CN116285337A - Polyamide composition, method for producing same, and molded article - Google Patents

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 that does not contain halogen, but is excellent in flame retardancy and has good long-term heat resistance when molded. A polyamide composition, which contains: (A) aliphatic polyamide; (B) semi-aromatic polyamide containing diamine units and dicarboxylic acid units; (C) selected from the group consisting of the following general formula (1 ) represented by phosphinates, diphosphinates represented by the following general formula (2) and their condensates constitute at least one phosphinate; and (D) the oxygen index is 27% The above polymer having an aromatic group on the main chain, wherein, with respect to the (A) aliphatic polyamide, the (B) semi-aromatic polyamide, and the (C) phosphinate The content of the (D) polymer is not less than 0.1% by mass and not more than 8% by mass based on the total mass of the (D) polymer.

Description

Polyamide composition, method for producing same, and molded article

This application is a divisional application of a Chinese patent application with an application date of September 24, 2019 and an application number of 201910903204.9.

technical field

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

Background technique

Compositions based on aliphatic polyamides have excellent properties and are therefore used in the manufacture of moldings in a wide variety of applications. Polyamide compositions having flame retardant properties are essential for building blocks in the electrical and electronics industry, especially in order to ensure proper fire protection.

Polyamides are often flame retardant treated by adding halogen compounds. However, recently, according to hazardous substance regulations such as RoHS (Restriction of Hazardous Substances Directive) and PoHS (Prohibition of Specific Hazardous Substances in Consumer Products), various regulations have been established so that products containing halogen-containing compounds are not used in electrical and electronic components. Therefore, various halogen-free flame retardants for polyamides have been developed.

As a non-halogen flame retardant, a phosphorus compound is mentioned, for example. Patent Document 1 discloses the use of calcium salts and aluminum salts of phosphinic acid or diphosphinic acid as a flame retardant for polyamides. A test piece with a test piece thickness of 1.2 mm manufactured from a polyamide composition containing these halogen-free flame retardants and reinforced with 30% by mass of glass fibers relative to the total mass of the composition achieved a flammability classification based on UL94 V-0.

In order to achieve the flammability classification V-0 of UL94, Patent Document 2 discloses that in a glass fiber-reinforced polyamide composition containing polyamide 6 as a main component, far more than 20% by mass is required relative to the total mass of the composition The amount of aluminum phosphinate; in the glass fiber reinforced polyamide composition with polyamide 66 as the main component, more than 30% by mass of aluminum phosphinate is required. It can be seen that, in order to achieve the flammability classification V-0 using a phosphinic acid-based flame retardant, it is necessary to add a large amount, and this has a problem of adversely affecting the mechanical properties.

Accordingly, Patent Document 3 discloses a polyamide composition based on a mixture of an aliphatic polyamide and a semiaromatic polyamide containing a phosphinate as a flame retardant. It is reported that by adding semi-aromatic polyamide, the amount of flame retardant used can be reduced and the tensile elongation can be improved.

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

prior art literature

patent documents

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 No. 2005-179362

Patent Document 6: Specification of European Patent Application Publication No. 699708

Patent Document 7: Japanese Patent Application Laid-Open No. 08-073720

Contents of the invention

The problem to be solved by the invention

However, although the polyamide composition described in Patent Document 3 improves the tensile elongation at break by reducing the amount of the flame retardant used, the flexural modulus under atmospheric equilibrium moisture absorption required for automobiles and various electrical parts , long-term heat resistance, etc. There is still room for improvement.

In addition, although the polyamide composition described in Patent Document 4 reduces the usage amount of the flame retardant and reduces outgassing by adding polyphenylene sulfide, it has the problem of increasing the amount of aliphatic polyamide relative to the aromatic polyamide. When the proportion of amide is low, it is difficult to maintain the flammability classification V-0 based on UL94. In addition, there is a particular concern about deterioration in CTI (comparative tracking index) required for electrical components.

Therefore, conventionally, no halogen-containing polyamide composition having excellent flame retardancy, tensile strength, flexural modulus of elasticity upon water absorption, and long-term heat resistance has been known.

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

means of solving problems

That is, the present invention includes the following aspects.

The polyamide composition according to the first aspect of the present invention, comprising:

(A) aliphatic polyamide;

(B) semi-aromatic polyamides 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 class; and

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

The (D) The content of the polymer is not less than 0.1% by mass and not more than 8% by mass,

(In general formula (1), R ¹¹ and R ¹² are each independently an alkyl group with 1 to 6 carbon atoms or an aryl group with 6 to 10 carbon atoms. ^{M n11+} is a metal ion with a valence of n11 .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, the plurality of R ¹¹ and R ¹² present are each Can be the same or different.

In the general formula (2), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. ^Y21 is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M' ^m21+ is a metal ion with m21 valence. 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. When n21 is 2 or 3, each of the plurality of R ²¹ , R ²² and Y ²¹ present may be the same or different. m21 is 2 or 3. x is 1 or 2. When x is 2, the plurality of M' that exist may be the same or different. n21, x and m21 are integers satisfying the relational expression of 2×n21=m21×x. )

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

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

The (A) aliphatic polyamide may be polyamide 66.

The (C) Content of phosphinic acid salts may be 0.1 mass % or more and 30 mass % or less.

The tan δ peak temperature of the polyamide composition may be 90° C. 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 isophthalic acid units in an amount of 75 mol % or more in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

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

The polyamide composition may have a weight average molecular weight of 10,000 or more and 50,000 or less.

The polyamide composition according to the first aspect may further contain at least one filler (E).

The molded article according to the second aspect of the present invention is obtained by molding the polyamide composition according to the above-mentioned first aspect.

The method for producing a polyamide composition according to a third aspect of the present invention is a method for producing the polyamide composition according to the above-mentioned first aspect, which comprises the above-mentioned (A) aliphatic polyamide, the above-mentioned (B ) A method of melt-kneading the raw material components of the semi-aromatic polyamide, the (C) phosphinates, and the (D) polymer.

Invention effect

According to the polyamide composition and its production method of the above aspect, a molded article having excellent flame retardancy and good long-term heat resistance can be obtained although no halogen is contained. The molded article of the above aspect does not contain halogen, and although it does not contain halogen, it has excellent flame retardancy and good long-term heat resistance.

Detailed ways

Hereinafter, a mode for implementing the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The present embodiment below is an example for explaining the present invention, and the present invention is not intended to be limited to the following contents, and the present invention can be implemented after being appropriately modified within the scope of the gist.

In addition, in this specification, "polyamide" means the polymer which has an amide group (-NHCO-) in a main chain.

"Polyamide composition"

The polyamide composition of this embodiment contains the following (A)-(D) components.

(A) aliphatic polyamide;

(B) semi-aromatic polyamides containing diamine units and dicarboxylic acid units;

(C) phosphinates;

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

In the polyamide composition of this embodiment, content of (D) component is 0.1 mass % or more and 8.0 mass % or less with respect to the total mass of (A)-(D) component.

The above-mentioned (C) phosphinates are selected from phosphinates represented by the following general formula (1) (hereinafter sometimes simply referred to as "phosphinate (1)"), and those represented by the following general formula (2). At least one phosphinic acid salt in the group which consists of a diphosphonate (it may abbreviate "a diphosphonate (2)" hereafter) and these condensates.

(In general formula (1), R ¹¹ and R ¹² are each independently an alkyl group with 1 to 6 carbon atoms or an aryl group with 6 to 10 carbon atoms. ^{M n11+} is a metal ion with a valence of n11 .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, the plurality of R ¹¹ and R ¹² present are each Can be the same or different.

In the general formula (2), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. ^Y21 is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M' ^m21+ is a metal ion with m21 valence. 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. When n21 is 2 or 3, each of the plurality of R ²¹ , R ²² and Y ²¹ present may be the same or different. m21 is 2 or 3. x is 1 or 2. When x is 2, the plurality of M' that exist may be the same or different. n21, x and m21 are integers satisfying the relational expression of 2×n21=m21×x).

The polyamide composition according to the present embodiment has the above-mentioned constitution, and it is possible to obtain a molded article that does not contain halogen, has excellent flame retardancy, tensile strength, flexural modulus of elasticity when absorbing water, and long-term heat resistance.

<Characteristics of polyamide composition>

The molecular weight and tan δ peak temperature of the polyamide composition according to the present embodiment can be set to the following configurations, and specifically, can be measured by the method described in Examples described later.

[Weight average molecular weight (Mw) of polyamide composition]

As an indicator of the molecular weight of the polyamide composition, weight average molecular weight (Mw) can be used.

The weight average molecular weight (Mw) of the polyamide composition is preferably 10,000 to 50,000, more preferably 17,000 to 45,000, still more preferably 20,000 to 45,000, still more preferably 25,000 to 45,000, particularly preferably 30,000 to 42,000, most preferably 35,000 to 40,000.

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

As a method of controlling the Mw of the polyamide composition within the above-mentioned range, for example, use (A) aliphatic polyamide, (B) semi-aromatic polyamide, and (D) a polymer whose Mw is within the range described below .

In addition, the measurement of Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography) as described in the Example mentioned later.

[tan δ peak temperature of polyamide composition]

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

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

That is, the tanδ peak temperature of the polyamide composition is 90°C or higher, preferably 105°C or higher and 150°C or lower, more preferably 110°C or higher and 140°C or lower, still more preferably 110°C or higher and 130°C or lower.

When the tan δ peak temperature of the polyamide composition is equal to or higher than the above 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 not more than the above-mentioned upper limit, a molded article obtained from a polyamide composition containing a component represented by (E) filler has a tensile strength and a water absorption temperature. Molded products tend to have better flexural modulus and long-term heat resistance.

As a method of controlling the tan δ peak temperature of the polyamide composition within the above-mentioned range, for example, a method of controlling the contents of (A) aliphatic polyamide and (B) semi-aromatic polyamide within the range described below can be mentioned.

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

<(A) Aliphatic polyamide>

(A) The structural unit of the aliphatic polyamide contained in the polyamide composition of this embodiment preferably satisfies at least one of the following conditions (1) and (2).

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

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

In the polyamide composition of the present embodiment, as (A) aliphatic polyamide, one or two or more polyamides satisfying at least one of the above-mentioned conditions (1) and (2) may be contained. Among them, it is particularly preferable that the constituent units of (A) aliphatic polyamide contained in the polyamide composition of the present embodiment satisfy the above (1).

[(A-a) Aliphatic dicarboxylic acid unit]

Examples of the aliphatic dicarboxylic acid constituting the (A-a) aliphatic dicarboxylic acid unit 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, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, diglycolic acid, etc.

The branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms is not limited to the following, for example, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3- Dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyl Adipic acid etc.

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

Among them, as the aliphatic dicarboxylic acid constituting the (A-a) aliphatic dicarboxylic acid unit, a straight-chain saturated aliphatic dicarboxylic acid having 6 or more carbon atoms is preferable because it has the heat resistance of the polyamide composition. Tendency to be more excellent in properties, fluidity, toughness, low water absorption and rigidity.

Examples of preferred straight-chain saturated aliphatic dicarboxylic acids having 6 or more carbon atoms include adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, and hexadecanedioic acid. Diacid, octadecanedioic acid, eicosanedioic acid, etc.

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

In addition, the (A) aliphatic polyamide may further contain a unit derived from a trivalent or higher polyhydric carboxylic acid as needed within a range that does not impair the effect of the polyamide composition of the present embodiment. As a trivalent or more polyvalent carboxylic acid, trimellitic acid, trimellitic acid, pyromellitic acid, etc. are mentioned, for example. These trivalent or higher polyhydric carboxylic acids may be used alone or in combination of two or more.

[(A-b) Aliphatic diamine unit]

Examples of the aliphatic diamine constituting the (A-b) aliphatic diamine unit include linear saturated aliphatic diamines having 2 to 20 carbon atoms and branched saturated aliphatic diamines having 3 to 20 carbon atoms. Chain saturated aliphatic diamines, etc.

The straight-chain saturated aliphatic diamine having 2 to 20 carbon atoms is not limited to the following, for example, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, Hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine , Thirteen methylene diamine, etc.

The branched saturated aliphatic diamines having 3 to 20 carbon atoms are not limited to the following, for example, 2-methylpentamethylenediamine (also called 2-methyl-1,5 -diaminopentane), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine Amine (also known as 2-methyloctamethylenediamine), 2,4-dimethyloctamethylenediamine, etc.

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

Among them, the number of carbon atoms of the aliphatic diamine constituting the (A-b) aliphatic diamine unit is preferably from 6 to 12, more preferably from 6 to 10. When the number of carbon atoms of the aliphatic diamine constituting the (A-b) aliphatic diamine unit is equal to or greater than the above lower limit, the heat resistance of the obtained molded article is more excellent. On the other hand, when this number of carbon atoms is below the said upper limit, the crystallinity and mold release property of the molded article obtained are more excellent.

Examples of preferred linear or branched saturated aliphatic diamines having 6 to 12 carbon atoms include, for example, hexamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-1,8-octanediamine, etc.

Among these, 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.

In addition, the (A) aliphatic polyamide may further contain a unit derived from a trivalent or higher aliphatic polyamine as needed within a range that does not impair the effect of the polyamide composition of the present embodiment. As a trivalent or more aliphatic polyamine, bis (hexamethylene) triamine etc. are mentioned, for example.

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

(A) The aliphatic polyamide may contain (A-c) at least one structural unit selected from the group consisting of lactam units and aminocarboxylic acid units. By containing such a unit, there exists a tendency for the polyamide excellent in toughness to be obtained.

In addition, the "lactam unit" and "aminocarboxylic acid unit" here refer to the polymerized (condensed) lactam and aminocarboxylic acid.

The lactam constituting the lactam unit is not limited to the following substances, for example, butyrolactam, valerolactam, ε-caprolactam, capryllactam, enantholactam, undecanolactam, laurolactam (laurolactam) amides) etc.

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

The aminocarboxylic acid constituting the aminocarboxylic acid unit is not limited to the following, and examples thereof include ω-aminocarboxylic acid, α,ω-amino acid, etc., which are compounds obtained by ring-opening a lactam.

The aminocarboxylic acid constituting the aminocarboxylic acid unit is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted by an amino group at the ω position. Such aminocarboxylic acids are not limited to the following, and examples thereof include 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Moreover, p-aminomethylbenzoic acid etc. are mentioned also as an aminocarboxylic acid.

These lactams and aminocarboxylic acids constituting at least one structural unit selected from the group consisting of lactam units and aminocarboxylic acid units (A-c) may be used alone or in combination of two or more.

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

The content of (A) aliphatic polyamide in the polyamide composition of the present embodiment can be set to, for example, 10% by mass or more and 100% by mass or less with respect to the total mass of the polyamide in the polyamide composition, for example, It is set to 50 mass % or more and 100 mass % or less, for example, can set it as 55 mass % or more and 100 mass % or less.

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

As an indicator of the molecular weight of (A) aliphatic polyamide, weight average molecular weight Mw(A) can be used. The weight average molecular weight Mw (A) of the aliphatic polyamide is preferably 10,000 to 50,000, more preferably 17,000 to 45,000, still more preferably 20,000 to 45,000, still more preferably 25,000 to 45,000, particularly preferably It is 30,000 to 45,000, most preferably 35,000 to 40,000.

When the weight-average molecular weight Mw (A) is within the above range, mechanical properties, especially water absorption rigidity, thermal rigidity, fluidity, tensile strength when molded, flexural modulus of water absorption and long-term durability can be obtained. A polyamide composition that is more excellent in heat resistance, etc.

In addition, the measurement of the weight average molecular weight Mw (A) can be measured using GPC as described in the following Example.

<(B) Semi-aromatic polyamide>

(B) The semi-aromatic polyamide contained in the polyamide composition of this embodiment is a polyamide containing a diamine unit and a dicarboxylic acid unit.

The (B) semiaromatic polyamide preferably contains 20 mol% to 80 mol% of aromatic structural units, more preferably 30 mol% to 70 mol% of all structural units of the (B) semiaromatic polyamide. % or less of aromatic structural units, more preferably 40 mol % or more and 60 mol % or less of aromatic structural units. Here, the "aromatic structural unit" means an aromatic diamine unit and an aromatic dicarboxylic acid unit.

In addition, the (B) semi-aromatic polyamide is preferably a polyamide containing (B-a) dicarboxylic acid units and (B-b) diamine units, and the total dicarboxylic acid units of (B) semi-aromatic polyamide , the (B-a) dicarboxylic acid unit contains 50 mol % or more of isophthalic acid units, and the (B-b) diamine unit contains a diamine unit having 4 or more and 10 or less carbon atoms.

In addition, at this time, the ratio of the isophthalic acid unit and the diamine unit having 4 to 10 carbon atoms in the (B) semiaromatic polyamide relative to all the constituent units of the (B) semiaromatic polyamide The total content 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, particularly preferably 100 mol %.

In addition, the ratio of the predetermined monomer unit which comprises (B) semi-aromatic polyamide can be measured by nuclear magnetic resonance spectroscopy (NMR) etc.

[(B-a) Dicarboxylic acid unit]

It does not specifically limit as (B-a) dicarboxylic acid unit, For example, an aromatic dicarboxylic acid unit, an aliphatic dicarboxylic acid unit, an alicyclic dicarboxylic acid unit etc. are mentioned.

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

(B-a) When the ratio of the isophthalic acid unit in the dicarboxylic acid unit is not less than the above-mentioned lower limit value, it is possible to obtain a polyamide composition capable of simultaneously satisfying mechanical properties, especially water absorption rigidity, thermal rigidity, fluidity, etc. Propensity. In addition, the molded article obtained from the polyamide composition tends to be more excellent in tensile strength, flexural modulus at the time of 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 or a naphthyl group. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or may have a substituent.

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 and its salt (sodium salt, etc.), and the like.

The alkyl group having 1 to 4 carbon atoms is not limited to the following groups, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

The aryl group having 6 to 10 carbon atoms is not limited to the following groups, and examples thereof include phenyl, naphthyl and the like.

The aralkyl group having 7 to 10 carbon atoms is not limited to the following groups, for example, benzyl group and the like are mentioned.

The alkylaryl group having 7 to 10 carbon atoms is not limited to the following groups, for example, tolyl, xylyl and the like can be mentioned.

The halogen group is not limited to the following groups, for example, a fluorine group, a chlorine group, a bromine group, an iodine group, etc. are mentioned.

The silyl group having 1 to 6 carbon atoms is not limited to the following groups, for example, a trimethylsilyl group, a tert-butyldimethylsilyl group, etc. are mentioned.

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 a specified An aromatic dicarboxylic acid having 8 to 20 carbon atoms substituted by a substituent.

As 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, specifically, it is not limited to the following: Substances, such as: terephthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, isophthalic acid-5-sulfonic acid Sodium etc.

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, and the like.

The linear saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms is not limited to the following, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, diglycolic acid, etc.

The branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms is not limited to the following, for example, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3- Dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyl Adipic acid etc.

(Cycloaliphatic 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, for example, carbon atoms of an alicyclic structure The alicyclic dicarboxylic acid whose number is 3 or more and 10 or less, etc. Among them, as the alicyclic dicarboxylic acid, an alicyclic dicarboxylic acid having 5 or more and 10 or less carbon atoms in the alicyclic structure is preferable.

Such alicyclic dicarboxylic acids are not limited to the following, for example, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, etc. . Among them, 1,4-cyclohexanedicarboxylic acid is preferable as the alicyclic dicarboxylic acid.

In addition, the alicyclic dicarboxylic acid which comprises an alicyclic dicarboxylic acid unit may be used individually by 1 type, and may use it in combination of 2 or more types.

The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms and the like. Examples of the alkyl group having 1 to 4 carbon atoms include the same groups as those exemplified in the above-mentioned "aromatic dicarboxylic acid unit".

As the dicarboxylic acid unit other than the isophthalic acid unit, it is preferable to contain an aromatic dicarboxylic acid unit, and it is more preferable to contain an aromatic dicarboxylic acid having 6 or more carbon atoms.

By using such a dicarboxylic acid, there is a tendency that a polyamide composition capable of simultaneously satisfying mechanical properties, especially water absorption rigidity, thermal rigidity, fluidity, and the like, can be obtained. In addition, the molded article obtained from the polyamide composition tends to be more excellent in tensile strength, flexural modulus at the time of water absorption, and long-term heat resistance.

(B) In the semi-aromatic polyamide, the dicarboxylic acid constituting the (B-a) dicarboxylic acid unit is not limited to the compounds described above as the dicarboxylic acid, and may be equivalent to the above dicarboxylic acid. compound.

The term "a compound equivalent to a dicarboxylic acid" as used herein refers to a compound capable of obtaining the same dicarboxylic acid structure as the dicarboxylic acid structure derived from the above-mentioned dicarboxylic acid. Such a compound is not limited to the following, For example, an acid anhydride of a dicarboxylic acid, an acid halide of a dicarboxylic acid, etc. are mentioned.

In addition, the (B) semi-aromatic polyamide may further contain a unit derived from a trivalent or higher polyhydric carboxylic acid as needed within the range not impairing the effect of the polyamide composition of the present embodiment.

As a trivalent or more polyvalent carboxylic acid, trimellitic acid, trimellitic acid, pyromellitic acid, etc. are mentioned, for example. These trivalent or higher polyhydric carboxylic acids may be used alone or in combination of two or more.

[(B-b) diamine unit]

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

(aliphatic diamine unit)

As an aliphatic diamine which comprises an aliphatic diamine unit, the linear saturated aliphatic diamine etc. which have 4-20 carbon atoms are mentioned, for example.

The straight-chain saturated aliphatic diamine having 4 to 20 carbon atoms is not limited to the following, for example, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, Hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine , Thirteen methylene diamine, etc.

(Cycloaliphatic diamine unit)

The alicyclic diamine (hereinafter sometimes referred to as "alicyclic diamine") constituting the alicyclic diamine unit is not limited to the following, for example, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine, etc.

(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. As an aromatic diamine, m-xylylenediamine etc. are mentioned specifically, for example.

In addition, the diamine which comprises each of these diamine units may be used individually by 1 type, and may use it in combination of 2 or more types.

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, and still more preferably 6 to 10 carbon atoms. straight-chain saturated aliphatic diamine units, particularly preferably hexamethylenediamine units.

By using such a diamine, there is a tendency to obtain a polyamide composition capable of simultaneously satisfying mechanical properties, especially water absorption rigidity, thermal rigidity, fluidity, and the like. In addition, the molded article obtained from the polyamide composition tends to be more excellent in tensile strength, flexural modulus at the time of water absorption, and long-term heat resistance.

As the (B) semi-aromatic polyamide contained in the polyamide composition of the present embodiment, polyamide 6I (polyhexamethylene isophthalamide), polyamide 9I or polyamide 10I is preferable, and more Polyamide 6I is preferred. Polyamide 6I is excellent in heat resistance, moldability, and flame retardancy, and thus is considered to be a material suitable for automotive parts.

The content of (B) semi-aromatic polyamide in the polyamide composition of the present embodiment can be set to 5 mass % or more and 90 mass % or less with respect to the total mass of the polyamide in the polyamide composition, preferably 10% by mass to 50% by mass, more preferably 15.0% by mass to 40% by mass, still more preferably 20% by mass to 45% by mass.

By setting the content of (B) semi-aromatic polyamide within the above-mentioned range, the mechanical properties of the molded article obtained from the polyamide composition are more excellent. In addition, by containing components typified by (E) filler, the molded article obtained from the polyamide composition tends to be more excellent in tensile strength, flexural modulus of elasticity when absorbing water, and long-term heat resistance.

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

As an index of the molecular weight of (B) semi-aromatic polyamide, weight average molecular weight Mw(B) can be used. The weight average molecular weight Mw (B) of the semi-aromatic polyamide is preferably 10,000 to 50,000, more preferably 15,000 to 45,000, still more preferably 15,000 to 40,000, still more preferably 17,000 to 30,000, especially Preferably it is 17,000 or more and 25,000 or less, most preferably 18,000 or more and 22,000 or less.

When the weight-average molecular weight Mw (B) is within the above range, mechanical properties, especially water absorption rigidity, thermal rigidity, fluidity, tensile strength when molded, flexural modulus of water absorption and long-term durability can be obtained. A polyamide composition that is more excellent in heat resistance, etc.

In addition, the measurement of the weight average molecular weight Mw(B) can be measured using GPC as described in the following Example.

<Blocking agent>

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

When producing a polyamide from the above-mentioned dicarboxylic acid and the above-mentioned diamine, or producing a polyamide from at least one selected from the group consisting of the above-mentioned lactam and the above-mentioned aminocarboxylic acid, such an end-blocking agent can be used as a molecular weight regulator. agent added.

The blocking agent is not limited to the following, and examples thereof include monocarboxylic acids, monoamines, acid anhydrides (phthalic anhydride, etc.), monoisocyanates, monoesters, monoalcohols, and the like. As the terminal blocking agent, only one kind may be used alone, or two or more kinds may be used in combination.

Among these, monocarboxylic acids or monoamines are preferable as the terminal blocking agent. By capping the terminal of the polyamide with a capping agent, the thermal stability of the molded article obtained from the polyamide composition tends to be more excellent.

As the monocarboxylic acid which can be used as an end-blocking agent, what is necessary is just what has reactivity with the amino group which may exist in the polyamide terminal. The monocarboxylic acid is not limited to the following, and examples thereof include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids.

Examples of aliphatic monocarboxylic acids 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, and pivalic acid. , isobutyric acid, etc.

As alicyclic monocarboxylic acid, cyclohexanecarboxylic acid etc. are mentioned, for example.

Examples of the aromatic monocarboxylic acid include benzoic acid, toluic acid, α-naphthoic acid, β-naphthoic acid, methylnaphthoic acid, and phenylacetic acid.

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

In particular, it is preferable that the terminal of the (B) semi-aromatic polyamide is blocked with acetic acid from the viewpoint of fluidity and mechanical strength.

As the monoamine that can be used as an end-blocking agent, any one may be used as long as it has reactivity with a carboxyl group that may be present at a polyamide terminal. The monoamine is not limited to the following, and examples thereof include aliphatic monoamines, alicyclic monoamines, and aromatic monoamines.

Examples of aliphatic monoamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine.

As alicyclic monoamine, cyclohexylamine, dicyclohexylamine, etc. are mentioned, for example.

As aromatic monoamine, aniline, toluidine, diphenylamine, naphthylamine etc. are mentioned, for example.

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

A polyamide composition containing a polyamide capped with a capping agent tends to be more excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.

<Method for producing (A) aliphatic polyamide and (B) semiaromatic polyamide>

When producing the polyamide ((A) aliphatic polyamide and (B) semiaromatic polyamide) contained in the polyamide composition of this embodiment, the addition amount of dicarboxylic acid and the addition amount of diamine It is preferably about the same molar amount. Regarding the molar ratio, the molar amount of all diamines relative to the molar amount of all dicarboxylic acids is preferably 0.9 or more and 1.2 in consideration of the escape of diamines in the polymerization reaction to the outside of the reaction system. or less, more preferably 0.95 or more and 1.1 or less, still more preferably 0.98 or more and 1.05 or less.

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

(1) A step of obtaining a polymer by polymerizing a combination of a dicarboxylic acid constituting a dicarboxylic acid unit and a diamine constituting a diamine unit.

(2) A step of polymerizing one or more selected from the group consisting of a lactam constituting a lactam unit and an aminocarboxylic acid constituting an aminocarboxylic acid unit to obtain a polymer.

In addition, the method for producing polyamide preferably further includes an increasing step of increasing the degree of polymerization of polyamide after the above-mentioned polymerization step. In addition, after the above-mentioned polymerization step and the above-mentioned raising step, a capping step of capping the terminal of the obtained polymer with a capping agent may be included as needed.

As a specific production method of polyamide, various methods as exemplified in the following 1)-4) are mentioned, for example.

1) heating an aqueous solution or an aqueous suspension of at least one selected from the group consisting of dicarboxylic acid-diamine salts, mixtures of dicarboxylic acids and diamines, lactams and aminocarboxylic acids, and A method of polymerizing while maintaining a molten state (hereinafter, may be referred to as "hot melt polymerization method").

2) A method of increasing the degree of polymerization of polyamide obtained by hot melt polymerization while maintaining a solid state at a temperature below the melting point (hereinafter sometimes referred to as "hot melt polymerization and solid phase polymerization").

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

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

Among them, as a specific production method of polyamide, a production method including a hot-melt polymerization method is preferable. In addition, when polyamide is produced by hot-melt polymerization, it is preferable to keep the molten state until the polymerization is completed. In order to maintain a molten state, it is necessary to perform production under polymerization conditions suitable for the polyamide composition. As polymerization conditions, the conditions etc. which are shown below are mentioned, for example. First, the polymerization pressure in the hot melt polymerization method is controlled at 14 kg/cm ² or more and 25 kg/cm ² or less (gauge pressure), and heating is continued. Next, the pressure was reduced over 30 minutes or more until the pressure in the tank reached atmospheric pressure (gauge pressure: 0 kg/cm ² ).

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

The polymerization apparatus used for the production of polyamide is not particularly limited, and known apparatuses can be used. As a polymerization apparatus, concretely, an autoclave type reactor, a drum type reactor, an extruder type reactor (kneader etc.) etc. are mentioned, for example.

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

First, a raw material component (a combination of a dicarboxylic acid and a diamine, and if necessary, at least a) in aqueous solution. Next, in a concentration tank operated at a temperature of 110° C. to 180° C. and a pressure of about 0.035 MPa to 0.6 MPa (gauge pressure), the aqueous solution is concentrated to about 65% by mass to about 90% by mass. % or less to obtain a concentrated solution.

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

Next, in the autoclave, while removing at least any one of water and gas components, the pressure is kept at about 1.2 MPa or more and about 2.2 MPa or less (gauge pressure). Next, when the temperature reaches approximately 220° C. to approximately 260° C., the pressure is lowered to atmospheric pressure (gauge pressure: 0 MPa). By reducing the pressure in the autoclave to atmospheric pressure and then reducing the pressure as necessary, by-produced water can be efficiently 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 to obtain polyamide pellets.

<Polymer end of polyamide>

The polymer terminal of the polyamide ((A) aliphatic polyamide and (B) semiaromatic polyamide) contained in the polyamide composition of the present embodiment is not particularly limited, and can be classified and defined as the following 1 )~4).

That is, 1) the amino terminal, 2) the carboxyl terminal, 3) the terminal formed by the blocking agent, and 4) the other terminal.

1) The amino terminal is a polymer terminal with an amino group (-NH ₂ group), derived from a diamine.

2) The carboxyl terminal is a polymer terminal having a carboxyl group (-COOH group), derived from a dicarboxylic acid.

3) The terminal formed by the blocking agent is the terminal formed when the blocking agent is added during polymerization. Examples of the terminal blocking agent include the above-mentioned terminal blocking agents.

4) Other terminals are polymer terminals that are not classified into the above-mentioned 1) to 3). Specific examples of other terminals include terminals produced by deamination reaction at the amino terminal, terminals produced by decarboxylation reaction from the carboxyl terminal, and the like.

<(C) Phosphinates>

The (C) phosphinates contained in the polyamide composition of this embodiment are selected from phosphinates represented by the following general formula (1) (phosphinate (1)), the following At least one kind of phosphinates in the group consisting of the bisphosphonate represented by the general formula (2) (diphosphonate (2)) and their condensates.

(In general formula (1), R ¹¹ and R ¹² are each independently an alkyl group with 1 to 6 carbon atoms or an aryl group with 6 to 10 carbon atoms. ^{M n11+} is a metal ion with a valence of n11 .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, the plurality of R ¹¹ and R ¹² present are each Can be the same or different.

In the general formula (2), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. ^Y21 is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M' ^m21+ is a metal ion with m21 valence. 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. When n21 is 2 or 3, each of the plurality of R ²¹ , R ²² and Y ²¹ present may be the same or different. m21 is 2 or 3. x is 1 or 2. When x is 2, the plurality of M' that exist may be the same or different. n21, x and m21 are integers satisfying the relational expression of 2×n21=m21×x).

[R ¹¹ , R ¹² , R ²¹ and R ²² ]

R ¹¹ , R ¹² , R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. When n11 is 2 or 3, the plurality of R ¹¹ and R ¹² present may be the same or different, but are preferably the same from the viewpoint of ease of manufacture. In addition, when n21 is 2 or 3, the plurality of ^R21 and ^R22 that exist may be the same or different, but are preferably the same from the viewpoint of ease of manufacture.

The alkyl group may be a chain or a ring, but is preferably a chain. The chain alkyl group may be a linear alkyl group or a branched chain alkyl group. Examples of straight-chain alkyl groups include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, n-pentyl groups, and n-hexyl groups. Examples of branched alkyl groups include: 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 1-methylbutyl, 2- Methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-methylpentyl, 2 -Methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2- Trimethylpropyl etc.

As an aryl group, a phenyl group, a naphthyl group etc. are mentioned, for example.

An alkyl group and an aryl group may have a substituent. As a substituent on an alkyl group, an aryl group etc. which have 6 to 10 carbon atoms are mentioned, for example. Examples of the substituent on the aryl group include an alkyl group having 1 to 6 carbon atoms, and the like.

As an alkyl group which has a substituent, a benzyl group etc. are mentioned specifically, for example.

As an aryl group which has a substituent, concretely, a tolyl group, a xylyl group, etc. are mentioned, for example.

Among them, R ¹¹ , R ¹² , R ²¹ and R ²² are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.

[Y ²¹ ]

^Y21 is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. When n21 is 2 or 3, each of the plurality ^{of Y21} that exists may be the same or different, but they are preferably the same from the viewpoint of ease of manufacture.

The alkylene group may be a chain or a ring, but is preferably a chain. The chained alkylene group may be a straight chain alkylene group or a branched chain alkylene group. As a linear alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group etc. are mentioned, for example. As a branched alkylene group, a 1-methylethylene group, a 1-methylpropylene group, etc. are mentioned, for example.

As an arylene group, a phenylene group, a naphthylene group etc. are mentioned, for example.

The alkylene group and the arylene group may have a substituent. As a substituent on an alkylene group, an aryl group etc. which have 6 to 10 carbon atoms are mentioned, for example. Examples of the substituent on the arylene group include an alkyl group having 1 to 6 carbon atoms, and the like.

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

Specific examples of the arylene group having a substituent include: methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butyl Kynaphthyl and others.

Among them, Y ²¹ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably a methylene group or an ethylene group.

[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 ions of elements belonging to Group 2 of the periodic table include calcium ions, magnesium ions, and the like. Examples of ions of elements belonging to Group 15 of the periodic table include bismuth ions and the like.

In addition, when x is 2, each of the plurality of M' existing may be the same or different, but they are preferably the same from the viewpoint of ease of manufacture.

Among them, M and M' are preferably calcium, zinc or aluminum, more preferably calcium or aluminum.

[x]

x represents the number of M', which is 1 or 2. x can be appropriately selected according to the type of M' and the amount of diphosphonic acid.

[n11 and n21]

n11 represents the number of phosphinic acid and the valence of M, and n11 is 2 or 3. n11 can be appropriately selected according to the type and valence of M.

n21 represents the number of objects of diphosphonic acid, and n21 is an integer of 1 or more and 3 or less. n21 can be appropriately selected according to the type and number of M'.

[m21]

m21 represents the valence of M', and m21 is 2 or 3.

n21, x and m21 are integers satisfying the relational expression of 2×n21=m21×x.

Specific examples of preferred phosphinates (1) include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate , calcium methylethylphosphinate, magnesium methylethylphosphinate, aluminum methylethylphosphinate, zinc methylethylphosphinate, calcium diethylphosphinate, diethylphosphinate Magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, formazan Zinc n-propylphosphinate, calcium methanebis(methylphosphinate), magnesium methanebis(methylphosphinate), aluminum methanebis(methylphosphinate), methanebis(methylphosphinate) ) zinc, benzene-1,4-(dimethylphosphinate) calcium, benzene-1,4-(dimethylphosphinate) magnesium, benzene-1,4-(dimethylphosphinate) aluminum , Benzene-1,4-(dimethylphosphinate) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, methylphenylphosphinate Zinc acid, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate, etc. Among them, calcium dimethylphosphinate or aluminum dimethylphosphinate are particularly preferred as the phosphinate (1) from the viewpoint of being excellent in flame retardancy.

As preferable bisphosphonate (2), specifically, for example, methane bis(methyl phosphinate) calcium, methane bis(methyl phosphinate) magnesium, methane bis(methyl phosphinate) ) aluminum, methane bis(methylphosphinate) zinc, benzene-1,4-bis(methylphosphinate) calcium, benzene-1,4-bis(methylphosphinate) magnesium, benzene-1, 4-bis(methylphosphinate)aluminum, benzene-1,4-bis(methylphosphinate)zinc, etc.

Although it does not specifically limit as a manufacturing method of phosphinic acid salt, For example, the method of patent document 5, patent document 6, patent document 7 etc. are mentioned. Specifically, it is produced in an aqueous solution using phosphinic acid and metal carbonates, metal hydroxides, or metal oxides. These phosphinates are essentially monomeric compounds, but polymeric phosphinates that are condensates having a degree of condensation of 1 to 3 may also be included depending on reaction conditions and environments.

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

By making content of (C) phosphinic acid salts more than the said lower limit, the polyamide composition more excellent in flame retardancy can be obtained. On the other hand, by setting the content of (C) phosphinic acid salts to be equal to or less than the upper limit, it is possible to obtain a polyamide composition having more excellent flame retardancy without impairing the properties of the polyamide copolymer.

<(D) A polymer having an oxygen index of 27% or more and having an aromatic group on the main chain>

The (D) polymer 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 ether, maleic anhydride-modified polyphenylene ether, polysulfone, polyetheretherketone, polyetherimide, and polyamide. imide, polyethersulfone, etc. Among them, as (D) polymer, polyphenylene sulfide, polyphenylene ether, maleic anhydride-modified polyphenylene ether, or polysulfone is preferable, and polyphenylene sulfide, polyphenylene ether, or maleic anhydride-modified Polyphenylene ether.

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

The content of (D) polymer is 0.1% by mass or more based on the total mass of (A) aliphatic polyamide, (B) semi-aromatic polyamide, (C) phosphinates, and (D) polymer, 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.

By making content of (D) polymer more than the said lower limit, the polyamide composition more excellent in flame retardancy can be obtained. On the other hand, by making content of (D) polymer into the said upper limit or less, the polyamide composition which is more excellent in long-term heat resistance can be obtained.

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

[(D) Weight average molecular weight Mw(D) of polymer]

(D) The weight average molecular weight Mw(D) can be used as an indicator of the molecular weight of a polymer. (D) The weight average molecular weight Mw(D) of the polymer is preferably 10,000 to 70,000, more preferably 15,000 to 60,000, still more preferably 20,000 to 60,000, still more preferably 25,000 to 60,000, especially Preferably it is 25,000 or more and 55,000 or less, most preferably 30,000 or more and 55,000 or less.

When the weight-average molecular weight Mw (D) is within the above range, mechanical properties, especially water absorption rigidity, thermal rigidity, fluidity, tensile strength when molded, flexural modulus of water absorption and long-term durability can be obtained. A polyamide composition that is more excellent in heat resistance, etc.

In addition, the measurement of the weight average molecular weight Mw (D) can be measured using GPC as described in the following Example.

<(E)Filling material>

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

The (E) filler contained in the polyamide composition of this embodiment is not particularly limited, and examples thereof include glass fibers, carbon fibers, calcium silicate fibers, potassium titanate fibers, aluminum borate fibers, glass flakes, Talc, kaolin, mica, hydrotalcite, zinc carbonate, calcium monohydrogen 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, swelling fluoromica, apatite, etc.

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

Among them, the (E) filler is preferably glass fiber, carbon fiber, glass flakes, talc, kaolin, mica, calcium monohydrogen phosphate, wollastonite, carbon nanotubes, graphite, fluoride, etc., from the viewpoint of rigidity and strength. Calcium, montmorillonite, swelling fluoromica or apatite. Moreover, as (E) filler, glass fiber or carbon fiber is more preferable, and glass fiber is still more preferable.

When the (E) filler is glass fiber or carbon fiber, the number average fiber diameter (D) is preferably 3 μm or more and 30 μm or less. In addition, the weight average fiber length (L) is preferably not less than 100 μm and not more than 750 μm. In addition, the aspect ratio ((L)/(D)) of the weight-average fiber length (L) to the number-average fiber diameter (D) is preferably 10 or more and 100 or less. Higher characteristics can be exhibited by using glass fiber or carbon fiber having the above-mentioned constitution.

Moreover, when (E) filler is a glass fiber, it is more preferable that a number average fiber diameter (D) is 3 micrometers or more and 30 micrometers or less. The weight average fiber length (L) is more preferably 103 μm or more and 500 μm or less. In addition, the aspect ratio ((L)/(D)) is more preferably 3 or more and 100 or less.

(E) The number average fiber diameter and weight average fiber length of a filler can be measured using the following method.

First, the molded article of the polyamide composition is dissolved in a solvent capable of dissolving polyamide such as formic acid. Next, from the obtained insoluble components, for example, 100 or more fillers are arbitrarily selected. Next, it can be determined by observing the filler 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 to 80% by mass, more preferably 10% by mass to 70% by mass, and even more preferably It is 15 mass % or more and 60 mass % or less, Especially preferably, it is 20 mass % or more and 50 mass % or less, Most preferably, it is 25 mass % or more and 40 mass % or less.

When the content of the (E) filler is equal to or greater than the above lower limit, the polyamide composition tends to have further improved mechanical properties such as strength and rigidity. On the other hand, when content of (E) filler is below the said upper limit, there exists a tendency for the polyamide composition more excellent in moldability to be obtained.

In particular, the (E) filler is glass fiber, and the content of the (E) filler is within the above range with respect to the total mass of the polyamide composition, thereby having further mechanical properties such as strength and rigidity of the polyamide composition. tendency to increase.

<(F)Other additives>

In the polyamide composition of the present embodiment, in addition to the above-mentioned components (A) to (E), (F) commonly used in polyamides may be contained within the range that does not impair the effect of the polyamide composition of the present embodiment. other additives. Examples of (F) other additives include (F1) moldability improvers, (F2) deterioration inhibitors, (F3) nucleating agents, (F4) heat stabilizers, and the like.

The content of (F) other additives in the polyamide composition of the present embodiment varies depending on the type, the use of the polyamide composition, etc., so as long as the effect of the polyamide composition of the present embodiment is not impaired, There is no special restriction.

[(F1) Formability Improver]

The moldability improving agent (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, and higher fatty acid amides. In addition, the formability improver is also used as a "lubricating material".

(higher fatty acid)

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

Examples of straight-chain saturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms include lauric acid, palmitic acid, stearic acid, behenic acid, and montanic acid.

Examples of branched saturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms include isopalmitic acid and isostearic acid.

Examples of straight-chain unsaturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms include oleic acid and erucic acid.

Examples of the branched unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include vaccinal 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 elements, Group 2 elements, and Group 3 elements of the periodic table, zinc, aluminum, and the like.

Examples of Group 1 elements of the periodic table include sodium, potassium, and the like.

As a group 2 element of the periodic table of elements, calcium, magnesium, etc. are mentioned, for example.

Examples of Group 3 elements of the periodic table include scandium, yttrium, and the like.

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

Specific examples of higher fatty acid metal salts include calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, and calcium palmitate.

Among these, the higher fatty acid metal salt is preferably a montanic acid metal salt or a stearic acid metal salt.

(higher fatty acid ester)

Higher fatty acid ester refers to the esterification of higher fatty acid and 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 higher fatty acid esters include stearyl stearate, behenyl behenate, and the like.

(higher fatty acid amide)

The higher fatty acid amide refers to an amide compound of a higher fatty acid.

Examples of higher fatty acid amides include: stearamide, oleamide, erucamide, ethylene bisstearamide, ethylene bisoleamide, N-stearyl stearamide, N-stearyl erucamide wait.

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) Deterioration Inhibitor]

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

The (F2) deterioration inhibitor is not particularly limited, and examples thereof include copper compounds, phenolic stabilizers, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, and benzotriazole stabilizers , Benzophenone stabilizers, cyanoacrylate stabilizers, salicylate stabilizers, sulfur stabilizers, etc.

As a copper compound, copper acetate, cuprous iodide, etc. are mentioned, for example.

As a phenolic stabilizer, a hindered phenol compound etc. are mentioned, for example.

These (F2) deterioration inhibitors may be used alone or in combination of two or more.

[(F3) Nucleating agent]

(F3) A nucleating agent is a substance which acquires at least any one effect among the following (1)-(3) by addition.

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

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

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

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

(F3) Nucleating agents may be used alone or in combination of two or more.

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

In addition, 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 a nucleating agent can be measured using the following method. First, the molded article is dissolved in a solvent capable of dissolving polyamide such as formic acid. Next, for example, 100 or more nucleating agents are arbitrarily selected from the obtained insoluble components. Next, it can be obtained by observing and measuring the particle diameter with 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 relative to 100 parts by mass of the polyamide ((A) aliphatic polyamide and (B) semiaromatic polyamide). Part or less, More preferably, it is 0.001 mass part or more and 0.5 mass part or less, More preferably, it is 0.001 mass part or more and 0.09 mass part or less.

By setting the content of the nucleating agent to 100 parts by mass of the polyamide or more, the heat resistance of the polyamide composition tends to be further improved, and by setting the content of the nucleating agent to 100 parts by mass of the polyamide By setting the part below the above-mentioned upper limit, a polyamide composition more excellent in toughness can be obtained.

[(F4) heat stabilizer]

As (F4) heat stabilizer, it is not limited to the following substances, for example, it can be enumerated: phenolic heat stabilizer, phosphorus heat stabilizer, amine heat stabilizer, the 3rd group, the 4th group and the 11th to 11th group of the periodic table. Metal salts of Group 14 elements, etc.

(phenolic heat stabilizer)

The phenolic heat stabilizer is not limited to the following, and examples thereof include hindered phenol compounds and the like. Hindered phenol compounds have the property 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 substances, for example, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropanamide) , Pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxy Hydrogenated cinnamamide), 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-hydroxybenzylphosphonate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy benzyl)benzene, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, etc.

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

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

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 generated can be further reduced.

(Phosphorus-containing heat stabilizer)

As the phosphorus-containing heat stabilizer, it is not limited to the following substances, for example, it can be listed: pentaerythritol type phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl phosphite di Phenyl ester, triisodecyl phosphite, diisodecyl phenyl phosphite, bis(tridecyl) phenyl phosphite, diphenyl isooctyl phosphite, phosphorous acid Diphenyl isodecyl ester, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-diphosphite) tert-butylphenyl) ester, tris(2,4-di-tert-butyl-5-methylphenyl) phosphite, tris(butoxyethyl) phosphite, 4,4'-diphosphite Butylene bis(3-methyl-6-tert-butylphenyl) ester-tetra(tridecyl) ester, diphosphite 4,4'-isopropylidene diphenyl ester-tetra(C12～C15 Mixed alkyl) esters, 4,4'-isopropylidenebis(2-tert-butylphenyl)-bis(nonylphenyl)phosphite, tris(biphenyl)phosphite, 1, 1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite tetrakis(tridecyl)ester, 4,4'-butylene bis( 3-methyl-6-tert-butylphenyl) ester-tetra(tridecyl) ester, diphosphite 4,4'-isopropylidene diphenyl ester-tetra(C1～C15 mixed alkyl) Ester, tris(mono-, di-mixed nonylphenyl) phosphite, 4,4'-isopropylidene bis(2-tert-butylphenyl)-bis(nonylphenyl)phosphite, 9 ,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'- Isopropylidene diphenyl polyphosphite, bis(4,4'-butylene bis(3-methyl-6-tert-butylphenyl))-1,6-hexanol diphosphite bis( Octylphenyl) ester, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane diphosphite hexa(tridecyl)ester, triphosphite (4,4'-isopropylidene bis(2-tert-butylphenyl)) ester, tris(1,3-stearyloxyisopropyl) phosphite, 2,2-methylene phosphite Bis(4,6-di-tert-butylphenyl) octyl ester, 2,2-methylene bis(3-methyl-4,6-di-tert-butylphenyl) phosphite 2-ethyl Hexyl ester, 4,4'-diphenylene diphosphite tetrakis(2,4-di-tert-butyl-5-methylphenyl) ester, 4,4'-diphenylene diphosphite tetrakis(2, 4-di-tert-butylphenyl) ester, etc.

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 substances, for example: 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 Phosphite 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-methyl phenyl phenyl ester-benzyl ester, pentaerythritol diphosphite 2,6-di-tert-butyl-4-methylphenyl ester-ethyl cellosolve ester, pentaerythritol diphosphite 2,6-di-tert-butyl 2,6-di-tert-butyl-4-methylphenyl-octylphenyl ester, pentaerythritol diphosphite 2,6-di-tert-butyl-4-methylphenyl ester-nonylphenyl ester, pentaerythritol diphosphite bis(2,6-di-tert-butyl-4-methylphenyl) ester, pentaerythritol diphosphite Phosphite bis(2,6-di-tert-butyl-4-ethylphenyl) ester, pentaerythritol diphosphite 2,6-di-tert-butyl-4-methylphenyl ester-2,6-di tert-butylphenyl ester, pentaerythritol diphosphite 2,6-di-tert-butyl-4-methylphenyl ester-2,4-di-tert-butylphenyl ester, 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-cyclo Hexyl phenyl ester, pentaerythritol diphosphite 2,6-di-tert-amyl-4-methylphenyl ester-phenyl ester, pentaerythritol diphosphite bis(2,6-di-tert-amyl-4-methyl phenyl) ester, pentaerythritol diphosphite bis(2,6-di-tert-octyl-4-methylphenyl) ester, etc.

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

In the case of using a phosphorus-containing heat stabilizer, the content of the phosphorus-containing heat stabilizer in the polyamide composition is preferably 0.01% by mass to 1% by mass, more preferably 0.05% by mass, relative to the total mass of the polyamide composition. Mass % or more and 1 mass % or less.

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)

As the amine heat stabilizer, it is not limited to the following substances, for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6, 6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2,2,6,6-tetramethyl Piperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyl Oxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6, 6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-tetramethyl Basepiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-2,2,6,6- Tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) oxalate ester, bis(2,2,6,6-tetramethyl-4-piperidinyl) malonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate ester, bis(2,2,6,6-tetramethyl-4-piperidinyl) adipate, bis(2,2,6,6-tetramethyl-4-piperidinyl) terephthalate ) ester, 1,2-bis(2,2,6,6-tetramethyl-4-piperidinyloxy)ethane, α,α'-bis(2,2,6,6-tetramethyl- 4-piperidinyloxy) p-xylene, bis(2,2,6,6-tetramethyl-4-piperidinyl) toluene-2,4-dicarbamate, hexamethylene-1,6 -Dicarbamic acid bis(2,2,6,6-tetramethyl-4-piperidinyl) ester, benzene-1,3,5-tricarboxylic acid tris(2,2,6,6-tetramethyl- 4-piperidinyl) ester, benzene-1,3,4-tricarboxylic acid tris(2,2,6,6-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]- 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β,β, β', β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5.5)undecane]diethanol condensate, etc.

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

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

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 Group 3, Group 4, and Groups 11 to 14 of the Periodic Table of Elements)

Metal salts of 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 these, 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, for example, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate , copper stearate, copper complex salt obtained by coordination of copper and chelating agent.

As a chelating agent, ethylenediamine, ethylenediaminetetraacetic acid, etc. are mentioned, for example.

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

Among them, copper acetate is preferable as the copper salt. When copper acetate is used, it is possible to obtain a polyamide composition that is more excellent in heat aging resistance and can more effectively suppress metal corrosion of the screw or barrel portion during extrusion (hereinafter sometimes simply referred to as "metal corrosion") .

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

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 metal corrosion can be more effectively suppressed.

In addition, from the viewpoint of improving the heat aging resistance of the polyamide composition, with respect to polyamide ((A) aliphatic polyamide and (B) semiaromatic polyamide) 10 ⁶ mass parts (1 million mass parts), The content concentration of the copper element derived from the copper salt is preferably 10 to 2000 parts by mass, more preferably 30 to 1500 parts by mass, further preferably 50 to 500 parts by mass.

The components of the heat stabilizer (F4) described above may be used alone or in combination of two or more.

"Manufacturing method of polyamide composition"

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

As a mixing method of each component of said (A)-(D) and each component of (E) and (F) as needed, the method of following (1) or (2), etc. are mentioned, for example.

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

(2) Each component of (A) to (D) and (E) component if necessary are mixed in advance using a Henschel mixer etc. to prepare each component containing (A) to (D) and ( F) A method of supplying and kneading the mixture of the ingredients to a melt kneader, and optionally compounding the (E) ingredient with a single-screw or twin-screw extruder from a side feeder.

Regarding the method of supplying the components constituting the polyamide composition to the melt-kneader, all the constituent components may be supplied at one time from the same supply port, or the constituent components may be supplied from different supply ports.

The temperature for melt kneading is preferably about 1°C to about 100°C higher than the melting point of (A) aliphatic polyamide, more preferably about 10°C to about 50°C higher than the melting point of (A) aliphatic polyamide below temperature.

The shear rate in the kneader is preferably about 100 sec ^{-1 or} more. In addition, the average residence time during kneading is preferably not less than about 0.5 minutes and not more than about 5 minutes.

As an 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.) and the like are preferably used.

The compounding quantity of each component when manufacturing the polyamide composition of this embodiment is the same as content of each component in the above-mentioned polyamide composition.

"Molded Products"

The molded article of this embodiment is obtained by molding the polyamide composition of the above-mentioned embodiment.

The molded article of this embodiment does not contain halogen, is excellent in flame retardancy, and has good tensile strength, flexural modulus of elasticity when absorbing water, and long-term heat resistance.

The method of obtaining a molded product is not particularly limited, and known molding methods can be used.

Examples of known molding methods include extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, heterogeneous material molding, gas-assisted injection molding, foam injection molding, low-pressure molding, ultra- Thin-wall injection molding (ultra-high-speed injection molding), in-mold composite molding (insert molding, insert-on-molding), etc.

<purpose>

The molded article of this embodiment contains the polyamide composition of the above-mentioned embodiment, has excellent flame retardancy and mechanical properties (particularly, flexural modulus of elasticity when absorbing water and long-term heat resistance), and can be used in various applications.

As applications of the molded article of the present embodiment, for example, it can be suitably used in the automotive field, electrical and electronic fields, mechanical and industrial fields, office equipment fields, and aviation and spaceflight fields.

[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.

Hereinafter, each constituent component of the polyamide composition used in this Example and a comparative example is demonstrated.

<Constituents>

[(A) Aliphatic polyamide]

A-1: Polyamide 66

A-2: polyamide 6 (manufactured by Ube Industries, model: SF1013A, molecular weight: 33000)

[(B) Semi-aromatic polyamide]

B-1: Polyamide 6I

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

B-3: Polyamide MXD6 (made in Toyobo Co., Ltd., brand name: Toyobo nylon, T-600)

[(C) Phosphinates]

C-1: Phosphinate-based flame retardant aluminum diethylphosphinate (manufactured by Clariant, trade name: "Exolit OP1230")

C-2: Phosphinic acid flame retardant calcium diethylphosphinate (manufactured by Taiping Chemical Industry Co., Ltd.)

[(C') Flame retardants other than phosphinates]

C'-1: Nitrogen-containing flame retardant melamine cyanurate (manufactured by Nissan Chemical Industries, Ltd.)

C'-2: Nitrogen- and phosphorus-containing flame retardant cyclic phenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd.)

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

D-1: polyphenylene sulfide (PPS) (manufactured by DIC Corporation) (oxygen index: 46%, molecular weight: 30000)

D-2: Maleic anhydride-modified polyphenylene ether (m-PPE) (manufactured by Asahi Kasei Corporation) (oxygen index: 28%, molecular weight: 54000)

D-3: polyphenylene ether (PPE) (manufactured by Asahi Kasei Co., Ltd.) (oxygen index: 28%, molecular weight: 30000)

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

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

D'-1: polycarbonate (PC) (manufactured by Teijin Corporation) (oxygen index: 25%, molecular weight: 40000)

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

In addition, the oxygen index of the said (D) polymer and the said (D') polymer was measured based on ISO 4589-2.

[(E) filling material]

E-1: Glass fiber (GF) (manufactured by NEC Glass, trade name: "ECS03T275H", average fiber diameter: 10 μmφ, cut length: 3 mm)

[(F) Other additives]

F-1: Phenolic heat stabilizer (manufactured by Ciba Specialty Chemicals, trade name "Irganox 1098")

<Manufacture of polyamide>

The respective production methods of the aliphatic polyamide A-1 and the semiaromatic polyamide B-1 will be described in detail below. It should be noted that the aliphatic polyamide A-1 and semi-aromatic polyamide B-1 obtained by the following production method were dried in a nitrogen stream to adjust the water content to about 0.2% by mass, and then used as The raw materials of the polyamide compositions in Examples and Comparative Examples were used.

[Synthesis Example 1] Synthesis of Aliphatic Polyamide A-1 (Polyamide 66)

The polymerization reaction of polyamide was implemented by the "hot-melt polymerization method" as follows.

First, 1,500 g of an equimolar salt of adipic acid and hexamethylenediamine was dissolved in 1,500 g of distilled water to prepare an equimolar 50 mass % homogeneous aqueous solution of the raw material monomers. This aqueous solution was poured into an autoclave having an internal volume of 5.4 L, and replaced with nitrogen. Next, while stirring at a temperature of about 110° C. to about 150° C., water vapor was slowly discharged to concentrate to a solution concentration of 70% by mass. Next, the internal temperature was raised to 220°C. At this time, the pressure of the autoclave was increased to 1.8 MPa. This state was maintained for 1 hour until the internal temperature reached 245° C., and the reaction was carried out for 1 hour while slowly discharging water vapor while maintaining the pressure at 1.8 MPa. Next, the pressure was reduced for 1 hour. Next, the inside of the autoclave was kept under a reduced pressure of 650 Torr (86.66 kPa) for 10 minutes using a vacuum device. At this time, the final internal temperature of the polymerization was 265°C. Next, it pressurizes with nitrogen gas, forms a strand form from a lower spinneret (nozzle), performs water cooling, cuts, and discharges in pellet form. Next, the pellets were dried at 100° C. under a nitrogen atmosphere for 12 hours to obtain aliphatic polyamide A-1 (polyamide 66).

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

[Synthesis Example 2] Synthesis of Semiaromatic Polyamide B-1 (Polyamide 6I)

Polyamide polymerization was carried out by the "hot melt polymerization method" as described above.

First, 1,500 g of an equimolar salt of isophthalic acid and hexamethylenediamine, and 1.5 mol% of adipic acid in excess relative to the entire equimolar salt component, and 0.5 mol% of acetic acid were dissolved in 1,500 g of distilled water, thereby An equimolar 50% by mass homogeneous aqueous solution of the raw material monomers was prepared. Next, while stirring at a temperature of about 110° C. to about 150° C., water vapor was slowly discharged to concentrate to a solution concentration of 70% by mass. Next, the internal temperature was raised to 220°C. At this time, the pressure of the autoclave was increased to 1.8 MPa. This state was maintained for 1 hour until the internal temperature reached 245° C., and the reaction was carried out for 1 hour while slowly discharging water vapor while maintaining the pressure at 1.8 MPa. Next, reduce the pressure for 30 minutes. Next, the inside of the autoclave was kept under a reduced pressure of 650 Torr (86.66 kPa) for 10 minutes using a vacuum device. At this time, the final internal temperature of the polymerization was 265°C. Next, pressurizing with nitrogen gas forms strands from the lower spinneret (nozzle), water-cools, cuts, and discharges in the form of pellets. Next, the pellets were dried at 100° C. under a nitrogen atmosphere for 12 hours to obtain a semi-aromatic polyamide B-1 (polyamide 6I).

The obtained semi-aromatic polyamide B-1 (polyamide 6I) had a content of isophthalic acid units in dicarboxylic acid units of 100 mol%. Mw=20000.

<Physical properties and evaluation>

First, the pellets of the polyamide compositions obtained in Examples and Comparative Examples were dried in a nitrogen stream to adjust the water content in the polyamide compositions to 500 ppm or less. Next, various physical property measurements and various evaluations were carried out by the following methods using the pellets of each polyamide composition whose water content was adjusted.

[Physical properties 1] tanδ peak temperature

Using a PS40E injection molding machine manufactured by Nissei Kogyo Co., Ltd., set the cylinder temperature to 290°C, set the mold temperature to 100°C, and conform to JIS-K7139 under the injection molding conditions of 10 seconds of injection time and 10 seconds of cooling time. Formed into moldings. The molded article was measured under the following conditions using a dynamic viscoelasticity evaluation device (manufactured by GABO Corporation, EPLEXOR500N).

(measurement conditions)

Measurement Mode: Tensile

Measurement frequency: 8.00Hz

Heating rate: 3°C/min

Temperature range: -100℃～250℃

Let the ratio (E2/E1) of the loss elastic modulus E2 and the storage elastic modulus E1 be tan δ, and let the highest temperature be tan δ peak temperature.

[Physical properties 2] Molecular weight (Mw) of polyamide composition

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

(measurement conditions)

Measuring device: Tosoh Corporation make, HLC-8020

Solvent: Hexafluoroisopropanol solvent

Standard sample: PMMA (polymethyl methacrylate) (manufactured by Polymer Laboratory Co., Ltd.) conversion

GPC column: TSK-GEL GMHHR-M and G1000HHR

[Evaluation 1] Flame retardancy

Measurement was performed using the method of UL94 (the standard established by Underwriters Laboratories, Inc.). It should be noted that the test piece (127 mm in length, 12.7 mm in width, and 1.6 mm in thickness) was produced by installing a mold for the UL test piece on an injection molding machine (PS40E manufactured by Nissei Industries, Ltd.) (mold temperature = 100°C), each polyamide composition was molded at a cylinder temperature of 290°C. Regarding the injection pressure, it was performed at a pressure of +2% of the full filling pressure at the time of molding the UL test piece. According to the UL94 standard (vertical burning test), evaluate whether the flame retardancy level is equivalent to any one of V-0, V-1, and V-2. It should be noted that the smaller the numerical value of the grade, the higher the flame retardancy.

[Evaluation 2] Tensile strength

Each polyamide composition was molded into a molded piece of multi-purpose test piece A type according to ISO 3167 using an injection molding machine "PS-40E: manufactured by Nissei Plastics Co., Ltd." The specific molding conditions are: set the injection + holding time to 25 seconds, set the cooling time to 15 seconds, set the mold temperature to 80°C, and set the molten resin temperature to the melting temperature of the high temperature side of the polyamide. Peak temperature (Tm2) +20°C.

Using the obtained molded piece of multipurpose test piece A type, a tensile test was performed at a temperature of 23° C. at a pulling speed of 5 mm/min in accordance with ISO 527, and the tensile yield stress was measured as the tensile strength.

[Evaluation 3] Flexural modulus of elasticity when absorbing water

An ISO dumbbell-shaped test piece having a thickness of 4 mm was produced as a test piece. Using the obtained test piece, the flexural modulus was measured according to ISO178. In addition, the ISO dumbbell-shaped test piece was placed in a constant temperature and constant humidity (23°C, 50RH%) atmosphere, and after reaching water absorption equilibrium, the flexural modulus was measured according to ISO 178.

[Evaluation 4] Long-term heat resistance

The multipurpose test piece (type A) in the above-mentioned tensile strength was heated at 150° C. in a hot-air circulation oven to perform thermal aging.

After being placed in the oven for 1000 hours, it was taken out from the oven, and cooled at 23° C. for 24 hours or more. Next, the cooled multipurpose test piece (type A) was subjected to a tensile test according to ISO 527 at a pulling speed of 5 mm/min by the same method as the above method, and each tensile strength was measured. The heat aging retention rate was calculated|required using the following formula.

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

[Evaluation 5] Leakage Resistance

A test piece having a thickness of 30 mm×30 mm and a thickness of 4 mm was prepared, and CTI was measured in accordance with IEC60112. In addition, the voltage application was performed in units of 50V.

Based on the relative tracking index (TI) obtained, the grades were assigned as follows.

(classification)

CTI Level 0: 600≤TI

CTI Level 1: 400≤TI＜600

CTI Level 2: 250≤TI＜400

CTI Level 3: 175≤TI＜250

CTI Level 4: 100≤TI＜175

CTI Level 5: 0≤TI＜100

[Example 1] Production of polyamide composition P-1a

(A) Aliphatic polyamide A- 1 and a mixture of (B) semi-aromatic polyamide B-1, (D) polymer D-1 and (F) other additive F-1. In addition, (C) Flame Retardant C-1 and (E) Filler E-1 were supplied from a side feed port on the downstream side of the extruder (in a state where the resin supplied from the top feed port was sufficiently melted). Next, the melt-kneaded product extruded from the die was cooled in a strand form and pelletized to obtain pellets of polyamide composition P-1a. The compounding quantity was set as (A) aliphatic polyamide A-1: 46.0 mass%, (B) semi-aromatic polyamide B-1: 11.6 mass%, (C) flame retardant C-1: 16.0 mass%, (D) Polymer D-1: 1.0% by mass, (E) Filler E-1: 25.0% by mass, and (F) Other additives F-1: 0.1% by mass.

[Example 2] Production of polyamide composition P-2a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 45.2% by mass, (B) semi-aromatic polyamide B-1: 11.4% by mass, and (D) polymer D-1: 2.0% by mass Except that, pellets of polyamide composition P-2a were obtained by the same method as in Example 1.

[Example 3] Production of polyamide composition P-3a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 44.4% by mass, (B) semi-aromatic polyamide B-1: 11.2% by mass, and (D) polymer D-1: 3.0% by mass Except that, pellets of polyamide composition P-3a were obtained by the same method as in Example 1.

[Example 4] Production of polyamide composition P-4a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 43.6 mass%, (B) semi-aromatic polyamide B-1: 11.0 mass%, and (D) polymer D-1: 4.0 mass% Except that, pellets of polyamide composition P-4a were obtained by the same method as in Example 1.

[Example 5] Production of polyamide composition P-5a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 46.2 mass%, (B) semi-aromatic polyamide B-1: 11.6 mass%, and (D) polymer D-2: 1.0 mass% Except that, pellets of polyamide composition P-5a were obtained by the same method as in Example 1.

[Example 6] Production of polyamide composition P-6a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 44.6% by mass, (B) semi-aromatic polyamide B-1: 11.2% by mass, and (D) polymer D-2: 3.0% by mass Except that, pellets of polyamide composition P-6a were obtained by the same method as in Example 1.

[Example 7] Production of polyamide composition P-7a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 42.8% by mass, (B) semiaromatic polyamide B-1: 10.8% by mass, and (D) polymer D-2: 5.0% by mass Except that, pellets of polyamide composition P-7a were obtained by the same method as in Example 1.

[Example 8] Production of polyamide composition P-8a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 40.0% by mass, (B) semi-aromatic polyamide B-1: 10.0% by mass, and (D) polymer D-2: 5.7% by mass Except that, pellets of polyamide composition P-8a were obtained by the same method as in Example 1.

[Example 9] Production of polyamide composition P-9a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 44.4% by mass, (B) semi-aromatic polyamide B-1: 11.2% by mass, and (D) polymer D-3: 3.0% by mass Except that, pellets of polyamide composition P-9a were obtained by the same method as in Example 1.

[Example 10] Production of polyamide composition P-10a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 44.4% by mass, (B) semi-aromatic polyamide B-1: 11.2% by mass, and (D) polymer D-4: 3.0% by mass Except that, pellets of polyamide composition P-10a were obtained by the same method as in Example 1.

[Example 11] Production of polyamide composition P-11a

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

[Example 12] Production of polyamide composition P-12a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 42.8% by mass, (B) semiaromatic polyamide B-2: 10.8% by mass, and (D) polymer D-2: 5.0% by mass Except that, pellets of polyamide composition P-12a were obtained by the same method as in Example 1.

[Example 13] Production of polyamide composition P-13a

Except for changing the compounding amount to (A) aliphatic polyamide A-2: 45.2% by mass, (B) semiaromatic polyamide B-1: 11.4% by mass, and (D) polymer D-1: 2.0% by mass Except that, pellets of polyamide composition P-13a were obtained by the same method as in Example 1.

[Example 14] Production of polyamide composition P-14a

Except for changing the compounding amount to (A) aliphatic polyamide A-2: 42.8 mass%, (B) semi-aromatic polyamide B-1: 10.8 mass%, and (D) polymer D-2: 5.0 mass% Except that, pellets of polyamide composition P-14a were obtained by the same method as in Example 1.

[Example 15] Production of polyamide composition P-15a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 48.2 mass%, (B) semi-aromatic polyamide B-1: 5.4 mass%, and (D) polymer D-2: 5.0 mass% Except that, pellets of polyamide composition P-15a were obtained by the same method as in Example 1.

[Example 16] Production of polyamide composition P-16a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 37.5% by mass, (B) semi-aromatic polyamide B-1: 16.1% by mass, and (D) polymer D-2: 5.0% by mass Except that, pellets of polyamide composition P-16a were obtained by the same method as in Example 1.

[Example 17] Production of polyamide composition P-17a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 32.2% by mass, (B) semi-aromatic polyamide B-1: 21.4% by mass, and (D) polymer D-2: 5.0% by mass Except that, pellets of polyamide composition P-17a were obtained by the same method as in Example 1.

[Example 18] Production of polyamide composition P-18a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 29.4% by mass, (B) semi-aromatic polyamide B-1: 7.4% by mass, (C) phosphinate C-1: 9.0 Except mass %, (D) polymer D-2: 3.8 mass %, and (E) filler: 50 mass %, the pellet of polyamide composition P-18a was obtained by the method similar to Example 1.

[Example 19] Production of polyamide composition P-19a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 22.2% by mass, (B) semi-aromatic polyamide B-1: 14.6% by mass, (C) phosphinate C-1: 9.0 Except mass %, (D) polymer D-2: 3.8 mass %, and (E) filler: 50.0 mass %, the pellet of polyamide composition P-19a was obtained by the method similar to Example 1.

[Example 20] Production of polyamide composition P-20a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 39.6 mass%, (B) semi-aromatic polyamide B-1: 10.0 mass%, (C) phosphinate C-2: 20.0 Mass %, (D) Polymer D-2: Except 5.0 mass %, the pellet of polyamide composition P-20a was obtained by the method similar to Example 1.

[Example 21] Production of polyamide composition P-21a

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 7.0% by mass, (B) semiaromatic polyamide B-3: 46.6% by mass, (C) phosphinate C-1: 16.0% Mass %, (D) Polymer D-2: except 5.0 mass %, the pellet of polyamide composition P-21a was obtained by the method similar to Example 1.

[Comparative Example 1] Production of Polyamide Composition P-1b

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 46.8% by mass, (B) semi-aromatic polyamide B-1: 11.8% by mass, and (D) polymer D-1: 0% by mass Except that, pellets of polyamide composition P-1b were obtained in the same manner as in Example 1.

[Comparative Example 2] Production of Polyamide Composition P-2b

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 46.8% by mass, (B) semi-aromatic polyamide B-2: 11.8% by mass, and (D) polymer D-1: 0% by mass Except that, pellets of polyamide composition P-2b were obtained in the same manner as in Example 1.

[Comparative Example 3] Production of Polyamide Composition P-3b

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 41.7% by mass, (B) semi-aromatic polyamide B-1: 10.4% by mass, and (D) polymer D-1: 6.5% by mass Except that, pellets of polyamide composition P-3b were obtained in the same manner as in Example 1.

[Comparative Example 4] Production of polyamide composition P-4b

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 41.7 mass%, (B) semi-aromatic polyamide B-1: 10.4 mass%, and (D) polymer D-2: 6.5 mass% Except that, pellets of polyamide composition P-4b were obtained by the same method as in Example 1.

[Comparative Example 5] Production of polyamide composition P-5b

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 42.8% by mass, (B) semi-aromatic polyamide B-1: 10.8% by mass, and (D') polymer D'-1: 5.0 Except mass %, the pellet of polyamide composition P-5b was obtained by the same method as Example 1.

[Comparative Example 6] Production of polyamide composition P-6b

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 42.8% by mass, (B) semi-aromatic polyamide B-1: 10.8% by mass, and (D') polymer D'-2: 5.0 Except mass %, the pellet of polyamide composition P-6b was obtained by the same method as Example 1.

[Comparative Example 7] Production of polyamide composition P-7b

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 24.3% by mass, (B) semiaromatic polyamide B-1: 16.3% by mass, (C) phosphinate C-1: 9.0 Mass % and (D) Polymer D-1: Except 0 mass %, the pellet of the polyamide composition P-7b was obtained by the method similar to Example 1.

[Comparative Example 8] Production of Polyamide Composition P-8b

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 42.8% by mass, (B) semiaromatic polyamide B-1: 10.8% by mass, (C') barriers other than phosphinates Except fuel C'-1: 16.0 mass %, and (D) polymer D-2: 5.0 mass %, the pellet of polyamide composition P-8b was obtained by the method similar to Example 1.

[Comparative Example 9] Production of Polyamide Composition P-9b

Except for changing the compounding amount to (A) aliphatic polyamide A-1: 42.8% by mass, (B) semiaromatic polyamide B-1: 10.8% by mass, (C') barriers other than phosphinates Except fuel C'-2: 16.0 mass %, and (D) polymer D-2: 5.0 mass %, the pellet of polyamide composition P-9b was obtained by the method similar to Example 1.

In addition, molded articles were produced by the above-mentioned method using the obtained 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 4

table 5

From Tables 1 to 3, it can be seen that by containing (A) aliphatic polyamide, (B) semi-aromatic polyamide, (C) phosphinates and (D) polymer, and relative to (A) to (D The total mass of the components (D) of the molded articles obtained from the polyamide compositions P-1a to P-21a (Examples 1 to 21) in which the content of the (D) polymer is in the range of 0.1% by mass to 8.0% by mass It is excellent in flame retardancy, and is excellent in tensile strength, flexural modulus of elasticity when absorbing water, and long-term heat resistance.

In addition, in the polyamide compositions P-3a, P-6a, P-9a and P-10a (Examples 3, 6, 9 and 10) containing different kinds of (D) polymers, by containing D-1 , D-2 and D-3 polyamide compositions P-3a, P-6a and P-9a (Examples 3, 6 and 9) obtained moldings and polyamide compositions containing D-4 P- Compared with the molded article obtained in 10a (Example 10), the tensile strength and long-term heat resistance were particularly good.

Also, in polyamide compositions P-2a and P-11a (Examples 2 and 11) and P-7a and P-12a (Examples 7 and 12) containing different kinds of (B) semiaromatic polyamides , the molded articles obtained from the polyamide compositions P-2a and P-7a (Examples 2 and 7) containing B-1 and the molded articles obtained from the polyamide compositions (Examples 11 and 12) containing B-2 Compared with other products, the tensile strength and flexural modulus of elasticity when absorbing water are particularly good.

In addition, in 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, The moldings obtained from the polyamide compositions P-2a and P-7a (Examples 2 and 7) containing A-1 were the same as those obtained from the polyamide compositions P-13a and P-14a containing A-2 (Example 13 Compared with the molded article obtained in 14), the tensile strength and the flexural modulus of elasticity at the time of water absorption are particularly good.

In addition, among the polyamide compositions P-8a and P-20a (Examples 8 and 20) containing different kinds of (C) phosphinates, the polyamide composition P-8a containing C-1 ( Example 8) The molded article obtained from the polyamide composition P-20a (Example 20) containing C-2 was particularly good in tensile strength and flexural modulus of elasticity when absorbing water.

On the other hand, as can be seen from Tables 4 to 5, the resistance of the molded articles obtained from the polyamide compositions P-1b, P-2b, and P-7b (Comparative Examples 1, 2, and 7) not containing the (D) polymer Flammability, flexural modulus of elasticity when absorbing water, and long-term heat resistance are poor.

In addition, moldings obtained from the polyamide compositions P-3b and P-4b (Comparative Examples 3 and 4) in which the content of the (D) polymer was greater than 8.0% by mass relative to the total mass of the components (A) to (D) The flame retardancy and leakage resistance of the product are poor.

In addition, the content of the (D') polymer relative to the total mass of the components (A) to (D') is 0.1% by mass to 8.0% by mass, but the oxygen content index is less than 27% and there is no The flame retardancy of the molded article obtained from polyamide composition P-5b (Comparative Example 5) having an aromatic group (D') polymer was poor.

In addition, the content of the (D') polymer relative to the total mass of the (A) to (D') components is 0.1% by mass or more and 8.0% by mass or less, but contains polymers that do not have an aromatic group on the main chain. (D') The polyamide composition P-6b (Comparative Example 6) of the polymer obtained was inferior in flexural modulus of elasticity when absorbing water, long-term heat resistance, and leakage resistance.

In addition, the polyamide composition P containing nitrogen-containing flame retardant C'-1 as (C') a flame retardant that does not contain halogen elements other than phosphinates instead of (C) phosphinates -8b (comparative example 8), and replace (C) phosphinate by containing nitrogen and phosphorus flame retardant C'-2 as (C') flame retardant that does not contain halogen elements except phosphinates The flame retardancy, tensile strength, and flexural modulus of elasticity of the molded article obtained from the salt-based polyamide composition P-9b (Comparative Example 9) were poor, and the molded article obtained from the polyamide composition P-9b (Comparative Example 9) The obtained molded article was also poor in leakage resistance.

From the above, it can be seen that according to the polyamide composition of the present embodiment, a molded article containing no halogen, excellent in flame retardancy, tensile strength, flexural modulus of elasticity when absorbing water, and long-term heat resistance can be obtained.

[Industrial Applicability]

According to the polyamide composition of the present embodiment, a molded article having excellent flame retardancy and excellent long-term heat resistance can be obtained although no halogen is contained. The molded article of the present embodiment can be suitably used in the automotive field, electrical and electronic fields, mechanical and industrial fields, office equipment fields, and aviation and spaceflight fields.

Claims (27)

1. A polyamide composition comprising:

(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% 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 (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 50 mol% or more of isophthalic acid units among all dicarboxylic acid units constituting the (B) semiaromatic polyamide,

the polymer (D) is polyphenylene sulfide or maleic anhydride modified polyphenyl ether,

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 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 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, the plurality M's present may be the sameMay be different; n21, x, and m21 are integers satisfying a relation of 2×n21=m21×x.

2. The polyamide composition according to claim 1, wherein the (A) aliphatic polyamide comprises diamine units and dicarboxylic acid units.

3. The polyamide composition of claim 1 wherein the (a) aliphatic polyamide is polyamide 66.

4. The polyamide composition of claim 2 wherein the (a) aliphatic polyamide is polyamide 66.

5. The polyamide composition according to any one of claims 1 to 4, wherein 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.

6. The polyamide composition according to any one of claims 1 to 4, wherein the polyamide composition has a tan delta peak temperature of 90 ℃ or higher.

7. The polyamide composition according to claim 5, wherein the polyamide composition has a tan delta peak temperature of 90℃or higher.

8. The polyamide composition according to any one of claims 1 to 4 and 7, wherein the (B) semiaromatic polyamide contains 75 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

9. The polyamide composition according to claim 5, wherein the (B) semiaromatic polyamide contains 75 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

10. The polyamide composition according to claim 6, wherein the (B) semiaromatic polyamide contains 75 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

11. The polyamide composition according to any one of claims 1 to 4, 7, 9 and 10, wherein the (B) semiaromatic polyamide contains 100 mol% of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

12. The polyamide composition according to claim 5, 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 claim 6, wherein the (B) semiaromatic polyamide contains 100 mol% of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

14. The polyamide composition according to claim 8, wherein the (B) semiaromatic polyamide contains 100 mol% of isophthalic acid units in all dicarboxylic acid units constituting the (B) semiaromatic polyamide.

15. The polyamide composition according to any one of claims 1 to 4, 7, 9, 10, 12 to 14, wherein the polyamide composition has a weight average molecular weight of 10000 or more and 50000 or less.

16. The polyamide composition according to claim 5, 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 6, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.

18. The polyamide composition according to claim 8, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.

19. The polyamide composition according to claim 11, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.

20. The polyamide composition of any one of claims 1-4, 7, 9, 10, 12-14, 16-19, wherein the polyamide composition further comprises at least one (E) filler material.

21. The polyamide composition of claim 5 wherein the polyamide composition further comprises at least one (E) filler material.

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

23. The polyamide composition of claim 8 wherein the polyamide composition further comprises at least one (E) filler material.

24. The polyamide composition of claim 11 wherein the polyamide composition further comprises at least one (E) filler material.

25. The polyamide composition of claim 15 wherein the polyamide composition further comprises at least one (E) filler material.

26. A molded article obtained by molding the polyamide composition according to any one of claims 1 to 25.

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

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