [2- {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy } butyl ] -4- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] -2, 6-tetramethylpiperidine 1,2,3, 4-butanetetracarboxylic acid with 1,2, 6-pentamethyl-4-piperidinol and beta, condensate of beta, beta' -tetramethyl-3, 9- [2,4,8, 10-tetraoxaspiro (5.5) undecane ] diethanol, and the like.

These amine heat stabilizers may be used alone or in combination of two or more.

When the amine heat stabilizer is used, the content of the amine heat stabilizer in the polyamide composition is preferably 0.01 mass% or more and 1 mass% or less, more preferably 0.05 mass% or more and 1 mass% or less, relative to the total mass of the polyamide composition.

When the content of the amine heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generation can be further reduced.

(metal salts of elements of groups 3, 4 and 11 to 14 of the periodic Table)

The metal salts of the elements of groups 3, 4 and 11 to 14 of the periodic table are not limited as long as they are salts of metals belonging to these groups.

Among them, copper salts are preferable from the viewpoint of further improving the heat aging resistance of the polyamide composition. The copper salt is not limited to the following, and examples thereof include: copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, copper complex salts obtained by complexing copper with chelating agents.

Examples of the chelating agent include: ethylenediamine, ethylenediamine tetraacetic acid, and the like.

These copper salts may be used singly or in combination of two or more.

Among them, copper acetate is preferable as copper salt. When copper acetate is used, a polyamide composition having more excellent thermal aging resistance and capable of more effectively suppressing metal corrosion of the screw or barrel portion during extrusion (hereinafter, sometimes simply referred to as "metal corrosion") can be obtained.

When a copper salt is used as the (F4) heat stabilizer, the content of the copper salt in the polyamide composition is preferably 0.01 mass% or more and 0.60 mass% or less, more preferably 0.02 mass% or more and 0.40 mass% or less, relative to the total mass of the polyamide ((a) aliphatic polyamide and (B) semiaromatic polyamide).

When the content of the copper salt is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the precipitation of copper and the corrosion of metal can be more effectively suppressed.

In addition, from the viewpoint of improving the heat aging resistance of the polyamide composition, the polyamide composition is composed of a polyamide ((A) aliphatic polyamide and (B) semiaromatic polyamide)Family polyamide) 10 ⁶ The content concentration of the copper element derived from the copper salt is preferably 10 parts by mass or more and 2000 parts by mass or less (100 ten thousand parts by mass), more preferably 30 parts by mass or more and 1500 parts by mass or less, and still more preferably 50 parts by mass or more and 500 parts by mass or less.

The above-described component (F4) may be used alone or in combination of two or more.

Process for producing polyamide composition

The method for producing the polyamide composition of the present embodiment is not particularly limited as long as the aliphatic polyamide (a) is mixed with the components (B) to (D) and, if necessary, (E) and (F).

Examples of the method for mixing the components (a) to (D) and, if necessary, (E) and (F) include the following methods (1) and (2).

(1) A method in which the components (A) to (D) and, if necessary, (E) and (F) are mixed by using a Henschel mixer or the like, and supplied to a melt kneader to be kneaded.

(2) A method in which the components (a) to (D) and, if necessary, the component (E) are mixed in advance using a henschel mixer or the like to prepare a mixture containing the components (a) to (D) and, if necessary, the component (F), the mixture is fed to a melt kneader and kneaded, and then the component (E) is optionally compounded by a side feeder using a single-screw or twin-screw extruder.

In the method of supplying the components constituting the polyamide composition to the melt kneader, all the components may be supplied at once at the same supply port, or the components may be supplied from different supply ports.

The temperature for melt kneading is preferably a temperature higher than the melting point of the aliphatic polyamide (A) by about 1℃or more and about 100℃or less, and more preferably a temperature higher than the melting point of the aliphatic polyamide (A) by about 10℃or more and about 50℃or less.

The shear rate in the mixer is preferably about 100 seconds ^-1 The above. In addition, anotherThe average residence time during kneading is preferably about 0.5 minutes to about 5 minutes.

As the apparatus for melt kneading, any known apparatus may be used, and for example, a single screw or twin screw extruder, a banbury mixer, a melt kneader (mixing roll, etc.), or the like is preferably used.

The amount of each component to be blended in the production of the polyamide composition of the present embodiment is the same as the content of each component in the polyamide composition described above.

Molded article

The molded article of the present embodiment is obtained by molding the polyamide composition of the above embodiment.

The molded article of the present embodiment does not contain halogen, is excellent in flame retardancy, and is excellent in tensile strength, flexural modulus upon water absorption, and long-term heat resistance.

The method for obtaining the molded article is not particularly limited, and a known molding method can be used.

Examples of known molding methods include: extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decoration molding, heterogeneous material molding, gas-assisted injection molding, foaming injection molding, low pressure molding, ultra-thin wall injection molding (ultra-high speed injection molding), in-mold composite molding (insert molding, insert over molding), and the like.

< use >

The molded article of the present embodiment contains the polyamide composition of the above embodiment, has excellent flame retardancy and mechanical properties (particularly, flexural modulus and long-term heat resistance upon water absorption), and can be used for various applications.

The molded article of the present embodiment can be suitably used in, for example, the fields of automobiles, electric and electronic fields, machinery and industry, office equipment, aviation and aerospace, and the like.

Examples (example)

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

The components of the polyamide compositions used in the present examples and comparative examples will be described below.

< constituent component >

[ (A) aliphatic Polyamide ]

A-1: polyamide 66

A-2: polyamide 6 (model SF1013A, molecular weight 33000, manufactured by Yu Kong Xing Co., ltd.)

[ (B) semi-aromatic Polyamide ]

B-1: polyamide 6I

B-2: polyamide 6I/6T (manufactured by EMS Co., ltd., model: G21, content of isophthalic acid unit in all dicarboxylic acid units: 70 mol%, molecular weight: 27000)

B-3: polyamide MXD6 (manufactured by Toyo-spun Co., ltd., trade name: toyo-spun nylon, T-600)

[ (C) phosphinates ]

C-1: aluminum diethylphosphinate (trade name: "Exolit OP1230", manufactured by Clariant Co., ltd.) as a phosphinate flame retardant

C-2: calcium diethylphosphinate (manufactured by Taiping chemical industry Co., ltd.) as a phosphinic acid flame retardant

[ (C') flame retardant other than phosphinates ]

C' -1: nitrogen-containing flame retardant melamine cyanurate (manufactured by Nissan chemical industry Co., ltd.)

C' -2: nitrogen and phosphorus containing flame retardant cyclic phenoxy phosphazene (manufactured by Otsuka chemical Co., ltd.)

[ (D) Polymer having an oxygen index of 27% or more and an aromatic group in the main chain ]

D-1: polyphenylene Sulfide (PPS) (manufactured by DIC Co., ltd.) (oxygen index: 46%, molecular weight: 30000)

D-2: maleic anhydride-modified polyphenylene ether (m-PPE) (manufactured by Asahi chemical Co., ltd.) (oxygen index: 28%, molecular weight: 54000)

D-3: polyphenylene Ether (PPE) (manufactured by Asahi chemical Co., ltd.) (oxygen index: 28%, molecular weight: 30000)

D-4: polysulfone (PSF) (manufactured by Solvay) (oxygen index: 30%, molecular weight: 50000)

[ (D') polymers having an oxygen index of less than 27% or no aromatic groups in the main chain ]

D' -1: polycarbonate (PC) (manufactured by Di people Co., ltd.) (oxygen index: 25%, molecular weight: 40000)

D' -2: polyvinyl chloride (PVC) (manufactured by Dayang polyvinyl chloride Co.) (oxygen index: 30%, molecular weight: 97000)

The oxygen index of the polymer (D) and the polymer (D') were measured in accordance with ISO 4589-2.

[ (E) filler ]

E-1: glass Fiber (GF) (trade name: ECS03T275H, manufactured by Nitro Kogyo Co., ltd., average fiber diameter: 10 μm phi, cut length: 3 mm)

[ (F) other additives ]

F-1: phenolic heat stabilizer (trade name "Irganox 1098", manufactured by Ciba refining Co., ltd.)

< production of Polyamide >

The following describes in detail the production methods of the aliphatic polyamide A-1 and the semiaromatic polyamide B-1. The aliphatic polyamide a-1 and the semiaromatic polyamide B-1 obtained by the following production methods were dried in a nitrogen gas stream to adjust the water content to about 0.2 mass%, and then used as raw materials for polyamide compositions in examples and comparative examples described later.

Synthesis example 1 Synthesis of aliphatic Polyamide A-1 (Polyamide 66)

The polymerization of polyamide was carried out by the "hot melt polymerization method" as described below.

First, 1500g of an equimolar salt of adipic acid and hexamethylenediamine was dissolved in 1500g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomers. This aqueous solution was charged into an autoclave having an internal volume of 5.4L, and nitrogen substitution was performed. Then, while stirring at a temperature of about 110 ℃ or higher and about 150 ℃ or lower, the vapor was slowly discharged and concentrated to a solution concentration of 70 mass%. Then, the internal temperature was raised to 220 ℃. At this time, the autoclave was pressurized to 1.8MPa. This state was maintained for 1 hour until the internal temperature reached 245 ℃, and the reaction was carried out for 1 hour while slowly discharging water vapor while maintaining the pressure at 1.8MPa. Then, the pressure was reduced for 1 hour. Then, the inside of the autoclave was kept under reduced pressure of 650 Torr (86.66 kPa) for 10 minutes by means of a vacuum apparatus. At this time, the final internal temperature of the polymerization was 265 ℃. Then, the resultant was pressurized with nitrogen gas, formed into a strand form from a lower spinning nozzle, cooled with water, cut, and discharged in the form of pellets. Next, the pellets were dried at 100℃under a nitrogen atmosphere for 12 hours, whereby aliphatic polyamide A-1 (polyamide 66) was obtained.

Mw (a) =40000 of the obtained aliphatic polyamide a-1 (polyamide 66).

Synthesis example 2 Synthesis of semi-aromatic Polyamide B-1 (Polyamide 6I)

The polymerization of polyamide was carried out by the "hot melt polymerization method" as described above.

First, 1500g of an equimolar salt of isophthalic acid and hexamethylenediamine, adipic acid in an amount of 1.5 mol% exceeding the total equimolar salt content, and acetic acid in an amount of 0.5 mol% were dissolved in 1500g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomers. Then, while stirring at a temperature of about 110 ℃ or higher and about 150 ℃ or lower, the vapor was slowly discharged and concentrated to a solution concentration of 70 mass%. Then, the internal temperature was raised to 220 ℃. At this time, the autoclave was pressurized to 1.8MPa. This state was maintained for 1 hour until the internal temperature reached 245 ℃, and the reaction was carried out for 1 hour while slowly discharging water vapor while maintaining the pressure at 1.8MPa. Then, the pressure was reduced for 30 minutes. Then, the inside of the autoclave was kept under reduced pressure of 650 Torr (86.66 kPa) for 10 minutes by means of a vacuum apparatus. At this time, the final internal temperature of the polymerization was 265 ℃. Next, the yarn was formed into a strand shape from a lower spinning nozzle (nozzle) by pressurizing with nitrogen gas, water-cooled, cut, and discharged in a pellet shape. Next, the pellets were dried at 100℃under a nitrogen atmosphere for 12 hours to obtain semi-aromatic polyamide B-1 (polyamide 6I).

The content of isophthalic acid unit in the dicarboxylic acid unit of the resulting semiaromatic polyamide B-1 (polyamide 6I) was 100 mol%. Mw=20000.

< physical Properties and evaluation >

First, pellets of the polyamide compositions obtained in examples and comparative examples were dried in a nitrogen gas stream, and the water content in the polyamide compositions was adjusted to 500ppm or less. Next, using pellets of each polyamide composition having a water content adjusted, measurement of various physical properties and various evaluations were performed by the following methods.

[ physical Property 1] tan delta Peak temperature

Using a PS40E injection molding machine manufactured by japanese industrial Co., ltd., the cylinder temperature was set to 290 ℃, the mold temperature was set to 100 ℃, and molded into a molded article according to JIS-K7139 under injection molding conditions of an injection time of 10 seconds and a cooling time of 10 seconds. The molded article was measured under the following conditions using a dynamic viscoelasticity evaluation device (EPLEXOR 500N, manufactured by GABO corporation).

(measurement conditions)

Measurement mode: stretching

Measuring frequency: 8.00Hz

Heating rate: 3 ℃/min

Temperature range: -100-250 DEG C

The ratio (E2/E1) of the loss elastic modulus E2 to the storage elastic modulus E1 was set to tan delta, and the highest temperature was set to tan delta peak temperature.

Physical Property 2 molecular weight (Mw) of Polyamide composition

The weight average molecular weight (Mw) of the polyamide compositions obtained in examples and comparative examples was measured using GPC under the following measurement conditions.

(measurement conditions)

Measurement device: HLC-8020 manufactured by Tosoh Co., ltd

Solvent: hexafluoroisopropanol solvent

Standard sample: PMMA (polymethyl methacrylate) (manufactured by Polymer laboratories Co., ltd.) conversion

GPC column: TSK-GEL GMHHR-M and G1000HHR

[ evaluation 1] flame retardance

The measurement was performed using the method of UL94 (standard established by underwriters laboratories, usa). Test pieces (length 127mm, width 12.7mm, thickness 1.6 mm) were produced in the following manner: the mold (mold temperature=100℃) for the UL test piece was mounted on an injection molding machine (PS 40E manufactured by japanese industrial Co., ltd.) and each polyamide composition was molded at a cylinder temperature of 290 ℃. Regarding the injection pressure, it was carried out at a total filling pressure +2% at the time of molding the UL test piece. Whether the flame retardant rating corresponds to any of V-0, V-1, V-2 was evaluated according to the UL94 standard (vertical burning test). The smaller the number of the grade, the higher the flame retardancy.

[ evaluation 2] tensile Strength

Using an injection molding machine "PS-40E: each polyamide composition was molded into a molded sheet of multipurpose test piece A according to ISO 3167, manufactured by Nikkin resin Co., ltd. The specific molding conditions are as follows: the injection+dwell time was set to 25 seconds, the cooling time was set to 15 seconds, the mold temperature was set to 80 ℃, and the molten resin temperature was set to the high temperature side melting peak temperature (Tm 2) +20 ℃ of the polyamide.

The obtained molded sheet of the multipurpose test piece type A was used to conduct a tensile test at a pulling rate of 5 mm/min at a temperature of 23℃according to ISO 527, and a tensile yield stress was measured as a tensile strength.

[ evaluation 3] flexural modulus of elasticity at Water absorption

An ISO dumbbell test piece with a thickness of 4mm was produced as a test piece. Using the obtained test piece, flexural modulus was measured according to ISO 178. In addition, after the ISO dumbbell test piece was placed under a constant temperature and humidity (23 ℃ C., 50 RH%) atmosphere to reach the water absorption equilibrium, the flexural modulus was measured according to ISO 178.

[ evaluation 4] Long-term Heat resistance

The multipurpose test piece (type a) of the tensile strength described above was heat aged by heating at 150 ℃ in a hot air circulation oven.

After 1000 hours in the oven, the mixture was taken out of the oven and cooled at 23℃for more than 24 hours. Next, the cooled multipurpose test piece (type A) was subjected to a tensile test according to ISO 527 and at a pulling rate of 5 mm/min by the same method as described above, and each tensile strength was measured. The heat aging retention was determined using the following formula.

Heat aging retention (%) =tensile strength after aging/tensile strength before aging×100

[ evaluation 5] leakage resistance

Test pieces of 30mm by 30mm and 4mm in thickness were prepared and CTI was measured according to IEC60112 standard. The voltage was applied in units of 50V.

The grades are classified according to the relative Tracking Index (TI) obtained as follows.

(grading)

CTI level 0: 600 is less than or equal to TI

CTI stage 1: TI is 400-600

CTI grade 2: TI is more than or equal to 250 and less than 400

CTI grade 3: TI is 175-250

CTI grade 4: TI is more than or equal to 100 and less than 175

CTI grade 5: TI is more than or equal to 0 and less than 100

EXAMPLE 1 production of Polyamide composition P-1a

A TEM35mm twin-screw extruder (set temperature: 280 ℃ C., screw rotation speed: 300 rpm) manufactured by Toshiba machinery Co., ltd.) was used, and (A) the aliphatic polyamide A-1 and (B) the semiaromatic polyamide B-1, (D) the polymer D-1 and (F) the other additive F-1 were fed from a top feed port provided at the uppermost stream portion of the extruder, and mixed in advance. In addition, (C) the flame retardant C-1 and (E) the filler E-1 are fed from a side feed port on the downstream side of the extruder (in a state where the resin fed from the top feed port is sufficiently melted). Next, the molten kneaded material extruded from the die is cooled in the form of strands and pelletized, thereby obtaining pellets of the polyamide composition P-1 a. The blending amount was set to (A) an aliphatic polyamide A-1:46.0 mass%, (B) semi-aromatic polyamide B-1:11.6 mass%, (C) flame retardant C-1: 16.0% by mass, (D) polymer D-1:1.0 mass%, (E) filler E-1:25.0 mass%, and (F) other additives F-1:0.1 mass%.

EXAMPLE 2 production of Polyamide composition P-2a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:45.2 mass%, (B) semi-aromatic polyamide B-1:11.4 mass%, and (D) Polymer D-1: pellets of polyamide composition P-2a were obtained in the same manner as in example 1 except for 2.0% by mass.

EXAMPLE 3 production of Polyamide composition P-3a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 44.4% by mass, (B) a semiaromatic polyamide B-1:11.2 mass%, and (D) Polymer D-1: pellets of polyamide composition P-3a were obtained in the same manner as in example 1 except for 3.0% by mass.

EXAMPLE 4 production of Polyamide composition P-4a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 43.6% by mass, (B) a semiaromatic polyamide B-1:11.0 mass%, and (D) Polymer D-1: pellets of polyamide composition P-4a were obtained in the same manner as in example 1 except for 4.0% by mass.

EXAMPLE 5 production of Polyamide composition P-5a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:46.2 mass%, (B) semi-aromatic polyamide B-1:11.6 mass%, and (D) Polymer D-2: pellets of polyamide composition P-5a were obtained in the same manner as in example 1 except for 1.0 mass%.

EXAMPLE 6 production of Polyamide composition P-6a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 44.6% by mass, (B) a semiaromatic polyamide B-1:11.2 mass%, and (D) Polymer D-2: pellets of polyamide composition P-6a were obtained in the same manner as in example 1 except for 3.0% by mass.

EXAMPLE 7 production of Polyamide composition P-7a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:42.8 mass%, (B) semi-aromatic polyamide B-1:10.8 mass%, and (D) Polymer D-2: pellets of polyamide composition P-7a were obtained in the same manner as in example 1 except for 5.0% by mass.

EXAMPLE 8 production of Polyamide composition P-8a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:40.0 mass%, (B) semi-aromatic polyamide B-1:10.0 mass%, and (D) Polymer D-2: pellets of polyamide composition P-8a were obtained in the same manner as in example 1 except for 5.7% by mass.

EXAMPLE 9 production of Polyamide composition P-9a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 44.4% by mass, (B) a semiaromatic polyamide B-1:11.2 mass%, and (D) Polymer D-3: pellets of polyamide composition P-9a were obtained in the same manner as in example 1 except for 3.0% by mass.

EXAMPLE 10 production of Polyamide composition P-10a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 44.4% by mass, (B) a semiaromatic polyamide B-1:11.2 mass%, and (D) Polymer D-4: pellets of polyamide composition P-10a were obtained in the same manner as in example 1 except for 3.0% by mass.

EXAMPLE 11 production of Polyamide composition P-11a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:45.2 mass%, (B) semi-aromatic polyamide B-2:11.4 mass%, and (D) Polymer D-1: pellets of polyamide composition P-11a were obtained in the same manner as in example 1 except for 2.0% by mass.

EXAMPLE 12 production of Polyamide composition P-12a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:42.8 mass%, (B) semi-aromatic polyamide B-2:10.8 mass%, and (D) Polymer D-2: pellets of polyamide composition P-12a were obtained in the same manner as in example 1 except for 5.0% by mass.

EXAMPLE 13 production of Polyamide composition P-13a

Except that the blending amount was changed to (A) the aliphatic polyamide A-2:45.2 mass%, (B) semi-aromatic polyamide B-1:11.4 mass%, and (D) Polymer D-1: pellets of polyamide composition P-13a were obtained in the same manner as in example 1 except for 2.0% by mass.

EXAMPLE 14 production of Polyamide composition P-14a

Except that the blending amount was changed to (A) the aliphatic polyamide A-2:42.8 mass%, (B) semi-aromatic polyamide B-1:10.8 mass%, and (D) Polymer D-2: pellets of polyamide composition P-14a were obtained in the same manner as in example 1 except for 5.0% by mass.

EXAMPLE 15 production of Polyamide composition P-15a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:48.2 mass%, (B) semi-aromatic polyamide B-1:5.4 mass%, and (D) Polymer D-2: pellets of polyamide composition P-15a were obtained in the same manner as in example 1 except for 5.0% by mass.

EXAMPLE 16 production of Polyamide composition P-16a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 37.5% by mass, (B) a semiaromatic polyamide B-1: 16.1% by mass, (D) Polymer D-2: pellets of polyamide composition P-16a were obtained in the same manner as in example 1 except for 5.0% by mass.

EXAMPLE 17 production of Polyamide composition P-17a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:32.2 mass%, (B) semi-aromatic polyamide B-1:21.4 mass%, and (D) Polymer D-2: pellets of polyamide composition P-17a were obtained in the same manner as in example 1 except for 5.0% by mass.

EXAMPLE 18 production of Polyamide composition P-18a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 29.4% by mass, (B) a semiaromatic polyamide B-1:7.4 mass%, (C) phosphinate salt C-1:9.0 mass%, (D) Polymer D-2:3.8 mass%, and (E) a filler: pellets of polyamide composition P-18a were obtained in the same manner as in example 1 except for 50% by mass.

EXAMPLE 19 production of Polyamide composition P-19a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:22.2 mass%, (B) semi-aromatic polyamide B-1:14.6 mass%, (C) phosphinate salt C-1:9.0 mass%, (D) Polymer D-2:3.8 mass%, and (E) a filler: pellets of polyamide composition P-19a were obtained in the same manner as in example 1 except for 50.0% by mass.

EXAMPLE 20 production of Polyamide composition P-20a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 39.6% by mass, (B) a semiaromatic polyamide B-1:10.0 mass%, (C) phosphinate salts C-2:20.0 mass%, (D) Polymer D-2: pellets of polyamide composition P-20a were obtained in the same manner as in example 1 except for 5.0% by mass.

EXAMPLE 21 production of Polyamide composition P-21a

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:7.0 mass%, (B) semi-aromatic polyamide B-3:46.6 mass%, (C) phosphinate C-1:16.0 mass%, (D) Polymer D-2: pellets of polyamide composition P-21a were obtained in the same manner as in example 1 except for 5.0% by mass.

Comparative example 1 production of Polyamide composition P-1b

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:46.8 mass%, (B) semi-aromatic polyamide B-1:11.8 mass%, and (D) Polymer D-1: pellets of the polyamide composition P-1b were obtained in the same manner as in example 1 except for 0% by mass.

Comparative example 2 production of Polyamide composition P-2b

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:46.8 mass%, (B) semi-aromatic polyamide B-2:11.8 mass%, and (D) Polymer D-1: pellets of polyamide composition P-2b were obtained in the same manner as in example 1 except for 0% by mass.

Comparative example 3 production of Polyamide composition P-3b

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 41.7% by mass, (B) a semiaromatic polyamide B-1:10.4 mass% of (D) a polymer D-1: pellets of polyamide composition P-3b were obtained in the same manner as in example 1 except for 6.5% by mass.

Comparative example 4 production of Polyamide composition P-4b

Except that the blending amount was changed to (A) the aliphatic polyamide A-1: 41.7% by mass, (B) a semiaromatic polyamide B-1:10.4 mass% of (D) a polymer D-2: pellets of polyamide composition P-4b were obtained in the same manner as in example 1 except for 6.5% by mass.

Comparative example 5 production of Polyamide composition P-5b

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:42.8 mass%, (B) semi-aromatic polyamide B-1:10.8 mass%, and (D ') Polymer D' -1: pellets of polyamide composition P-5b were obtained in the same manner as in example 1 except for 5.0% by mass.

Comparative example 6 production of Polyamide composition P-6b

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:42.8 mass%, (B) semi-aromatic polyamide B-1:10.8 mass%, and (D ') polymer D' -2: pellets of polyamide composition P-6b were obtained in the same manner as in example 1 except for 5.0% by mass.

Comparative example 7 production of Polyamide composition P-7b

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:24.3 mass%, (B) semi-aromatic polyamide B-1:16.3 mass%, (C) phosphinate salt C-1:9.0 mass%, and (D) Polymer D-1: pellets of polyamide composition P-7b were obtained in the same manner as in example 1 except for 0% by mass.

Comparative example 8 production of Polyamide composition P-8b

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:42.8 mass%, (B) semi-aromatic polyamide B-1:10.8 mass%, (C ') flame retardant other than phosphinates C' -1:16.0 mass%, and (D) a polymer D-2: pellets of polyamide composition P-8b were obtained in the same manner as in example 1 except for 5.0% by mass.

Comparative example 9 production of Polyamide composition P-9b

Except that the blending amount was changed to (A) the aliphatic polyamide A-1:42.8 mass%, (B) semi-aromatic polyamide B-1:10.8 mass%, (C ') flame retardant other than phosphinates C' -2:16.0 mass%, and (D) a polymer D-2: pellets of polyamide composition P-9b were obtained in the same manner as in example 1 except for 5.0% by mass.

Further, molded articles were produced by the above method using the pellets of each polyamide composition, and various physical properties were measured and evaluated. The evaluation results are shown in tables 1 to 5 below.

TABLE 1

TABLE 2

TABLE 3 Table 3

TABLE 4 Table 4

TABLE 5

From tables 1 to 3, it is understood that the molded articles obtained from the polyamide compositions P-1a to P-21a (examples 1 to 21) which contain the aliphatic polyamide (a), the semiaromatic polyamide (B), the phosphinate (C) and the polymer (D) and have the content of the polymer (D) in the range of 0.1 mass% or more and 8.0 mass% or less relative to the total mass of the components (a) to (D) are excellent in flame retardancy, tensile strength, flexural modulus at the time of water absorption and long-term heat resistance.

In addition, among the polyamide compositions P-3a, P-6a, P-9a and P-10a (examples 3, 6, 9 and 10) containing different kinds of (D) polymers, molded articles obtained from the polyamide compositions P-3a, P-6a and P-9a (examples 3, 6 and 9) containing D-1, D-2 and D-3 are particularly good in tensile strength and long-term heat resistance as compared with molded articles obtained from the polyamide composition P-10a (example 10) containing D-4.

In addition, among the polyamide compositions P-2a and P-11a (examples 2 and 11) and P-7a and P-12a (examples 7 and 12) containing the different kinds of (B) semiaromatic polyamides, molded articles obtained from the polyamide compositions P-2a and P-7a (examples 2 and 7) containing B-1 were particularly excellent in tensile strength and flexural modulus upon water absorption as compared with molded articles obtained from the polyamide compositions containing B-2 (examples 11 and 12).

In addition, among the polyamide compositions P-2a and P-13a (examples 2 and 13) and P-7a and P-14a (examples 7 and 14) containing different kinds of (A) aliphatic polyamides, molded articles obtained from the polyamide compositions P-2a and P-7a (examples 2 and 7) containing A-1 were particularly excellent in tensile strength and flexural modulus upon water absorption as compared with molded articles obtained from the polyamide compositions P-13a and P-14a (examples 13 and 14) containing A-2.

In addition, among the polyamide compositions P-8a and P-20a (examples 8 and 20) containing different kinds of (C) phosphinates, the molded article obtained from the polyamide composition P-8a containing C-1 (example 8) is particularly excellent in tensile strength and flexural modulus at the time of water absorption as compared with the molded article obtained from the polyamide composition P-20a containing C-2 (example 20).

On the other hand, as is clear from tables 4 to 5, the molded articles obtained from the polyamide compositions P-1b, P-2b and P-7b (comparative examples 1, 2 and 7) containing no polymer (D) were inferior in flame retardancy, flexural modulus of elasticity upon absorption of water and long-term heat resistance.

The molded articles obtained from the polyamide compositions P-3b and P-4b (comparative examples 3 and 4) having a content of the polymer (D) of more than 8.0 mass% relative to the total mass of the components (A) to (D) were inferior in flame retardancy and electric leakage resistance.

The flame retardancy of molded articles obtained from polyamide compositions P-5b (comparative example 5) containing (D ') polymers having an oxygen index of less than 27% and having no aromatic groups in the main chain, in which the content of (D ') polymers is 0.1 mass% or more and 8.0 mass% or less relative to the total mass of the components (A) to (D ').

The molded article obtained from the polyamide composition P-6b (comparative example 6) containing the (D ') polymer having no aromatic group in the main chain, which contained the (D ') polymer in an amount of 0.1 mass% or more and 8.0 mass% or less relative to the total mass of the components (A) to (D '), had poor flexural modulus, long-term heat resistance and leakage resistance upon water absorption.

In addition, the flame retardancy, tensile strength and flexural modulus at the time of water absorption of the molded article obtained from the polyamide composition P-9b (comparative example 9) were poor, as well as the leakage resistance of the molded article obtained from the polyamide composition P-9b (comparative example 9) obtained from the polyamide composition P-8b containing the nitrogen-and phosphorus-containing flame retardant C ' -1 as (C ') and the flame retardant containing no halogen element other than phosphinates instead of (C ') instead of (C) phosphinates (comparative example 8).

As described above, the polyamide composition according to the present embodiment can provide a molded article which does not contain halogen, has flame retardancy, tensile strength, flexural modulus at the time of water absorption, and has excellent long-term heat resistance.

[ industrial applicability ]

According to the polyamide composition of the present embodiment, a molded article which does not contain halogen, but is excellent in flame retardancy and long-term heat resistance can be obtained. The molded article of the present embodiment can be suitably used in the fields of automobiles, electric and electronic fields, machinery and industry, office equipment, aviation and aerospace.

Claims

1. A polyamide composition comprising:

(A) Aliphatic polyamides;

(D) A polymer having an oxygen index of 27% or more and an aromatic group in the main chain, the oxygen index being measured according to ISO 4589-2, wherein,

the content of the polymer (D) is 0.1 to 8 mass% based on the total mass of the aliphatic polyamide (A), the semiaromatic polyamide (B), the phosphinate (C) and the polymer (D),

the content of the (C) phosphinate is 0.1% by mass or more and 30% by mass or less relative to the total mass of the (A) aliphatic polyamide, the (B) semiaromatic polyamide, the (C) phosphinate and the (D) polymer,

the content of the (B) semiaromatic polyamide in the polyamide composition is 5 to 50 mass% inclusive relative to the total mass of the polyamide in the polyamide composition,

The (B) semiaromatic polyamide contains at least 75 mol% of isophthalic acid units among all dicarboxylic acid units constituting the (B) semiaromatic polyamide,

in the general formula (1), R ¹¹ And R is ¹² Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; m is M ⁿ¹¹⁺ A metal ion of valence n 11; m is calcium, magnesium or aluminum; n11 is 2 or 3; in the case where n11 is 2 or 3, a plurality ofR ¹¹ And R is ¹² Each of which may be the same or different;

in the general formula (2), R ²¹ And R is ²² Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; y is Y ²¹ An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms; m's' ^m21+ A metal ion having a valence of m 21; m' is calcium, magnesium or aluminum; n21 is an integer of 1 to 3 inclusive; in the case where n21 is 2 or 3, a plurality of R's are present ²¹ 、R ²² And Y ²¹ Each of which may be the same or different; m21 is 2 or 3; x is 1 or 2; in the case where x is 2, a plurality of M's may be the same or different; n21, x, and m21 are integers satisfying a relation of 2×n21=m21×x.

2. The polyamide composition of claim 1 wherein the (D) polymer is polyphenylene sulfide, polyphenylene ether, or maleic anhydride modified polyphenylene ether.

3. The polyamide composition according to claim 1 or 2, wherein the (a) aliphatic polyamide contains diamine units and dicarboxylic acid units.

4. The polyamide composition according to claim 1 or 2, wherein the (a) aliphatic polyamide is polyamide 66.

5. A polyamide composition according to claim 3 wherein the (a) aliphatic polyamide is polyamide 66.

6. The polyamide composition according to any one of claims 1, 2 and 5, wherein the polyamide composition has a tan delta peak temperature of 90 ℃ or higher.

7. The polyamide composition according to claim 3, wherein the polyamide composition has a tan delta peak temperature of 90 ℃ or higher.

8. The polyamide composition as claimed in claim 4, wherein the polyamide composition has a tan delta peak temperature of 90℃or higher.

9. The polyamide composition according to any one of claims 1, 2, 5, and 7 to 8, wherein the (B) semiaromatic polyamide contains 100 mol% of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

10. The polyamide composition according to claim 3, wherein the (B) semiaromatic polyamide contains 100 mol% of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

11. The polyamide composition as claimed in claim 4, wherein said (B) semiaromatic polyamide contains 100 mol% of isophthalic acid units among all dicarboxylic acid units constituting said (B) semiaromatic polyamide.

12. The polyamide composition according to claim 6, wherein the (B) semiaromatic polyamide contains 100 mol% of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

13. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, wherein the polyamide composition has a weight average molecular weight of 10000 or more and 50000 or less.

14. The polyamide composition according to claim 3, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.

15. The polyamide composition as claimed in claim 4, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.

16. The polyamide composition according to claim 6, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.

17. The polyamide composition according to claim 9, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.

18. The polyamide composition of any one of claims 1, 2, 5, 7-8, 10-12, 14-17, wherein the polyamide composition further comprises at least one (E) filler material.

19. A polyamide composition according to claim 3 wherein the polyamide composition further comprises at least one (E) filler material.

20. The polyamide composition of claim 4 wherein the polyamide composition further comprises at least one (E) filler material.

21. The polyamide composition of claim 6 wherein the polyamide composition further comprises at least one (E) filler material.

22. The polyamide composition of claim 9 wherein the polyamide composition further comprises at least one (E) filler material.

23. The polyamide composition of claim 13 wherein the polyamide composition further comprises at least one (E) filler material.

24. A molded article obtained by molding the polyamide composition according to any one of claims 1 to 23.

25. A process for producing the polyamide composition according to any one of claims 1 to 23, wherein,

The raw material components comprising the (A) aliphatic polyamide, the (B) semiaromatic polyamide, the (C) phosphinate and the (D) polymer are melt kneaded.