JP5042263B2 - Polyamide composition - Google Patents

Description

  The present invention relates to a polyamide composition, a molded article comprising the polyamide composition, and electrical and electronic parts.

  Polyamides represented by polyamide 6 and polyamide 66 (hereinafter sometimes abbreviated as “PA6” and “PA66”, respectively) and the like are excellent in molding processability, mechanical properties or chemical resistance. Polyamides are widely used as various component materials for automobiles, machine industries, electric and electronic, industrial materials, industrial materials, daily products, and household products.

In the automobile industry, as an environmental measure, there is a demand for reducing the weight of the vehicle body by replacing metal in order to reduce exhaust gas. In order to meet these requirements, polyamides are increasingly used for exterior materials and interior materials, and the level of required properties such as heat resistance, strength, and appearance for polyamide materials is further improved. Above all, since the temperature in the engine room is also increasing, there is an increasing demand for higher heat resistance for the polyamide material.
Further, in the electrical and electronic industries such as home appliances, in order to cope with the lead-free surface mount (SMT) solder, it is required to increase the heat resistance of the polyamide material that can withstand the rise in melting point of the solder.
Polyamides such as PA6 and PA66 have a low melting point and cannot satisfy these requirements in terms of heat resistance.

In order to solve the above problems of conventional polyamides such as PA6 and PA66, high melting point polyamides have been proposed. Specifically, a polyamide composed of terephthalic acid and hexamethylenediamine (hereinafter sometimes abbreviated as “PA6T”) has been proposed.
However, since PA6T is a high-melting-point polyamide having a melting point of about 370 ° C., even if an attempt is made to obtain a molded product by melt molding, the polyamide undergoes severe thermal decomposition, making it difficult to obtain a molded product having sufficient characteristics.

  In order to solve the above-mentioned problems of PA6T, PA6T may be abbreviated as aliphatic polyamide such as PA6 and PA66 or amorphous aromatic polyamide (hereinafter referred to as “PA6I”) composed of isophthalic acid and hexamethylenediamine. ) And the like, and a high melting point semi-aromatic polyamide mainly composed of terephthalic acid and hexamethylenediamine (hereinafter referred to as “6T copolymer polyamide”) whose melting point is lowered to about 220 to 340 ° C. Have been proposed).

  As a 6T copolymer polyamide, Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as “a mixture of hexamethylene diamine and 2-methylpentamethylene diamine”), which is composed of an aromatic dicarboxylic acid and an aliphatic diamine. May be abbreviated as “PA6T / 2MPDT”).

  Further, in contrast to an aromatic polyamide composed of an aromatic dicarboxylic acid and an aliphatic diamine, a high melting point aliphatic polyamide composed of adipic acid and tetramethylene diamine (hereinafter sometimes abbreviated as “PA46”) or an alicyclic ring. An alicyclic polyamide composed of an aliphatic dicarboxylic acid and an aliphatic diamine has been proposed.

Patent Documents 2 and 3 disclose semialicyclic polyamides of alicyclic polyamides (hereinafter sometimes referred to as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and other polyamides. (Hereinafter, it may be abbreviated as “PA6C copolymer polyamide”).
Patent Document 2 discloses that the heat and heat resistance of semi-alicyclic polyamide blended with 1 to 40% of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit is improved in solder heat resistance. Is disclosed that the automobile parts are excellent in fluidity and toughness.

Furthermore, Patent Document 4 discloses that a polyamide comprising a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine is light resistance, toughness, moldability, lightness, And excellent heat resistance and the like. In addition, as a method for producing the polyamide, 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine are reacted at 230 ° C. or less to form a prepolymer, and the prepolymer is solid-phase polymerized at 230 ° C. to have a melting point of 311 ° C. The production of polyamides is disclosed.
In Patent Document 5, a polyamide using 1,4-cyclohexanedicarboxylic acid having a trans / cis ratio of 50/50 to 97/3 as a raw material is excellent in heat resistance, low water absorption, light resistance, and the like. It is disclosed.

JP-T 6-503590 Japanese National Patent Publication No. 11-512476 Special table 2001-514695 gazette Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 Pamphlet

  Although the 6T copolymer polyamide certainly has the characteristics of low water absorption, high heat resistance, and high chemical resistance, it has low flowability and insufficient moldability and molded product surface appearance. Inferior in light resistance. Therefore, the appearance of a molded product such as an exterior part is required, or improvement is desired in applications where it is exposed to sunlight or the like. In addition, the specific gravity is large, and improvement in lightness is also desired.

  The PA6T / 2MPDT disclosed in Patent Document 1 can partially improve the problems of the conventional PA6T copolymer polyamide, but in terms of fluidity, moldability, toughness, molded product surface appearance, and light resistance. The level of improvement is insufficient.

  PA46 has good heat resistance and moldability, but has a high water absorption rate, and has a problem that dimensional change due to water absorption and deterioration of mechanical properties are remarkably large. Dimensional change required for automotive applications, etc. There are cases where the demand cannot be met.

The PA6C copolymer polyamides disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity. The polyamides disclosed in Patent Documents 4 and 5 also have toughness, rigidity, and fluidity. In terms of sex, the improvement is insufficient.

  The problem to be solved by the present invention is to provide a polyamide composition that is excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, and flame retardancy.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have as main constituents an alicyclic dicarboxylic acid and a diamine having a substituent branched from the main chain, a polyamide, and a halogen flame retardant. And the present invention has been completed.

That is, the present invention is as follows.
(1)
(A) (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) at least 50 mol% of a diamine containing a diamine having a substituent branched from the main chain were polymerized. Polyamide,
(B) A polyamide composition containing a halogen-based flame retardant.
(2)
The polyamide composition according to (1), wherein the diamine having a substituent branched from the main chain is 2-methylpentamethylenediamine.
(3)
The polyamide composition according to (1) or (2), wherein the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.
(4)
The polyamide composition according to any one of (1) to (3), wherein the dicarboxylic acid further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms.
(5)
The polyamide composition according to any one of (1) to (4), wherein the (A) polyamide is a polyamide obtained by further copolymerizing (c) a lactam and / or an aminocarboxylic acid.
(6)
The polyamide composition according to any one of (1) to (5), wherein the polyamide (A) has a melting point of 270 to 350 ° C.
(7)
The polyamide composition according to any one of (1) to (6), wherein the trans isomer ratio in the (A) polyamide is 50 to 85%.
(8)
(A) Polyamide composition in any one of (1)-(7) containing 30-60 mass parts of said (B) halogenated flame retardants with respect to 100 mass parts of polyamides.
(9)
The polyamide composition according to any one of (1) to (8), wherein the (B) halogen flame retardant is brominated polystyrene.
(10)
(B) 30 to 60 parts by mass of the halogen-based flame retardant, (C) 0 to 30 parts by mass of a flame retardant aid, and (D) an α, β unsaturated dicarboxylic acid anhydride relative to 100 parts by mass of the (A) polyamide. The polyamide composition according to any one of (1) to (9), comprising 0 to 20 parts by mass of a polymer containing a product and (E) 0 to 200 parts by mass of an inorganic filler.
(11)
The polyamide composition according to (10), wherein the flame retardant aid (C) is antimony oxides and / or magnesium hydroxide.
(12)
A molded article comprising the polyamide composition according to any one of (1) to (11).
(13)
Electrical and electronic parts comprising the polyamide composition according to any one of (1) to (11).

  According to the present invention, it is possible to provide a polyamide composition that is excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, and excellent in flame retardancy.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The polyamide composition of the present embodiment is
(A) Polyamide and (B) Halogen flame retardant are contained.

[(A) Polyamide]
The polyamide used in the present embodiment is a polyamide obtained by polymerizing the following (a) and (b):
(A) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid,
(B) A diamine containing at least 50 mol% of a diamine having a substituent branched from the main chain.
In the present embodiment, the polyamide means a polymer having an amide (—NHCO—) bond in the main chain.

(A) Dicarboxylic acid (a) The dicarboxylic acid used in the present embodiment contains at least 50 mol% of an alicyclic dicarboxylic acid.
(A) By containing at least 50 mol% of the alicyclic dicarboxylic acid as the dicarboxylic acid, it is possible to obtain a polyamide that simultaneously satisfies heat resistance, fluidity, toughness, low water absorption, rigidity, and the like.

(A-1) Examples of alicyclic dicarboxylic acids (also referred to as alicyclic dicarboxylic acids) include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentane. Examples thereof include alicyclic dicarboxylic acids having 3 to 10 carbon atoms, preferably 5 to 10 carbon atoms, such as dicarboxylic acid.
The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.

  In this embodiment, examples of the substituent include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Etc.

The alicyclic dicarboxylic acid is preferably 1,4-cyclohexanedicarboxylic acid from the viewpoints of heat resistance, fluidity, rigidity, and the like.
As the alicyclic dicarboxylic acid, one kind may be used, or two or more kinds may be used in combination.

An alicyclic dicarboxylic acid has a trans isomer and a cis geometric isomer.
As the alicyclic dicarboxylic acid as a raw material monomer, either a trans isomer or a cis isomer may be used, or a mixture of various ratios of a trans isomer and a cis isomer may be used.
Since alicyclic dicarboxylic acids are isomerized at a high temperature to a certain ratio, and the cis isomer has higher water solubility in the equivalent salt with the diamine than the trans isomer, the trans isomer / cis cis is used as a raw material monomer. The body ratio in terms of molar ratio is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and still more preferably 35/65 to 15/85.
The trans isomer / cis isomer ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or NMR.

  Examples of dicarboxylic acids other than (a-2) alicyclic dicarboxylic acids of (a) dicarboxylic acids used in the present embodiment include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.

  Examples of the aliphatic dicarboxylic acid include malonic acid, dimethyl malonic acid, succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl glutaric acid, 2,2-diethyl succinic acid, and 2,3-diethyl glutaric acid. , Glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecane Examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as diacid, eicosane diacid, and diglycolic acid.

Examples of the aromatic dicarboxylic acid include unsubstituted or various terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. And aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with the above substituent.
Examples of the various substituents include halogen groups such as an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a chloro group and a bromo group, and 3 carbon atoms. Groups of 10 to 10 alkylsilyl groups and sulfonic acid groups and salts thereof such as sodium salts.

The dicarboxylic acid other than the alicyclic dicarboxylic acid is preferably an aliphatic dicarboxylic acid in terms of heat resistance, fluidity, toughness, low water absorption, and rigidity, and more preferably has 6 or more carbon atoms. It is an aliphatic dicarboxylic acid.
Among these, aliphatic dicarboxylic acids having 10 or more carbon atoms are preferable from the viewpoints of heat resistance and low water absorption.
Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid.
Of these, sebacic acid and dodecanedioic acid are preferable from the viewpoint of heat resistance and the like.
As dicarboxylic acid other than alicyclic dicarboxylic acid, you may use by 1 type and may be used in combination of 2 or more types.

(A) As the dicarboxylic acid, a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid may be further included within the range not impairing the object of the present embodiment.
As the polyvalent carboxylic acid, one kind may be used, or two or more kinds may be used in combination.

The proportion of (a-1) alicyclic dicarboxylic acid in (a) dicarboxylic acid is at least 50 mol%. The ratio of alicyclic dicarboxylic acid is 50-100 mol%, and it is preferable that it is 60-100 mol%. When the ratio of the alicyclic dicarboxylic acid is at least 50 mol%, a polyamide that simultaneously satisfies heat resistance, fluidity, toughness, low water absorption, rigidity, and the like can be obtained.
(A) The ratio of dicarboxylic acid other than (a-2) alicyclic dicarboxylic acid in dicarboxylic acid is 0 to 50 mol%, and preferably 0 to 40 mol%.

  (A-1) The alicyclic dicarboxylic acid is preferably 50.0 to 99.9 mol% and (a-2) the aliphatic dicarboxylic acid having 10 or more carbon atoms is preferably 0.1 to 50.0 mol%, More preferably, (a-1) the alicyclic dicarboxylic acid is 60.0 to 90.0 mol% and (a-2) the aliphatic dicarboxylic acid having 10 or more carbon atoms is 10.0 to 40.0 mol%. The (a-1) alicyclic dicarboxylic acid is 70.0 to 85.0 mol% and (a-2) the aliphatic dicarboxylic acid having 10 or more carbon atoms is 15.0 to 30.0 mol%. preferable.

In the present embodiment, the (a) dicarboxylic acid is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.
The compound equivalent to the dicarboxylic acid is not particularly limited as long as it can be a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the dicarboxylic acid, and examples thereof include anhydrides and halides of dicarboxylic acids. Can be mentioned.

(B) Diamine (b) The diamine used in the present embodiment contains at least 50 mol% of a diamine having a substituent branched from the main chain.
(B) By containing at least 50 mol% of a diamine having a substituent branched from the main chain as the diamine, a polyamide that simultaneously satisfies fluidity, toughness, rigidity, and the like can be obtained.

  Examples of the substituent branched from the main chain include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. Is mentioned.

(B-1) Examples of the diamine having a substituent branched from the main chain include 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane) and 2,2,4-. Examples include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine. .
The diamine having a substituent branched from the main chain is preferably 2-methylpentamethylenediamine from the viewpoint of rigidity and the like.
As the diamine having a substituent branched from the main chain, one kind may be used, or two or more kinds may be used in combination.

  Examples of the diamine other than the diamine having a substituent branched from the (b-2) main chain of the (b) diamine used in the present embodiment include an aliphatic diamine, an alicyclic diamine, and an aromatic diamine. Can be mentioned.

  Examples of the aliphatic diamine include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, And straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms such as tridecamethylenediamine.

  Examples of the alicyclic diamine (also referred to as alicyclic diamine) include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine, and the like.

  Examples of the aromatic diamine include metaxylylenediamine.

The diamine other than the diamine having a substituent branched from the main chain is preferably an aliphatic diamine and an alicyclic diamine, more preferably in terms of heat resistance, fluidity, toughness, low water absorption, rigidity, and the like. Is a linear saturated aliphatic diamine having 4 to 13 carbon atoms, more preferably a linear saturated aliphatic diamine having 6 to 10 carbon atoms, and still more preferably hexamethylene diamine.
As the diamine other than the diamine having a substituent branched from the main chain, one kind may be used, or two or more kinds may be used in combination.

(B) As the diamine, a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine may be further included within a range not impairing the object of the present embodiment.
As the polyvalent aliphatic amine, one kind may be used, or two or more kinds may be used in combination.

  (B) The ratio of the diamine having a substituent branched from the (b-1) main chain in the diamine is at least 50 mol%. The ratio of the diamine having a substituent branched from the main chain is 50 to 100 mol%, and preferably 60 to 100 mol%. When the ratio of the diamine having a substituent branched from the main chain is at least 50 mol%, a polyamide having excellent fluidity, toughness, rigidity, and the like can be obtained.

  (B) The ratio of diamine other than the diamine having a substituent branched from the (b-2) main chain in the diamine is 0 to 50 mol%, and preferably 0 to 40 mol%.

  The amount of (a) dicarboxylic acid added is preferably about the same molar amount as the amount of (b) diamine added. Considering the escape of (b) diamine out of the reaction system during the polymerization reaction, the molar amount of (b) diamine as a whole is preferably 0. It is 90-1.20, More preferably, it is 0.95-1.10, More preferably, it is 0.98-1.05.

(C) Lactam and / or aminocarboxylic acid From the viewpoint of toughness, the polyamide used in the present embodiment is preferably further copolymerized with (c) lactam and / or aminocarboxylic acid.
The (c) lactam and / or aminocarboxylic acid used in the present embodiment means a lactam and / or aminocarboxylic acid capable of polycondensation.
The lactam and / or aminocarboxylic acid is preferably a lactam and / or aminocarboxylic acid having 4 to 14 carbon atoms, and more preferably a lactam and / or aminocarboxylic acid having 6 to 12 carbon atoms.

Examples of the lactam include butyrolactam, pivalolactam, ε-caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like.
Among these, from the viewpoint of toughness, ε-caprolactam and laurolactam are preferable, and ε-caprolactam is more preferable.

Examples of the aminocarboxylic acid include ω-aminocarboxylic acid and α, ω-amino acid that are compounds in which the lactam is ring-opened.
The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ω position, such as 6-aminocaproic acid, 11-aminoundecanoic acid, And 12-aminododecanoic acid and the like, and examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.

  As the lactam and / or aminocarboxylic acid, one kind may be used, or two or more kinds may be used in combination.

  (C) It is preferable that the addition amount of a lactam and / or aminocarboxylic acid is 0-20 mol% with respect to the molar amount of the whole monomer of (a), (b) and (c).

When the polyamide is polymerized from (a) dicarboxylic acid and (b) diamine, a known end-capping agent can be further added to adjust the molecular weight.
Examples of the end-capping agent include monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. In view of the above, monocarboxylic acid and monoamine are preferable.
As the terminal blocking agent, one kind may be used, or two or more kinds may be used in combination.

The monocarboxylic acid that can be used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid , Caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and benzoic acid, toluyl And aromatic monocarboxylic acids such as acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
As monocarboxylic acid, you may use by 1 type and may be used in combination of 2 or more types.

The monoamine that can be used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; Etc.
Monoamines may be used alone or in combination of two or more.

The combination of (a) dicarboxylic acid and (b) diamine is not limited to the following: (a-1) at least 50 mol% alicyclic dicarboxylic acid and (b-1) at least 50 mol% 2 -A combination of methylpentamethylenediamine is preferred, (a-1) at least 50 mol% 1,4-cyclohexanedicarboxylic acid and (b-1) at least 50 mol% 2-methylpentamethylenediamine are more preferred.
By polymerizing these combinations as polyamide components, it is possible to obtain a high-melting-point polyamide that simultaneously satisfies heat resistance, fluidity, toughness, low water absorption, and excellent rigidity.

In the polyamide used in the present embodiment, the alicyclic dicarboxylic acid structure exists as a geometric isomer of a trans isomer and a cis isomer.
The trans isomer ratio of the alicyclic dicarboxylic acid structure in the polyamide represents the ratio of the trans isomer in the entire alicyclic dicarboxylic acid in the polyamide, and the trans isomer ratio is preferably 50 to 85 mol%. More preferably, it is 50-80 mol%, More preferably, it is 60-80 mol%.
(A-1) As the alicyclic dicarboxylic acid, it is preferable to use an alicyclic dicarboxylic acid having a trans isomer / cis isomer ratio (molar ratio) of 50/50 to 0/100. And (b) the polyamide obtained by polymerization of the diamine preferably has a trans isomer ratio of 50 to 85 mol%.
When the trans isomer ratio is within the above range, in addition to the characteristics of high melting point, toughness, and rigidity, polyamide has properties that are contrary to thermal rigidity due to high glass transition temperature and usually heat resistance. It has the property of simultaneously satisfying fluidity, high crystallinity and low water absorption.
These characteristics of the polyamide consist of a combination of (a) at least 50 mol% 1,4-cyclohexanedicarboxylic acid, (b) at least 50 mol% 2-methylpentamethylenediamine, and the trans isomer ratio is from 50 to This is particularly noticeable with polyamides of 85 mol%.
In the present embodiment, the trans isomer ratio can be measured by the method described in the Examples below.

The production method of polyamide used in the present embodiment includes (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid, and (b) at least 50 mol% of a substituent branched from the main chain. If it is a manufacturing method of polyamide including the process of superposing | polymerizing the diamine containing the aliphatic diamine which has, it will not specifically limit.
The method for producing the polyamide preferably further includes a step of increasing the degree of polymerization of the polyamide.

Examples of the method for producing the polyamide include various methods as exemplified below:
1) Suspension of aqueous solution or water of dicarboxylic acid and diamine or suspension of water or water of a mixture of dicarboxylic acid and diamine salt and other components (hereinafter abbreviated as “the mixture” in this paragraph). A method of polymerizing a suspended liquid while heating and maintaining a molten state (hereinafter sometimes abbreviated as “hot melt polymerization method”),
2) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (hereinafter, sometimes abbreviated as “hot melt polymerization / solid phase polymerization method”). ,
3) A method in which an aqueous solution or a suspension of water of dicarboxylic acid and diamine or a mixture thereof is heated, and the precipitated prepolymer is further melted again by an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as “prepolymer · Sometimes abbreviated as "extrusion polymerization method").
4) A method in which an aqueous solution or a suspension of water of dicarboxylic acid and diamine or a mixture thereof is heated, and the degree of polymerization is increased while maintaining the solid state of the precipitated prepolymer at a temperature below the melting point of the polyamide (hereinafter referred to as “ Abbreviated as “prepolymer / solid phase polymerization method”),
5) A method of polymerizing a dicarboxylic acid and a diamine or a mixture thereof while maintaining a solid state (hereinafter sometimes abbreviated as “solid phase polymerization method”),
6) A “solution method” in which a dicarboxylic acid halide and a diamine equivalent to dicarboxylic acid are used for polymerization.

In the polyamide production method, it is preferable to carry out the polymerization while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid at 50 to 85%, and from the viewpoint of the fluidity of the polyamide, the polymerization should be carried out at 50 to 80%. Is more preferable.
By maintaining the trans isomer ratio within the above range, particularly 80% or less, it is possible to obtain a polyamide having an excellent color tone and tensile elongation and a high melting point.
In the production method of polyamide, in order to increase the degree of polymerization and increase the melting point of the polyamide, it is necessary to increase the heating temperature and / or lengthen the heating time. The tensile elongation may decrease due to coloring or thermal deterioration. In addition, the rate at which the molecular weight increases may decrease significantly.
Since it is possible to prevent a decrease in tensile elongation due to polyamide coloring or thermal deterioration, it is preferable to perform polymerization while maintaining the trans isomer ratio at 80% or less.

  As a method for producing polyamide, since it is easy to maintain the trans isomer ratio at 80% or less and the obtained polyamide is excellent in color tone, 1) hot melt polymerization method and 2) hot melt polymerization Polyamide is preferably produced by a solid phase polymerization method.

In the method for producing polyamide, the polymerization form may be a batch type or a continuous type.
The polymerization apparatus is not particularly limited, and examples thereof include known apparatuses such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.

The method for producing the polyamide is not particularly limited, and the polyamide can be produced by a batch-type hot melt polymerization method described below.
Examples of the batch-type hot melt polymerization method include, for example, a polyamide component ((a) dicarboxylic acid, (b) diamine, and, if necessary, (c) lactam and / or aminocarboxylic acid) using water as a solvent. About 40 to 60% by mass of the contained solution is concentrated to about 65 to 90% by mass in a concentration tank operated at a temperature of 110 to 180 ° C. and a pressure of about 0.035 to 0.6 MPa (gauge pressure). To obtain a concentrated solution. The concentrated solution is then transferred to an autoclave and heating is continued until the pressure in the container is about 1.5-5.0 MPa (gauge pressure). Thereafter, the pressure is maintained at about 1.5 to 5.0 MPa (gauge pressure) while draining water and / or gas components, and when the temperature reaches about 250 to 350 ° C., the pressure is reduced to atmospheric pressure (gauge pressure is , 0 MPa). By reducing the pressure to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed. Thereafter, pressurization is performed with an inert gas such as nitrogen to extrude the polyamide melt as a strand. The strand is cooled and cut to obtain pellets.

The method for producing the polyamide is not particularly limited, and the polyamide can be produced by a continuous hot melt polymerization method described below.
As a continuous hot melt polymerization method, for example, a solution of about 40 to 60% by mass containing water and a polyamide component as a solvent is preheated to about 40 to 100 ° C. in a container of a preliminary apparatus, and then a concentrated layer / Concentrated to about 70-90% at a pressure of about 0.1-0.5 MPa (gauge pressure) and a temperature of about 200-270 ° C. to obtain a concentrated solution. The concentrated solution is discharged into a flasher maintained at a temperature of about 200 to 350 ° C., and then the pressure is reduced to atmospheric pressure (gauge pressure is 0 MPa). After reducing the pressure to atmospheric pressure, reduce the pressure as necessary. The polyamide melt is then extruded into strands, cooled and cut into pellets.

As the molecular weight of the polyamide in the present embodiment, a relative viscosity ηr at 25 ° C. was used as an index.
The molecular weight of the polyamide in the present embodiment is preferably a 98% sulfuric acid concentration of 1% and a relative viscosity ηr at 25 ° C. measured according to JIS-K6810 from the viewpoint of mechanical properties such as toughness and rigidity, and moldability. Is 1.5 to 7.0, more preferably 1.7 to 6.0, and even more preferably 1.9 to 5.5.
The relative viscosity at 25 ° C. can be measured according to JIS-K6810 as described in the following examples.

The melting point of the polyamide in the present embodiment is preferably 270 to 350 ° C. as Tm2 from the viewpoint of heat resistance. Melting | fusing point Tm2 becomes like this. Preferably it is 270 degreeC or more, More preferably, it is 275 degreeC or more, More preferably, it is 280 degreeC or more. The melting point Tm2 is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
By setting the melting point Tm2 of the polyamide to 270 ° C. or higher, a polyamide having excellent heat resistance can be obtained. By setting the melting point Tm2 of the polyamide to 350 ° C. or lower, the thermal decomposition of the polyamide in the melt processing such as extrusion and molding can be suppressed.

  The heat of fusion ΔH of the polyamide in the present embodiment is preferably 10 J / g or more, more preferably 14 J / g or more, still more preferably 18 J / g or more, and still more preferably, from the viewpoint of heat resistance. Is 20 J / g or more.

The measurement of the melting point (Tm1 or Tm2) and the heat of fusion ΔH of the polyamide in the present embodiment can be performed according to JIS-K7121 as described in the following examples.
Examples of the measuring device for the melting point and the heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER.

The glass transition temperature Tg of the polyamide in the present embodiment is preferably 90 to 170 ° C. The glass transition temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 110 ° C. or higher. The glass transition temperature is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
By setting the glass transition temperature to 90 ° C. or higher, a polyamide having excellent heat resistance and chemical resistance can be obtained. Further, by setting the glass transition temperature to 170 ° C. or less, a molded product having a good appearance can be obtained.
The glass transition temperature can be measured according to JIS-K7121 as described in the following examples.
Examples of the glass transition temperature measuring device include Diamond-DSC manufactured by PERKIN-ELMER.

The melt shear viscosity ηs of the polyamide in the present embodiment is preferably 20 to 140 Pa · s, more preferably 25 to 115 Pa · s, and further preferably 30 to 90 Pa · s.
The melt shear viscosity can be measured by the method described in the following examples.
When the melt shear viscosity is within the above range, a polyamide having excellent fluidity can be obtained.

The tensile strength of the polyamide in the present embodiment is preferably 70 MPa or more, more preferably 80 MPa or more, and further preferably 85 MPa or more.
The tensile strength can be measured according to ASTM D638 as described in the following examples.
When the tensile strength is 70 MPa or more, a polyamide having excellent rigidity can be obtained.

The tensile elongation of the polyamide in the present embodiment is preferably 3.0% or more, more preferably 5.0% or more, and further preferably 7.0% or more.
The tensile elongation can be measured according to ASTM D638 as described in the following examples.
When the tensile elongation is 3.0% or more, a polyamide having excellent toughness can be obtained.

The water absorption rate of the polyamide in the present embodiment is preferably 5.0% or less, more preferably 4.0% or less, and even more preferably 3.0% or less.
The water absorption rate can be measured by the method described in the following examples.
When the water absorption is 5.0% or less, a polyamide having excellent low water absorption can be obtained.

[(B) Halogen flame retardant]
The polyamide composition of the present embodiment is a polyamide composition containing the (A) polyamide and (B) a halogen-based flame retardant.
As the polyamide composition in the present embodiment, by containing (B) a halogen-based flame retardant, the polyamide composition does not impair the properties of polyamide excellent in heat resistance, fluidity, toughness, rigidity, and low water absorption. However, it can be set as the polyamide composition which is excellent in heat resistance, fluidity | liquidity, toughness, rigidity, and low water absorption, and also excellent in a flame retardance.
Moreover, even if the polyamide composition of this Embodiment contains (B) halogenated flame retardant, it is excellent in light resistance and is excellent also as a color tone of a polyamide composition.

The (B) halogen flame retardant used in the present embodiment is not particularly limited as long as it is a flame retardant containing a halogen element, and examples thereof include a chlorine flame retardant and a bromine flame retardant. .
These flame retardants may be used alone or in combination of two or more.

  Examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene (Dechlorane Plus 25 <registered trademark> manufactured by Occidental Chemical), and heptic anhydride. Can be mentioned.

  Examples of brominated flame retardants include hexabromocyclododecane (HBCD), decabromodiphenyl oxide (DBDPO), octabromodiphenyl oxide, tetrabromobisphenol A (TBBA), bis (tribromophenoxy) ethane, and bis (pentabromo). Phenoxy) ethane (BPBPE), tetrabromobisphenol A epoxy resin (TBBA epoxy), tetrabromobisphenol A carbonate (TBBA-PC), ethylene (bistetrabromophthal) imide (EBTBPI), ethylene bispentabromodiphenyl, tris (tri Bromophenoxy) triazine (TTBPTA), bis (dibromopropyl) tetrabromobisphenol A (DBP-TBBA), bis (dibromopropyl) tetrabromobi Phenol S (DBP-TBBS), brominated polyphenylene ether (including poly (di) bromophenylene ether) (BrPPE), brominated polystyrene (including polydibromostyrene, polytribromostyrene, crosslinked brominated polystyrene, etc.) ( BrPS), brominated cross-linked aromatic polymer, brominated epoxy resin, brominated phenoxy resin, brominated styrene-maleic anhydride polymer, tetrabromobisphenol S (TBBS), tris (tribromoneopentyl) phosphate (TTBNPP) , Polybromotrimethylphenylindane (PBPI), and tris (dibromopropyl) -isocyanurate (TDBPIC).

  (B) As halogenated flame retardant, brominated polyphenylene is used from the viewpoint of low generation amount of corrosive gas at the time of melt processing such as extrusion and molding, and further from mechanical properties such as expression of flame retardancy, toughness and rigidity. Ether (including poly (di) bromophenylene ether) and brominated polystyrene (including polydibromostyrene, polytribromostyrene, and cross-linked brominated polystyrene) are preferable, and brominated polystyrene is more preferable.

The brominated polystyrene is not particularly limited. For example, after polystyrene is produced by polymerizing a styrene monomer, the benzene ring of the polystyrene is brominated or brominated styrene monomer (bromostyrene, dibromo). Styrene, tribromostyrene, etc.) can be produced by a polymerization method.
The bromine content in the brominated polystyrene is preferably 55 to 75% by mass. By setting the bromine content to 55% by mass or more, the amount of bromine necessary for flame retardancy can be satisfied with a small blended amount of brominated polystyrene, and heat resistance and fluidity are maintained without impairing the properties of the polyamide. Thus, a polyamide composition having excellent toughness, low water absorption, rigidity, and excellent flame retardancy can be obtained. Further, by setting the bromine content to 75% by mass or less, a polyamide composition that hardly causes thermal decomposition during melt processing such as extrusion and molding, can suppress gas generation, and is excellent in heat discoloration. Obtainable.

  The polyamide composition may further contain any one of (C) a flame retardant aid, (D) a polymer containing an α, β unsaturated dicarboxylic acid anhydride, and (E) an inorganic filler.

By further containing (C) a flame retardant aid as the polyamide composition, a polyamide composition having further excellent flame retardancy can be obtained.
The flame retardant aid (C) used in the present embodiment is not particularly limited. For example, antimony oxides such as antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate. , Tin oxide such as tin monoxide and tin dioxide, iron oxides such as ferric oxide and gamma iron oxide, other zinc oxide, zinc borate, calcium oxide, aluminum oxide (alumina), aluminum oxide (boehmite), oxidation Metal oxides such as silicon (silica), titanium oxide, zirconium oxide, manganese oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, nickel oxide, copper oxide, and tungsten oxide; magnesium hydroxide, and water Metal hydroxides such as aluminum oxide; aluminum, iron, titanium, manganese, Metal powders such as lead, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, and tungsten; metal carbonates such as zinc carbonate, calcium carbonate, magnesium carbonate, and barium carbonate; magnesium borate, calcium borate And metal borates such as aluminum borate; and silicone.
These flame retardant aids may be used alone or in combination of two or more.

  As the flame retardant aid (C) used in the present embodiment, antimony oxides such as diantimony trioxide, diantimony tetroxide, diantimony pentoxide, sodium antimonate, water, etc. Preferred are tin oxide such as magnesium oxide, tin monoxide and tin dioxide, iron oxides such as ferric oxide and gamma iron oxide, zinc oxide and zinc borate. Antimony trioxide, antimony tetroxide, pentoxide Antimony oxides such as antimony oxide, magnesium hydroxide and zinc borate are more preferable, and antimony trioxide and magnesium hydroxide are more preferable.

In order to increase the flame retardant effect, it is preferable to use (C) a flame retardant aid having an average particle size of 0.01 to 10 μm.
The average particle size can be measured using a laser diffraction scattering method particle size distribution measuring device or a precision particle size distribution measuring device.

By further including (D) a polymer containing an α, β-unsaturated dicarboxylic acid anhydride as a polyamide composition, it is possible to obtain a polyamide composition that is further excellent in flame retardancy and mechanical properties such as toughness and rigidity. it can.
Examples of the polymer containing (D) α, β unsaturated dicarboxylic anhydride used in the present embodiment include a polymer containing α, β unsaturated dicarboxylic anhydride as a copolymerization component, and α, β. And polymers modified with unsaturated dicarboxylic acid anhydrides.

Examples of the α, β unsaturated dicarboxylic acid anhydride include compounds represented by the following general formula (1).
General formula (1):
In General formula (1), R < ¹ > and R < ² > are respectively independently hydrogen or a C1-C3 alkyl group.

Examples of the α, β unsaturated dicarboxylic acid anhydride include maleic anhydride and methyl maleic anhydride, and maleic anhydride is preferable.
Examples of the polymer containing an α, β unsaturated dicarboxylic acid anhydride as a copolymerization component include a copolymer of an aromatic vinyl compound and an α, β unsaturated dicarboxylic acid anhydride.
Examples of the polymer modified with α, β unsaturated dicarboxylic acid anhydride include polyphenylene ether resin and polypropylene resin modified with α, β unsaturated dicarboxylic acid anhydride.

  (D) As a polymer containing an α, β unsaturated dicarboxylic acid anhydride, an aromatic vinyl compound and an α, β unsaturated dicarboxylic acid are used from the viewpoint of efficiency to improve flame retardancy (expressed with a small addition amount). An acid anhydride copolymer is preferred.

As an aromatic vinyl compound used in this Embodiment, the compound represented by following General formula (2) is mentioned, for example.
General formula (2):
In general formula (2), ^{R 3} and ^{R 4} are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, k is an integer of 1 to 5.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, and the like, and styrene is preferable.
In the present embodiment, when the polymer containing (D) α, β unsaturated dicarboxylic acid anhydride contains an aromatic vinyl compound component, the aromatic vinyl compound component is a halogen-based flame retardant (brominated polystyrene or the like). ), And the α, β unsaturated dicarboxylic acid anhydride moiety is compatible with or reacts with the polyamide, thereby helping to disperse the (B) halogen flame retardant in the polyamide matrix. It is thought that the flame retardant can be finely dispersed.

The ratio of aromatic vinyl compound component and α, β unsaturated dicarboxylic acid anhydride component in the copolymer of aromatic vinyl compound and α, β unsaturated dicarboxylic acid anhydride is flame retardant, fluidity, and heat decomposability. In view of the above, it is preferable that the aromatic vinyl compound component is 50 to 99% by mass and the α, β unsaturated dicarboxylic anhydride component is 1 to 50% by mass. The proportion of the α, β unsaturated dicarboxylic anhydride component is more preferably 5 to 20% by mass, further preferably 8 to 15% by mass.
By setting the proportion of the α, β unsaturated dicarboxylic anhydride component to 1% by mass or more, a polyamide composition excellent in mechanical properties such as toughness and rigidity and flame retardancy can be obtained. Further, by setting the proportion of the α, β unsaturated dicarboxylic acid anhydride component to 50% by mass or less, the deterioration of the polyamide composition due to the α, β unsaturated dicarboxylic acid anhydride can be prevented.

  By further containing (E) an inorganic filler as the polyamide composition, a polyamide composition having further excellent mechanical properties such as toughness and rigidity can be obtained.

The (E) inorganic filler used in the present embodiment is not particularly limited. For example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, Talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, Calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite , Swellable fluorine mica, and apatite, and the like.
As the inorganic filler, one kind may be used, or two or more kinds may be used in combination.

  (E) As an inorganic filler, in terms of rigidity and strength, glass fiber, carbon fiber, glass flake, talc, kaolin, mica, calcium carbonate, calcium monohydrogen phosphate, wollastonite, silica, carbon nanotube, Graphite, calcium fluoride, montmorillonite, swellable fluorine mica, apatite, and the like are preferable.

(E) As an inorganic filler, glass fiber and carbon fiber are more preferable. Among glass fiber and carbon fiber, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 100 to 750 μm, and the weight average Those having an aspect ratio (L / D) between the fiber length and the number average fiber diameter of 10 to 100 are more preferably used from the viewpoint of expressing high characteristics.
(E) As the inorganic filler, wollastonite is more preferable. Among the wollastonites, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 10 to 500 μm, and the aspect ratio ( Those having L / D) of 3 to 100 are more preferably used.
Furthermore, as the (E) inorganic filler, talc, mica, kaolin, silicon nitride, and the like are more preferable. Among talc, mica, kaolin, silicon nitride, and the like, the number average fiber diameter is 0.1 to 3 μm. Those are more preferably used.

  The number average fiber diameter and the weight average fiber length of the inorganic filler are measured by dissolving a polyamide composition molded article with a solvent in which polyamide is soluble, such as formic acid, and, for example, 100 of the obtained insoluble components. The above inorganic fillers can be arbitrarily selected and observed and obtained with an optical microscope or a scanning electron microscope.

The method for producing the polyamide composition of the present embodiment is not particularly limited as long as it is a method of mixing (A) polyamide and (B) halogen flame retardant. Moreover, as a manufacturing method of a polyamide composition, the method of further mixing (C) a flame retardant adjuvant, (D) the polymer containing (alpha), (beta) unsaturated dicarboxylic acid anhydride, and / or (E) inorganic filler. Is mentioned.
Examples of the mixing method of (A) polyamide and (B) halogen flame retardant include (A) polyamide and (B) halogen flame retardant, optionally (C) flame retardant aid, (D) α, A method of mixing a polymer containing β-unsaturated dicarboxylic acid anhydride and / or (E) an inorganic filler using a Henschel mixer or the like, supplying the mixture to a melt-kneader, and kneading or a single-screw or twin-screw extruder (A) Polyamide, (B) halogen-based flame retardant, and optionally (C) a flame retardant aid and / or (D) a polymer containing α, β unsaturated dicarboxylic acid anhydride in advance, such as a Henschel mixer A method of blending (E) an inorganic filler from a side feeder is optionally used after supplying and mixing to a melt kneader and kneading.

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

The melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
The melt kneading time is preferably about 0.5 to 5 minutes.
As an apparatus for performing melt kneading, a known apparatus, for example, a melt kneader such as a single or twin screw extruder, a Banbury mixer, and a mixing roll is preferably used.

(B) Blend amount of halogenated flame retardant, and optionally (C) Flame retardant aid, (D) Polymer containing α, β unsaturated dicarboxylic acid anhydride, and / or (E) Inorganic filler The blending amount of is not particularly limited.
The blending amount of the (B) halogen flame retardant in the polyamide composition is preferably 30 to 60 parts by mass, more preferably 35 to 55 parts by mass, with respect to 100 parts by mass of the (A) polyamide. Preferably it is 40-50 mass parts.
(B) The polyamide composition which is excellent in a flame retardance can be obtained by the compounding quantity of a halogenated flame retardant being 30 mass parts or more. In addition, by making the blending amount of (B) halogen flame retardant 60 parts by mass or less, generation of decomposition gas at the time of melt-kneading, decrease in fluidity at the time of molding processing, and adhesion of pollutants to the molding die Can be suppressed. Furthermore, deterioration of mechanical properties such as toughness and rigidity and appearance of the molded product can be suppressed.

The blending amount of the flame retardant aid (C) in the polyamide composition is preferably 0 to 30 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the (A) polyamide. Preferably it is 2-20 mass parts, More preferably, it is 4-15 mass parts.
(C) By mix | blending a flame retardant adjuvant, the polyamide composition which is further excellent in a flame retardance can be obtained. In addition, by setting the blending amount of (C) the flame retardant aid to 30 parts by mass or less, it is possible to control the viscosity at the time of melt processing to an appropriate range, increase in torque at the time of extrusion, and formability at the time of molding. The decrease and the deterioration of the appearance of the molded product can be suppressed. Further, a polyamide composition having excellent toughness can be obtained without impairing the properties of polyamide having excellent mechanical properties such as toughness and rigidity.

The blending amount of the polymer containing (D) α, β unsaturated dicarboxylic acid anhydride in the polyamide composition is preferably 0 to 20 parts by mass, more preferably 100 parts by mass of the polyamide (A). It is 0.5-20 mass parts, More preferably, it is 1-15 mass parts, More preferably, it is 2-10 mass parts.
(D) By blending a polymer containing α, β-unsaturated dicarboxylic acid anhydride, the fine dispersion effect of (B) halogen flame retardant in the polyamide composition by compatibilization can be enhanced. Thus, it is possible to obtain a polyamide composition excellent in the effect of improving property and strength. In addition, by setting the blending amount of the polymer containing (D) α, β-unsaturated dicarboxylic acid anhydride to 20 parts by mass or less, the strength and the like can be obtained without impairing the properties of the polyamide having excellent mechanical properties such as toughness and rigidity. Can be obtained.

In the present embodiment, (D) the amount of the α, β unsaturated dicarboxylic acid anhydride component in the polymer containing the α, β unsaturated dicarboxylic acid anhydride is the amount of (A), (B) and (D). A polyamide composition containing (D) a polymer containing an α, β-unsaturated dicarboxylic acid anhydride so as to be 0.02 to 1.00% by mass with respect to the total amount is preferable. The amount of the α, β-unsaturated dicarboxylic acid anhydride component is more preferably 0.06 to 0.75% by mass, still more preferably 0.1 to 0.6% by mass, and still more preferably 0.00. 2 to 0.5% by mass.
By setting the amount of the α, β unsaturated dicarboxylic anhydride component to 0.02% by mass or more, a fine dispersion of the halogen-based flame retardant can be achieved, and a polyamide composition having excellent flame retardancy can be obtained. Obtainable. Further, by setting the amount of the α, β unsaturated dicarboxylic anhydride component to 1.00% by mass or less, the melt viscosity of the polyamide composition is increased due to the affinity of the α, β unsaturated dicarboxylic anhydride component with the polyamide. Can be suppressed, and an appropriate melt viscosity excellent in workability can be obtained.

The compounding amount of the (E) inorganic filler in the polyamide composition is suitably 0 to 240 parts by mass, preferably 0 to 200 parts by mass, more preferably 100 parts by mass of the polyamide. It is 0.1-200 mass parts, More preferably, it is 1-180 mass parts, More preferably, it is 5-150 mass parts.
By blending the inorganic filler, mechanical properties such as toughness and rigidity of the polyamide composition are improved satisfactorily, and the blending amount of the inorganic filler is 240 parts by mass or less, preferably 200 parts by mass or less. Thus, a polyamide composition having excellent moldability can be obtained.

  In the polyamide composition, for example, colorants such as pigments and dyes (including colored master batches), fibrillating agents, other flame retardants, lubricants, and fluorescent bleaching agents, as long as the object of the present embodiment is not impaired. Contains plasticizers, antistatic agents, fluidity improvers, other fillers, antioxidants, stabilizers, UV absorbers, nucleating agents, rubbers, spreading agents, other polymers, reinforcing materials and reinforcing agents You can also

  The relative viscosity ηr at 25 ° C., the melting point Tm2, the heat of fusion ΔH, and the glass transition temperature Tg of the polyamide composition of the present embodiment can be measured by the same method as that for the polyamide. Moreover, since the measured value in the polyamide composition is in the same range as the preferable value as the measured value of the polyamide, it has a high melting point excellent in mechanical properties such as heat resistance, moldability, toughness and rigidity, and chemical resistance. A polyamide composition can be obtained.

The tensile strength of the polyamide composition is preferably 160 MPa or more, more preferably 170 MPa or more, further preferably 180 MPa or more, and still more preferably 190 MPa or more.
The tensile strength can be measured according to ASTM D638 as described in the following examples.
When the tensile strength is 160 MPa or more, a polyamide composition having excellent rigidity can be obtained.

The tensile elongation of the polyamide composition is preferably 2.1% or more, more preferably 2.5% or more, and further preferably 3.0% or more.
The tensile elongation can be measured according to ASTM D638 as described in the following examples.
The tensile elongation can be measured according to ASTM D638 as described in the following examples.
When the tensile elongation is 2,1% or more, a polyamide composition having excellent toughness can be obtained.

The water absorption of the polyamide is preferably 4.0% or less, more preferably 3.0% or less, still more preferably 2.6% or less, and even more preferably 2.4% or less, Most preferably, it is 2.2% or less.
The water absorption rate can be measured by the method described in the following examples.
When the water absorption is 4.0% or less, a polyamide composition excellent in low water absorption can be obtained.

The flame retardancy of the polyamide composition was measured according to UL-94VB.
The flame retardancy of the polyamide composition is preferably V-2 or more, more preferably V-1 or more, and further preferably V-0.

The flow length of the polyamide composition is preferably 15 cm or more, more preferably 17 cm or more, and further preferably 20 cm or more.
The flow length can be measured by the method described in the examples below.
When the flow length is 15 cm or more, a polyamide composition having excellent fluidity can be obtained.

[Molding]
The polyamide composition of the present embodiment is a known molding method such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melt spinning. Various molded products can be obtained using

Molded articles of the polyamide composition of the present embodiment are known molding methods such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melting. It can be obtained by using a generally known plastic molding method such as spinning.
The molded product obtained from the polyamide composition of the present embodiment is excellent in heat resistance, toughness, moldability, and flame retardancy. Therefore, the polyamide composition of the present embodiment is suitable for various parts materials such as for automobiles, machine industries, electric and electronic, industrial materials, daily and household goods, and for extrusion applications. Can be used. Among them, connectors and switches that support SMT (surface mount technology) because of excellent reflow characteristics (requires low water absorption and heat resistance) in the reflow soldering process required for automotive electrical components such as wire harness connectors and surface mounting It can be suitably used for electrical and electronic parts such as a coil bobbin, a breaker, an electromagnetic switch, a holder, a plug, and a switch.

Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples, but the present embodiment is not limited to only these examples.
The raw materials and measurement methods used in Examples and Comparative Examples are shown below. In this example, 1 kg / cm ² means 0.098 MPa.

[raw materials]
The following compounds were used in this example.
(A) Dicarboxylic acid (1) 1,4-cyclohexanedicarboxylic acid (CHDA) manufactured by Eastman Chemical Co., Ltd. Product name 1,4-CHDA HP grade (trans isomer / cis isomer (molar ratio) = 25/75)
(2) Terephthalic acid (TPA) Wako Pure Chemical Industries product name Terephthalic acid (3) Adipic acid (ADA) Wako Pure Chemical Industries product name Adipic acid (4) Suberic acid (C8DA) Wako Pure Chemical Industries product name Suberin Acid (5) Azelaic acid (C9DA) Wako Pure Chemical Industries product name Azelaic acid (6) Sebacic acid (C10DA) Wako Pure Chemical Industries product name Sebacic acid (7) Dodecanedioic acid (C12DA) Wako Pure Chemical Industries product Name Dodecanedioic acid (8) Tetradecanedioic acid (C14DA) manufactured by Tokyo Chemical Industry Product name Tetradecanedioic acid (9) Hexadecanedioic acid (C16DA) Product name manufactured by Tokyo Chemical Industry Hexadecanedioic acid

(B) Diamine (10) 2-Methylpentamethylenediamine (2MPD) Product name 2-methyl-1,5-diaminopentane (11) Hexamethylenediamine (HMD) Product name Hexamethylene Diamine (12) 1,9-nonamethylenediamine (NMD) Aldrich product name 1,9-nonanediamine (13) 2-methyloctamethylenediamine (2MOD) Refer to the production method described in JP-A No. 05-17413 Manufactured.
(14) Mixture of 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl-1,6-hexanediamine (TMHD) Aldrich product name C, C, C-1, 6 -Hexamethylenediamine

(C) Lactam and / or aminocarboxylic acid (15) ε-caprolactam (CPL) Wako Pure Chemical Industries, Ltd. Product name ε-caprolactam

(B) Halogen-based flame retardant (16) Brominated polystyrene Albemarle Corporation product name SAYTEX (registered trademark) HP-7010G (from elemental analysis bromine content: 63 mass%)

(C) Flame retardant aid (17) Antimony trioxide, manufactured by Dai-ichi F.R. Product name: Antimony trioxide (18) Magnesium hydroxide, manufactured by Kyowa Chemical Co., Ltd.

(D) Polymer containing α, β-unsaturated dicarboxylic acid anhydride (19) Copolymer of styrene and maleic anhydride Product name DYLARK (registered trademark) 332 (85% by mass of styrene and 15% by mass of maleic anhydride) manufactured by NOVA Chemicals % Copolymer)

(E) Inorganic filler (20) Glass fiber (GF) Made by Nippon Electric Glass Product name ECS03T275H Average fiber diameter 10 μmφ, cut length 3 mm

[Calculation of polyamide content]
(A-1) The mol% of the alicyclic dicarboxylic acid is (the number of moles of (a-1) alicyclic dicarboxylic acid added as a raw material monomer / the number of moles of all (a) dicarboxylic acids added as raw material monomers. ) × 100.
(B-1) The mol% of the diamine having a substituent branched from the main chain was added as the raw material monomer (b-1) The number of moles of the diamine having the substituent branched from the main chain / the raw material monomer. All (b) moles of diamine) × 100 were obtained by calculation.
In addition, (c) lactam and / or aminocarboxylic acid, BR> c, and (c) mole number of lactam and / or aminocarboxylic acid added as a raw material monomer / all ( It was determined by calculation as a) mole number of dicarboxylic acid + (b) mole number of all diamines + (c) mole number of lactam and / or aminocarboxylic acid) × 100.
In addition, when calculating by the above formula, the denominator and the numerator do not include the number of moles of diamine having a substituent branched from the main chain (b-1) added as an additional component.

[Measuring method]
(1) Melting points Tm1, Tm2 (° C.)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER. The measurement condition is that the temperature of an endothermic peak (melting peak) that appears when about 10 mg of a sample is heated to 300 to 350 ° C. according to the melting point of the sample at a heating rate of 20 ° C./min in a nitrogen atmosphere is Tm1 (° C.). After maintaining the temperature in the molten state at the highest temperature rise for 2 minutes, the temperature was lowered to 30 ° C. at a temperature drop rate of 20 ° C./min, held at 30 ° C. for 2 minutes, and the same at the temperature rise rate of 20 ° C./min. The maximum peak temperature of the endothermic peak (melting peak) that appears when the temperature was raised to the melting point was Tm2 (° C.), and the total peak area was the heat of fusion ΔH (J / g). When there were a plurality of peaks, those having ΔH of 1 J / g or more were regarded as peaks. For example, when two peaks of melting point 295 ° C., ΔH = 20 J / g and melting point 325 ° C., ΔH = 5 J / g are present, the melting point is 325 ° C.

(2) Trans isomer ratio 30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride and measured by ¹ H-NMR. In the case of 1,4-cyclohexanedicarboxylic acid, the trans isomer ratio was determined from the ratio of the peak area of 1.98 ppm derived from the trans isomer and the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer.

(3) Glass transition temperature Tg (° C)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER. Measurement conditions were such that a sample in a molten state obtained by melting a sample on a hot stage (EP80 manufactured by Mettler) was rapidly cooled using liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the sample, the glass transition temperature was measured by raising the temperature in the range of 30 to 350 ° C. under a temperature raising speed of 20 ° C./min.

(4) Relative viscosity ηr at 25 ° C
It implemented according to JIS-K6810. Specifically, a 1% concentration solution ((polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid and measured under a temperature condition of 25 ° C.

(5) Tensile strength (MPa) and tensile elongation (%)
Using a dumbbell injection molding test piece (3 mm thickness) for the ASTM tensile test, it was performed according to ASTM D638. The molding test piece is a cylinder with a dumbbell test piece (3 mm thickness) for ASTM tensile test (ASTM D638) (mold temperature = Tg + 20 ° C.) attached to an injection molding machine (PS40E manufactured by Nissei Resin Co., Ltd.). Molding was performed at a temperature = (Tm2 + 10) ° C. to (Tm2 + 30) ° C.

(6) Water absorption rate (%)
A pre-test mass (mass before water absorption) was measured in a dry as mold of a dumbbell injection molded test piece (3 mm thick) for ASTM tensile test. It was immersed in pure water at 80 ° C. for 24 hours. Then, the test piece was taken out from the water, the surface adhering moisture was wiped off, and after standing in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere for 30 minutes, the mass after test (mass after water absorption) was measured. The increment of the mass after water absorption with respect to the mass before water absorption was taken as the water absorption amount, the ratio of the water absorption amount with respect to the mass before water absorption was determined by the number of trials n = 3, and the average value was taken as the water absorption rate (%).

(7) Flame retardancy The measurement was performed using the method of UL94 (standard defined by Under Writers Laboratories Inc., USA). The specimen (length 127 mm, width 12.7 mm, thickness 1/32 inch) is attached to the injection molding machine (PS40E manufactured by Nissei Plastic Co., Ltd.) with the mold of the UL specimen (mold temperature = Tg + 20 ° C.). Molding was performed at a cylinder temperature = Tm2 + 20 ° C. The injection pressure was the full filling pressure at the time of forming the UL test piece + 2% pressure.
The flame retardant grade conformed to UL94 standard (vertical combustion test). Moreover, the thing of V-2 failure was described as V-2out.

(8) Flow length (cm)
The molding machine set to the following conditions was used to mold a 2 mm thickness × 15 mm width, and the fluidity was evaluated from the flow length (filled length, cm).
A mold (mold temperature = Tg + 20 ° C.) for fluidity evaluation (2 mm thickness × 15 mm width spiral flow path) is attached to an injection molding machine (FN 3000 manufactured by Nissei Resin Co., Ltd.), cylinder temperature = Tm2 + 20 ° C., injection Molding was performed with the speed set at 20% and the injection pressure set at 34%.

Polyamide [Production Example 1]
Polymerization reaction of polyamide was carried out by “hot melt polymerization method”.
(A) CHDA 896 g (5.20 mol) and (b) 2MPD 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of raw material monomers. To this homogeneous aqueous solution, 15 g (0.13 mol) of 2MPD was added.
The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C. until the pressure in the autoclave tank reached about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank was expressed as gauge pressure). (The liquid temperature in this system was about 145 ° C.). While maintaining the pressure in the tank at about 2.5 Kg / cm ² , water was removed from the system while heating was continued until the concentration of the aqueous solution was about 75% (the liquid temperature in this system was about It was 160 ° C.). The removal of water was stopped and heating was continued until the pressure in the tank reached about 30 Kg / cm ² (the liquid temperature in this system was about 245 ° C.). Heating was continued until the final temperature was −50 ° C. while removing water out of the system in order to keep the pressure in the tank at about 30 Kg / cm ² . After the liquid temperature rose to the final temperature of −50 ° C. (here, 300 ° C.), while continuing heating, the pressure in the tank was decreased while taking about 120 minutes until the pressure in the tank reached atmospheric pressure (gauge pressure was 0 Kg / cm ² ). .
Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 350 ° C. With the resin temperature kept in this state, the inside of the tank was maintained for 30 minutes under a reduced pressure of 400 torr with a vacuum apparatus. Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain a polyamide. The measurement results of the obtained polyamide based on the above measurement method are shown in Table 4 (melting point Tm2, glass transition temperature Tg, trans isomer ratio, and relative viscosity at 25 ° C.).

[Production Examples 2 to 21]
In Production Example 1, (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, the compounds and amounts shown in Table 1 or 2 were used, and the final temperature of the resin temperature. The polyamide was polymerized by the method described in Production Example 1 except that the temperature was changed to the temperature described in Table 4 or 5 ("heat melt polymerization method").
Tables 4 and 5 show the measurement results of the obtained polyamide based on the above measurement method.

[Comparative Production Example 1]
In Production Example 1, the compounds and amounts shown in Table 3 were used as (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, and the final temperature of the resin temperature was expressed. Polymerization of polyamide was carried out by the method described in Production Example 1 except that the temperature was set to 6 (“hot melt polymerization method”).
In Comparative Production Example 1, since it was solidified in the autoclave during the polymerization, it could not be taken out as a strand. Therefore, after cooling, it was taken out as a lump and pulverized with a pulverizer to a size about pellets. Since the foaming was severe, the molded product could not be obtained.

[Comparative Production Examples 2 to 7]
In Production Example 1, the compounds and amounts shown in Table 3 were used as (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, and the final temperature of the resin temperature was expressed. Polymerization of polyamide was carried out by the method described in Production Example 1 except that the temperature was set to 6 (“hot melt polymerization method”). Table 6 shows the measurement results of the obtained polyamide based on the above measurement method.

Polyamide composition [Example 1]
The polyamide of Production Example 1 was dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass. Twin screw extruder (Toshiba Machine Co., Ltd. TEM35φL / D = 47.6, set temperature is the melting point of polyamide (Tm2) + 20 ° C. (specifically, when the polyamide of Production Example 1 is used, 327 + 20 = 347 ° C.) (A) Polyamide, (B) Halogen flame retardant, (C) Flame retardant aid from the top feed port provided in the most upstream part of the extruder using a screw rotation speed of 300 rpm and a discharge rate of 50 kg / hr). And (D) a polymer previously blended with an α, β unsaturated dicarboxylic acid anhydride is supplied to the downstream side of the extruder (the resin supplied from the top feed port is sufficiently melted). (E) Inorganic filler was supplied from the side feed port, and the melt-kneaded product extruded from the die head was cooled in a strand shape and pelletized to obtain polyamide composition pellets. The blending amount is (B) 45.0 parts by mass of a halogen-based flame retardant, (C) 7.0 parts by mass of a flame retardant aid, and (D) α, β unsaturated dicarboxylic acid with respect to 100 parts by mass of (A) polyamide. It was set as 4.0 mass parts of polymers containing an anhydride, and 70.0 mass parts of (E) inorganic filler. Table 4 shows the measurement results of the obtained polyamide composition based on the above measurement method.

[Examples 2 to 21]
It implemented similarly to Example 1 except having replaced with the polyamide of manufacture example 1 and using the polyamide of manufacture examples 2-21. Tables 4 and 5 show the measurement results of the obtained polyamide composition based on the above measurement method.

[Example 22]
(D) Except for blending polymer containing α, β unsaturated dicarboxylic acid anhydride, (C) 15.0 parts by mass of flame retardant aid, and (E) 75.0 parts by mass of inorganic filler Was carried out in the same manner as in Example 5. Table 5 shows the results of measurements performed on the obtained polyamide composition based on the above measurement method.

[Example 23]
(C) The same procedure as in Example 5 was carried out except that 7.0 parts by mass of magnesium hydroxide was used as a flame retardant aid. Table 5 shows the results of measurements performed on the obtained polyamide composition based on the above measurement method.

[Comparative Example 1]
An attempt was made in the same manner as in Example 73 except that the polyamide of Comparative Production Example 1 was used in place of the polyamide of Production Example 1, but the extrusion state was very unstable, and a polyamide composition could not be obtained.
[Comparative Examples 2 to 7]
The same procedure as in Example 1 was performed except that the polyamides of Comparative Production Examples 2 to 7 were used in place of the polyamide of Production Example 1. Table 6 shows the measurement results of the obtained polyamide composition based on the above measurement method.

From the results of Table 4-6, the polyamide compositions of Examples 1 to 23 containing a polyamide obtained by polymerizing specific (a) and (b) and a halogen-based flame retardant have low heat resistance, fluidity, toughness, and low resistance. It had particularly excellent characteristics in all points of water absorption, rigidity, and flame retardancy.
On the other hand, Comparative Example 1 containing a polyamide (Comparative Production Example 1) obtained by polymerizing a diamine having a substituent branched from a main chain of less than 50 mol% and less than 50 mol% (2-methylpentamethylenediamine). Then, the extruded state was unstable, and a polyamide composition could not be obtained.
Further, Comparative Examples 2, 3, and 6 containing polyamides (Comparative Production Examples 2, 3, and 6) obtained by polymerizing less than 50 mol% of alicyclic dicarboxylic acid are sufficient in terms of heat resistance and rigidity. It wasn't.
Furthermore, as disclosed in Patent Document 1, a comparative example 4 containing a polyamide produced by using an aromatic dicarboxylic acid instead of an alicyclic dicarboxylic acid (Comparative Production Example 4) and a polyamide of Comparative Production Example 5 and In No. 5, the flow length was short, the fluidity was too low, and the moldability was not sufficient. Moreover, the tensile elongation was small and the toughness was not sufficient.
Comparative Example 7 containing PA66 (Comparative Production Example 7) was inferior in terms of heat resistance and low water absorption.

  The present invention can provide a polyamide composition having excellent heat resistance, fluidity, toughness, low water absorption, rigidity, and excellent flame retardancy. The polyamide composition of the present invention can be suitably used as a molding material for various parts such as for automobiles, machinery industry, electricity and electronics, industrial materials, industrial materials, daily use and household goods. It has industrial applicability.

Claims (13)

(A) (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) a diamine containing at least 50 mol% of a branched saturated aliphatic diamine having 3 to 20 carbon atoms. Polyamide made to,
(B) A polyamide composition containing a halogen-based flame retardant. The polyamide composition according to claim 1, wherein the branched saturated aliphatic diamine having 3 to 20 carbon atoms is 2-methylpentamethylenediamine.   The polyamide composition according to claim 1 or 2, wherein the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.   The polyamide composition according to any one of claims 1 to 3, wherein the dicarboxylic acid further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms.   The polyamide composition according to any one of claims 1 to 4, wherein the (A) polyamide is a polyamide obtained by further copolymerizing (c) a lactam and / or an aminocarboxylic acid.   The polyamide composition according to any one of claims 1 to 5, wherein the melting point of the (A) polyamide is 270 to 350 ° C.   The polyamide composition according to any one of claims 1 to 6, wherein the trans isomer ratio in the (A) polyamide is 50 to 85%.   The polyamide composition according to any one of claims 1 to 7, comprising 30 to 60 parts by mass of the (B) halogen flame retardant with respect to 100 parts by mass of the (A) polyamide.   The polyamide composition according to any one of claims 1 to 8, wherein the (B) halogen flame retardant is brominated polystyrene.   (B) 30 to 60 parts by mass of the halogen-based flame retardant, (C) 0 to 30 parts by mass of a flame retardant aid, and (D) an α, β unsaturated dicarboxylic acid anhydride relative to 100 parts by mass of the (A) polyamide. The polyamide composition in any one of Claims 1-9 containing 0-20 mass parts of polymers containing a thing, and (E) inorganic filler 0-200 mass parts.   The polyamide composition according to claim 10, wherein the flame retardant aid (C) is antimony oxides and / or magnesium hydroxide.   The molded article which consists of a polyamide composition in any one of Claims 1-11.   Electrical and electronic parts comprising the polyamide composition according to any one of claims 1-11.