JP5718089B2 - Long fiber reinforced polyamide resin composition and molded body - Google Patents

Description

  The present invention relates to a long fiber reinforced polyamide resin composition and a molded body.

  Polyamides typified by polyamide 6 and polyamide 66 (hereinafter sometimes abbreviated as “PA6” and “PA66”, respectively) and the like are excellent in molding processability, mechanical properties and chemical resistance. Widely used as various parts materials for automobiles, electric and electronic, industrial materials, daily use and household goods.

In the automobile industry, as an environmental measure, there is a demand for weight reduction of a vehicle body using a metal substitute material in order to reduce exhaust gas. In order to meet this requirement, polyamide materials have been used as exterior materials and interior materials, and as a result, the level of required properties such as heat resistance, strength, and appearance for polyamide materials has been further improved. . In particular, since the temperature in the engine room tends to rise, there is an increasing demand for higher heat resistance for polyamide materials.
In addition, in the electrical and electronic industries such as home appliances, a polyamide material having high heat resistance that can withstand the rise in the melting point of solder is required in order to cope with lead-free surface mount (SMT) 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 problems related to the heat resistance 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, it is difficult to obtain a molded product having sufficient characteristics due to severe pyrolysis of the polyamide.

In order to solve the problems related to the thermal decomposition of PA6T, PA6T is composed of an aliphatic polyamide such as PA6 and PA66, or an amorphous aromatic polyamide composed of isophthalic acid and hexamethylenediamine (hereinafter abbreviated as “PA6I”). High melting point semi-aromatic polyamide (hereinafter referred to as “PA6T copolymer”) having terephthalic acid and hexamethylenediamine as main components, which are copolymerized to a low melting point of about 220 to 340 ° C. Is sometimes abbreviated as ")".
As a PA6T copolymer, Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as “PA6T”) which is composed of an aromatic dicarboxylic acid and an aliphatic diamine, and the aliphatic diamine is a mixture of hexamethylenediamine and 2-methylpentamethylenediamine. / 2MPDT "may be abbreviated as") ".

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”), An alicyclic polyamide composed of an alicyclic dicarboxylic acid and an aliphatic diamine has been proposed.
For example, Patent Documents 2 and 3 disclose semi-fats of an alicyclic polyamide (hereinafter sometimes abbreviated as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and another polyamide. A cyclic polyamide (hereinafter sometimes abbreviated as “PA6C copolymer”) is disclosed.
Patent Document 2 discloses that semi-alicyclic polyamide electrical and electronic members containing 1 to 40% 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit have improved solder heat resistance. Discloses that semi-alicyclic polyamide automobile parts are excellent in fluidity and toughness.

In Patent Document 4, an alicyclic polyamide composed of an alicyclic dicarboxylic acid and a diamine having a branched substituent has excellent heat resistance, fluidity, toughness, low water absorption, rigidity, and a high melting point. It is disclosed to be a polyamide.
Patent Document 5 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 It is disclosed that it is excellent in heat resistance and the like. Further, as a method for producing the polyamide, 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine are reacted at 230 ° C. or lower to prepare a prepolymer, and the prepolymer is solid-phase polymerized at 230 ° C. to obtain a melting point of 311 ° C. Is disclosed.
In Patent Document 6, 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.

In Patent Document 7, in the production of a polyamide comprising a diamine component containing an aromatic diacid containing terephthalic acid and 2-methylpentanediamine, cyclization of 2-methylpentamethylenediamine by addition of formic acid (with cyclic amino group and Is significantly reduced.
In Patent Documents 8 and 9, in polypentamethylene adipamide resin, the retention of the polyamide is stabilized by reducing the bonding of the cyclic amino group derived from pentamethylenediamine to the polymer terminal by controlling the polymerization temperature. It is disclosed that the heat resistance and the heat resistance can be improved.

JP-T 6-503590 Japanese National Patent Publication No. 11-512476 Special table 2001-514695 gazette International Publication No. 2009/113590 Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 Pamphlet Japanese National Patent Publication No. 8-503018 JP 2003-292612 A JP 2004-75932 A

Although PA6T copolymer has the characteristics of low water absorption, high heat resistance, and high chemical resistance, it is low in fluidity and insufficient from the viewpoint of moldability and surface appearance characteristics of molded products. Furthermore, it is inferior to toughness and light resistance. Therefore, when used as an exterior part, appearance characteristics are required, and when used for applications such as exposure to sunlight, improvement of those characteristics is required.
Further, PA6T copolymer has a large specific gravity, 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, but it has fluidity, moldability, toughness, molded product surface appearance, and light resistance. However, the level of improvement is insufficient.
In addition, PA46 has good heat resistance and moldability, but has a high water absorption rate, and has a problem that a dimensional change and a decrease in mechanical properties due to water absorption are remarkably large. There are cases where the requirements cannot be met in terms of dimensional changes.

The PA6C copolymers disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity.
The polyamides disclosed in Patent Documents 5 and 6 are also insufficiently improved in terms of toughness, strength, and fluidity.

In addition, regarding the polyamide disclosed in Patent Document 7, it is described that a high molecular weight product can be obtained by reducing the amount of cyclic amino group bonded to the polymer terminal, but cyclic amino bonded to the polymer terminal is described. There is no mention of the advantages of having a certain amount of groups.
In addition, with respect to the polyamides disclosed in Patent Documents 8 and 9, there is no description about the advantage of having a certain amount or more of the cyclic amino group bonded to the polymer terminal, and the polymer is obtained by lowering the polycondensation temperature. Since the amount of the cyclic amino group bonded to the terminal is reduced, it is not assumed that a polyamide having a high melting point of 300 ° C. or higher is produced.

  The long fiber reinforced polyamide compositions containing these conventionally proposed polyamides cannot satisfy the demand for high heat resistance in the automobile industry, the electric and electronic industries, particularly in terms of strength during heat and heat stability.

  The problem to be solved by the present invention is to provide a long fiber reinforced polyamide resin composition that is excellent in strength, strength at heat, durability, low water absorption, and heat stability.

As a result of intensive studies to solve the above problems, the present inventors have obtained a polyamide obtained by polymerizing alicyclic dicarboxylic acid and a diamine having a pentamethylenediamine skeleton as main constituent components, The present invention is completed by finding that the above-mentioned problems can be solved by using a long-fiber reinforced polyamide resin composition containing polyamide having a constant end amount and reinforcing fibers having a weight average fiber length of 1 to 15 mm. It came to.
That is, the present invention is as follows.

[1]
A pellet of a long fiber reinforced polyamide resin composition,
(A) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid;
(B) a diamine containing a diamine having a pentamethylenediamine skeleton of at least 50 mol%;
A polyamide obtained by polymerizing
(A) polyamide whose cyclic amino terminal amount of the polyamide is 30 to 60 μequivalent / g
In the long fiber reinforced polyamide resin composition, 20 to 80% by mass,
(B) Reinforcing fiber having a weight average fiber length of 1 to 15 mm in the long fiber reinforced polyamide resin composition, 20 to 80% by mass,
A pellet of a long fiber reinforced polyamide resin composition.
[2]
The pellet of the long fiber-reinforced polyamide resin composition according to [1], wherein the (A) polyamide has a sulfuric acid relative viscosity ηr at 25 ° C. of 2.3 or more.
[3]
[1] or [A] wherein the amino terminal amount of the polyamide (A) is 20 μeq / g or more.
2] pellets of the long fiber reinforced polyamide resin composition described in [2].
[4]
The long fiber reinforced polyamide resin composition pellets according to any one of [1] to [3], wherein the polyamide (A) is a polyamide polymerized at a reaction temperature higher than 300 ° C.
[5]
The long fiber reinforced polyamide resin according to any one of [1] to [4], wherein the cyclic amino terminal of the polyamide (A) is formed by a cyclization reaction of a diamine having a pentamethylenediamine skeleton. Composition pellets .
[6]
The long fiber reinforced polyamide resin composition pellets according to any one of [1] to [5], wherein the polyamide (A) is a polyamide obtained through a solid phase polymerization step in at least a part of the polymerization step. .
[7]
The long fiber reinforced polyamide resin according to any one of [1] to [6], wherein the (B) reinforcing fiber is at least one selected from the group consisting of glass fiber, carbon fiber, boron fiber, and metal fiber. Composition pellets .
[8]
A molded body using pellets of the long fiber reinforced polyamide resin composition according to any one of [1] to [7], wherein the (B) reinforcing fiber is dispersed with a weight average fiber length of 1 mm to 10 mm. Forming body.

  ADVANTAGE OF THE INVENTION According to this invention, the long fiber reinforced polyamide resin composition excellent in intensity | strength, strength at the time of a heat | fever, durability, low water absorption, and heat-resistant stability can be provided.

  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.

[Long fiber reinforced polyamide resin composition]
The long fiber reinforced polyamide resin composition of the present embodiment comprises (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid, and (b) a diamine containing a diamine having a pentamethylenediamine skeleton of at least 50 mol%. Are polymerized, the cyclic amino terminal amount is 30 to 60 μeq / g, (A) 20 to 80% by mass of polyamide, and (B) reinforcing fibers 20 to 80 having a weight average fiber length of 1 to 15 mm. It is a long fiber reinforced polyamide resin composition containing a mass%.

((A) Polyamide)
(A) Polyamide is a polyamide obtained by polymerizing the following (a) and (b) as described above.
(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 pentamethylenediamine skeleton.
In the present specification, polyamide means a polymer having an amide bond (—NHCO—) in the main chain.

<(A) Dicarboxylic acid>
(A) The (a) dicarboxylic acid constituting the polyamide contains at least 50 mol% of an alicyclic dicarboxylic acid.
(A) By using a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid, a polyamide having excellent strength, hot strength, durability and the like and having a high melting point can be obtained. Further, the polyamide constituting the long fiber reinforced polyamide resin composition of the present embodiment can be obtained as a polyamide having excellent heat stability and low water absorption.

Examples of the alicyclic dicarboxylic acid (hereinafter sometimes referred to as (a-1) alicyclic dicarboxylic acid, or simply referred to as alicyclic dicarboxylic acid) include, for example, 1, Fatty acids such as 4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid having an alicyclic structure of 3 to 10 carbon atoms, preferably 5 to 10 carbon atoms A cyclic dicarboxylic acid is mentioned.
The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.
Examples of the substituent in the alicyclic dicarboxylic acid include alkyl 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. Groups and the like.
As the alicyclic dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid is preferable from the viewpoint of heat resistance, low water absorption, strength, and the like.
As the alicyclic dicarboxylic acid, one kind may be used alone, or two or more kinds may be used in combination.

Alicyclic dicarboxylic acids have trans and cis geometric isomers.
As the alicyclic dicarboxylic acid as a raw material monomer for polyamide, either a trans isomer or a cis isomer may be used, or a mixture of a trans isomer and a cis isomer may be used.
The alicyclic dicarboxylic acid is isomerized at a high temperature to have a certain ratio, and the cis isomer has higher water solubility of the equivalent salt with the diamine than the trans isomer. From these viewpoints, as a raw material monomer, the trans isomer / cis isomer ratio is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and still more preferably 35 in terms of molar ratio. / 65 to 15/85.
The trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).

  Examples of (a) dicarboxylic acids other than alicyclic carboxylic acids (hereinafter referred to as (a-2) dicarboxylic acids other than alicyclic dicarboxylic acids) in dicarboxylic acids include, for example, fatty acids. Group dicarboxylic acid and aromatic dicarboxylic acid.

  Examples of the aliphatic dicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, and 2,3-diethylglutaric acid. 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, Examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

Examples of the aromatic dicarboxylic acid include unsubstituted terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. Examples thereof include aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with various substituents.
Examples of the various substituents in the aromatic dicarboxylic acid include an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, a chloro group, and a bromo group. Examples thereof include halogen groups, silyl groups having 1 to 6 carbon atoms, and sulfonic acid groups and salts thereof such as sodium salts.

(A-2) When a dicarboxylic acid other than an alicyclic dicarboxylic acid is copolymerized, it is preferably an aliphatic dicarboxylic acid, more preferably in terms of heat resistance, fluidity, toughness, low water absorption, strength, and the like. Is an aliphatic dicarboxylic acid having 6 or more carbon atoms.
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 the dicarboxylic acid other than the alicyclic dicarboxylic acid, one kind may be used alone, or two or more kinds may be used in combination.

(A) The dicarboxylic acid may further contain a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid as long as the object of the present embodiment is not impaired.
As the polyvalent carboxylic acid, one kind may be used alone, or two or more kinds may be used in combination.

The proportion (mol%) 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%, Preferably it is 60-100 mol%, More preferably, it is 70-100 mol%, More preferably, it is 100 mol%.
When the ratio of the alicyclic dicarboxylic acid is at least 50 mol%, that is, 50 mol% or more, a polyamide having excellent strength and toughness and a high melting point can be obtained.
(A) The proportion (mol%) of dicarboxylic acid other than (a-2) alicyclic dicarboxylic acid in dicarboxylic acid is 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0. ˜30 mol%.

  When (a) dicarboxylic acid other than (a-2) alicyclic dicarboxylic acid in dicarboxylic acid contains aliphatic dicarboxylic acid having 10 or more carbon atoms, preferably (a-1) alicyclic dicarboxylic acid. The acid is 50 to 99.9 mol% and (a-2) the aliphatic dicarboxylic acid having 10 or more carbon atoms is 0.1 to 50 mol%, more preferably (a-1) the alicyclic dicarboxylic acid is 60 to 99 mol% and (a-2) 1 to 40 mol% of aliphatic dicarboxylic acid having 10 or more carbon atoms, more preferably (a-1) 70 to 99 mol% of alicyclic dicarboxylic acid and (a-2) ) 1 to 30 mol% of an aliphatic dicarboxylic acid having 10 or more carbon atoms.

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. It is done.

<(B) Diamine>
(A) The (b) diamine constituting the polyamide is at least 50 mol% of a diamine having a pentamethylenediamine skeleton (hereinafter, referred to as (b-1) a diamine having a pentamethylenediamine skeleton). including.
(B) By using a diamine containing at least 50 mol% of a diamine having a pentamethylenediamine skeleton, a polyamide having excellent strength, strength at heat, durability, and the like can be obtained. It can also be obtained as a polyamide having excellent moldability.

(B-1) The diamine having a pentamethylenediamine skeleton can also be expressed as a diamine having a 1,5-diaminopentane skeleton.
Examples of the diamine having a pentamethylenediamine skeleton include pentamethylenediamine, 2-methylpentamethylenediamine, 2-ethylpentamethylenediamine, 3-n-butylpentamethylenediamine, 2,4-dimethylpentamethylenediamine, 2- Examples thereof include saturated aliphatic diamines having 5 to 20 carbon atoms such as methyl-3-ethylpentamethylenediamine and 2,2,4-trimethylpentamethylenediamine.
The diamines having the pentamethylenediamine skeleton are 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 2-ethyl-1,5-diaminopentane, and 3-n-butyl-1,5, respectively. -Diaminopentane, 2,4-dimethyl-1,5-diaminopentane, 2-methyl-3-ethyl-1,5-diaminopentane, 2,2,4-trimethyl-1,5-diaminopentane .
The diamine having a pentamethylenediamine skeleton is preferably pentamethylenediamine and 2-methylpentamethylenediamine, more preferably 2-methylpentamethylenediamine, from the viewpoints of heat resistance and strength.
One type of diamine having a pentamethylenediamine skeleton may be used alone, or two or more types may be used in combination.

  (B) Among diamines, diamines other than diamines having a pentamethylenediamine skeleton (hereinafter referred to as (b-2) diamines other than diamines having a pentamethylenediamine skeleton) may be, for example, Aliphatic diamines, alicyclic diamines, aromatic diamines and the like can be mentioned.

Examples of the aliphatic diamine include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, 2-methylhexamethylenediamine, 2,4-dimethylhexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Examples thereof include saturated aliphatic diamines having 2 to 20 carbon atoms such as 2-methyloctamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.
The aliphatic diamine does not include a diamine having a pentamethylenediamine skeleton.

  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 diamines having an aromatic structure such as metaxylylenediamine.

(B-2) The diamine other than the diamine having a pentamethylenediamine skeleton is preferably an aliphatic diamine and an alicyclic diamine in terms of heat resistance, fluidity, toughness, low water absorption, strength, and the like. More preferably, it 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 even more preferably hexamethylene diamine.
(B-2) One type of diamine other than the diamine having a pentamethylenediamine skeleton may be used alone, or two or more types 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 alone, or two or more kinds may be used in combination.

The ratio (mol%) of the diamine having (b-1) pentamethylenediamine skeleton in (b) diamine is at least 50 mol%. The proportion of the diamine having a pentamethylenediamine skeleton is 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 80 to 100 mol%, still more preferably 85 to 100 mol%, More preferably, it is 90-100 mol%, Most preferably, it is 100 mol%.
(B-1) When the ratio of the diamine having a pentamethylenediamine skeleton is at least 50 mol%, that is, 50 mol% or more, a polyamide having excellent toughness and strength can be obtained.
The ratio (mol%) of diamine other than the diamine having (b-2) pentamethylenediamine skeleton in (b) diamine is 0 to 50 mol%, preferably 0 to 40 mol%, more preferably. It is 0-20 mol%, More preferably, it is 0-15 mol%, More preferably, it is 0-10 mol%, Most preferably, it is 0 mol%.

  The addition amount of (a) dicarboxylic acid and the addition amount of (b) diamine are preferably around the same molar amount. In view of the molar ratio of (b) the escape of diamine out of the reaction system during the polymerization reaction, the molar amount of (b) diamine is preferably Is 0.9 to 1.2, more preferably 0.95 to 1.1, and still more preferably 0.98 to 1.05.

<(C) Lactam and / or aminocarboxylic acid>
The polyamide constituting the long fiber reinforced polyamide resin composition of the present embodiment may be a polyamide obtained by further copolymerizing (c) lactam and / or aminocarboxylic acid from the viewpoint of toughness.
The (c) lactam and / or aminocarboxylic acid used in the present embodiment means a lactam and / or aminocarboxylic acid that can be polymerized to polyamide.
When the polyamide is a polyamide obtained by copolymerizing (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, (c) lactam and / or aminocarboxylic acid is carbon A lactam and / or aminocarboxylic acid having 4 to 14 carbon atoms is preferred, and a lactam and / or aminocarboxylic acid having 6 to 12 carbon atoms is more preferred.

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

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

<End sealant>
When the polyamide is polymerized from (a) dicarboxylic acid and (b) diamine, a known end-capping agent can be further added for polymerization 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, monoalcohols, and the like, from the viewpoint of thermal stability. And monocarboxylic acids and monoamines are preferred.
As a terminal blocker, one type may be used alone, or two or more types 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, isobutyric acid and other aliphatic monocarboxylic acids; cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids; 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, one type may be used alone, or two or more types may be used in combination.

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; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and And cyclic amines such as pyrrolidine, piperidine, 3-methylpiperidine; and the like.
As the monoamine, one type may be used alone, or two or more types may be used in combination.

The combination of (a) dicarboxylic acid and (b) diamine is not particularly limited. For example, (a-1) at least 50 mol% of alicyclic dicarboxylic acid and (b-1) at least 50 mol% of 2-methylpentamethylenediamine or a combination of pentamethylenediamine is preferred, (a-1) at least 50 mol% 1,4-cyclohexanedicarboxylic acid and (b-1) at least 50 mol% 2-methylpentamethylenediamine. More preferred.
By polymerizing these combinations (a) dicarboxylic acid and (b) diamine as components of polyamide, polyamide having excellent strength, heat strength, durability, low water absorption and heat stability, and having a high melting point; can do.

((A) Polyamide production method)
The production method of the polyamide (A) constituting the long fiber reinforced polyamide resin composition of the present embodiment is not particularly limited, and (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (B) It can manufacture with the manufacturing method of polyamide including the process of superposing | polymerizing the diamine containing the diamine which has a pentamethylenediamine frame | skeleton of at least 50 mol%. (A) The polyamide is preferably a polyamide obtained through a solid phase polymerization step in at least a part of the polymerization step.
(A) As a manufacturing method of polyamide, it is preferable to further include the process of raising the polymerization degree of polyamide.

(A) It does not specifically limit as a manufacturing method of polyamide, For example, the method etc. which are illustrated below are mentioned:
1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter sometimes referred to 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 suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as “prepolymer”).・ It may be abbreviated as “extrusion polymerization method”),
4) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated, and the degree of polymerization is further increased while maintaining the solid state of the precipitated prepolymer at a temperature below the melting point of the polyamide (hereinafter, And may be abbreviated as “prepolymer / solid phase polymerization method”).
5) A method of polymerizing in one step while maintaining the dicarboxylic acid / diamine salt or mixture thereof in a solid state (hereinafter sometimes abbreviated as “one-step solid phase polymerization method”),
6) A method of polymerizing using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine (hereinafter sometimes abbreviated as “solution method”).

(A) The production method of polyamide is preferably 1) hot melt polymerization method, 2) hot melt polymerization / solid phase polymerization method, 4) prepolymer / solid phase polymerization method, and 5) one-stage solid phase polymerization method. More preferably, 2) hot melt polymerization / solid phase polymerization and 4) prepolymer / solid phase polymerization.
(A) In the method for producing a polyamide, it is preferable to perform solid phase polymerization in terms of improving the molecular weight of the polyamide, and the method for improving the molecular weight of the polyamide by performing solid phase polymerization is to increase the molecular weight by a hot melt polymerization method. Rather than improving, it is preferable in that the cyclic amino terminal amount of the polyamide can be controlled to a predetermined amount.

(A) In the method for producing polyamide, when performing hot melt polymerization, it is preferable to add an additive during the polymerization.
As an additive at the time of polymerization, (b) diamine which is a raw material of polyamide is mentioned.
The amount of (b) diamine added as an additive during polymerization means the amount of diamine added to (b) diamine used in the production of an equimolar amount of dicarboxylic acid / diamine salt, preferably 0. 0.1 to 10 mol%, more preferably 0.5 to 5 mol%, still more preferably 1.5 to 4.5 mol%, still more preferably 2.6 to 4 mol%. .
(B) When the addition amount of the diamine is within the above range, the cyclic amino terminal amount and the amino terminal amount can be controlled to target values.

  As additives during polymerization, organic acids such as formic acid and acetic acid can also be added. By adding formic acid or the like, it may be possible to more easily control the amount of cyclic amino terminal at the polymer terminal.

(A) In the production method of polyamide, the polymerization form may be a batch type or a continuous type.
In the hot melt polymerization method, for example, the polymerization reaction can be performed using an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, or the like.

(A) The method for producing the polyamide is not particularly limited, and the polyamide can be produced by a batch-type hot melt polymerization method.
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., pressure reduction is started to atmospheric pressure (gauge The 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. It is preferable to control the temperature so that the reaction temperature at the end of the reaction becomes the maximum temperature, and the maximum temperature is preferably 280 to 400 ° C. Pressurize with an inert gas such as nitrogen to extrude the polyamide melt as a strand. The strand is cooled and cut to obtain pellets.

(A) The method for producing the polyamide is not particularly limited, and the polyamide can be produced by a continuous hot melt polymerization method.
Examples of the continuous 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 40-60 wt% solution containing is preheated to about 40-100 ° C. in a pre-container vessel and then transferred to a concentrator / reactor and about 0.1-0.5 MPa (gauge pressure) Concentrate to about 70-90% under pressure and temperature of about 200-270 ° C. to obtain a concentrated solution. Next, the concentrated solution is discharged to a flasher maintained at a temperature of about 200 to 400 ° 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. It is preferable to control the temperature so that the reaction temperature at the end of the reaction becomes the maximum temperature, and the maximum temperature is preferably 280 to 400 ° C. The polyamide melt is extruded into strands, cooled and cut into pellets.

  The maximum reaction temperature in the hot melt polymerization is preferably 280 to 400 ° C, more preferably a temperature exceeding 300 ° C. The maximum temperature is more preferably 360 ° C. or lower. In the hot melt polymerization, the amount of the cyclic amino terminal can be easily controlled while suppressing the thermal decomposition of the polyamide by setting the reaction temperature to the highest temperature within the above range.

(A) It does not specifically limit as a manufacturing method of polyamide, Polyamide can be manufactured with the solid-phase polymerization method described below.
As the solid phase polymerization method, for example, a tumbler type reactor, a vibration dryer type reactor, a nauter mixer type reactor, a stirring type reactor, or the like can be used.
Put polyamide pellets, flakes, or powder into the above reactor, under an inert gas stream such as nitrogen, argon, and helium, or under reduced pressure, and while pulling the internal gas under reduced pressure at the top of the reactor An inert gas may be supplied from below, and the molecular weight of the polyamide is improved by heating at a temperature below the melting point of the polyamide. The reaction temperature of the solid phase polymerization is preferably 100 to 350 ° C, more preferably 120 to 300 ° C, and further preferably 150 to 270 ° C.
The inert gas may be supplied from the lower part of the reactor under the flow of inert gas or under reduced pressure, and while pulling the internal gas to the reduced pressure at the upper part of the reactor, and the heating is stopped, preferably 0 to 100 ° C. More preferably, after the reaction temperature is lowered from room temperature to 60 ° C., the polyamide can be taken out from the reactor.

  (A) As a production method of polyamide, preferably, hot melt polymerization is performed at a maximum reaction temperature exceeding 300 ° C., and dicarboxylic acid and diamine (including lactam and / or aminocarboxylic acid, if necessary). And a polyamide produced by polymerizing a polyamide obtained by a hot melt polymerization method or a prepolymer method by solid phase polymerization at a reaction temperature not higher than the melting point of the polyamide. preferable. By these production methods, the amount of the cyclic amino terminus can be easily controlled to increase the molecular weight, and the polyamide having excellent strength, durability during heat, hydrolysis resistance, etc. can be obtained. The fiber reinforced polyamide resin composition is excellent in strength, strength at heat, and heat stability.

The polymer terminal of (A) polyamide is any of 1) amino terminal, 2) carboxyl terminal, 3) cyclic amino terminal, 4) terminal by end-capping agent, and 5) other terminal, 3) cyclic It has an amino terminus of 30-60 μeq / g.
The polymer terminal of the polyamide means a terminal part of a polymer chain of a polymer obtained by polymerizing dicarboxylic acid and diamine (including lactam and / or aminocarboxylic acid, if necessary) by an amide bond.

1) The amino terminal means that the polymer terminal is an amino group (—NH ₂ group), and the terminal of the polymer chain is derived from the raw material diamine.
2) The carboxyl end means that the polymer end is a carboxyl group (—COOH group), and the end of the polymer chain is derived from the raw dicarboxylic acid.
3) Cyclic amino terminal means that the polymer terminal is a cyclic amino group.
The cyclic amino group is a group represented by the following formula.

In said formula, R shows a C1-C4 alkyl group, such as a hydrogen atom or a methyl group, an ethyl group, and a t-butyl group.
The cyclic amino terminal may be a piperidine structure formed by cyclization by a deammonification reaction of a diamine having a pentamethylenediamine skeleton as a raw material. In this case, R is a pentamethylene skeleton of a diamine having a pentamethylenediamine skeleton. The alkyl group of the side chain part other than is shown. In the above formula, R is exemplified as mono-substitution, but may be di-substitution or poly-substitution of three or more substitutions so as to match the side chain portion of the diamine having a pentamethylenediamine skeleton. Also good.

4) The end by the end-capping agent means that the end of the polymer is capped by the end-capping agent added at the time of polymerization, and has a structure derived from end-capping agents such as monocarboxylic acid and monoamine. .
5) The other terminal is a polymer terminal not classified in 1) to 4), and examples thereof include a terminal generated by deammonia reaction at the amino terminal and a terminal generated by decarboxylation reaction at the carboxyl terminal.

(A) The cyclic amino terminal amount of polyamide is 30-60 microequivalent / g as mentioned above, Preferably it is 35-55 microequivalent / g.
When the cyclic amino terminal amount is within the above range, the strength, hot strength, durability, and heat resistance stability of the long fiber reinforced polyamide resin composition can be improved.

The cyclic amino terminal amount is represented by the number of moles of cyclic amino terminal present in 1 g of polyamide.
The amount of cyclic amino terminal can be measured using 1H-NMR as described in the following examples.
For example, it can be calculated based on the integral ratio of hydrogen bonded to carbon adjacent to the nitrogen atom of the piperidine ring and hydrogen bonded to carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain.

The cyclic amino terminus is generated by (1) a dehydration reaction between a cyclic amine compound having a piperidine ring and a carboxyl terminus, or (2) a deammonia reaction within the polymer molecule at the amino terminus of the polymer terminus. .
(1) The cyclic amino terminus generated by the dehydration reaction between the cyclic amine compound and the carboxyl terminus may be (1a) a cyclic amine compound having a piperidine ring may be added to the polymerization reaction system as a terminal blocking agent. (1b) A diamine having a pentamethylenediamine skeleton can be produced from a cyclic amine compound produced in a polymerization reaction system by deammonia reaction in the monomer molecule.

(A) The cyclic amino terminal of the polyamide is preferably a terminal derived from a cyclization reaction of a raw material diamine having a pentamethylenediamine skeleton. That is, (1b) the diamine having a pentamethylenediamine skeleton can be obtained by deammonia reaction in the monomer molecule to cause dehydration reaction between the cyclic amine compound generated in the polymerization reaction system and the carboxyl group, or (2 It is preferable that the amino terminal of the polymer terminal is obtained by deammonification reaction in the polymer molecule.
Adding a cyclic amine compound having a piperidine ring as an end capping agent at the initial stage of polymerization results in the low molecular weight carboxyl end being capped at the initial stage of polymerization, thus reducing the polymerization reaction rate of the polyamide. While it is difficult to obtain a high molecular weight product, a cyclic amine having a piperidine ring generated in the middle of the reaction will be sealed at a later stage of polymerization after a certain degree of high molecular weight. Getting a body becomes easier.
Although it is possible to add a cyclic amine compound having a piperidine ring as an end-capping agent in the latter stage of polymerization with a high molecular weight, it is necessary to provide equipment to be added to the polymerization system in a high pressure state. It is preferable because the production methods 1b) and (2) are simple.

In order to produce a cyclic amino terminus from a raw material diamine having a pentamethylenediamine skeleton in the polymerization system and adjust the amount of cyclic amino terminus within the scope of the present invention, a polymerization temperature, a reaction time, and a diamine that produces a cyclic amine. A method of controlling by appropriately adjusting the amount of addition and the like is effective.
(A) In order to bring the cyclic amino terminal amount of the polyamide within the scope of the present invention, it is necessary to promote the formation of a cyclic amine having a piperidine ring, and the reaction temperature of the polymerization of the polyamide is preferably 280 to 400 ° C. More preferably, it exceeds 300 ° C., more preferably 320 ° C. or higher. The reaction temperature for polyamide polymerization is preferably 360 ° C. or lower.
The reaction temperature is preferably 280 ° C. or higher from the viewpoint of promoting the formation of the cyclic amino terminus, while 400 ° C. or lower is preferable from the viewpoint of suppressing the formation of an excessive cyclic amino terminus.
Moreover, the adjustment of the reaction time is also an effective method, and it is particularly effective to adjust the time of the reaction temperature exceeding 300 ° C. as appropriate.

(A) The amino terminal amount of polyamide is preferably 20 μeq / g or more, more preferably 20 to 100 μeq / g, and further preferably 25 to 70 μeq / g.
When the amino terminal amount is within the above range, the hydrolysis resistance and heat retention stability of the (A) polyamide can be improved.

The amino terminal amount is represented by the number of moles of amino terminal present in 1 g of polyamide.
Amino terminal amount can be measured using the method described in the following Example.

(A) The molecular weight of polyamide is preferably 25 ° C. sulfuric acid relative viscosity ηr, and the sulfuric acid relative viscosity ηr at 25 ° C. is preferably 2.3 or more. More preferably, it is 2.3-7.0, More preferably, it is 2.5-5.5, More preferably, it is 2.8-4.0.
When the relative viscosity ηr of sulfuric acid at 25 ° C. is 2.3 or more, the long fiber reinforced polyamide resin composition is excellent in strength, durability, and the like. (A) When the relative viscosity ηr of sulfuric acid at 25 ° C. of the polyamide is 7.0 or less, a long fiber reinforced polyamide resin composition having excellent fluidity can be obtained.

  Measurement of the relative viscosity of sulfuric acid at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920 as described in the following examples.

(A) The melting point of polyamide 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.
When the melting point Tm2 of the polyamide is 270 ° C. or higher, a polyamide having excellent heat resistance can be obtained. Moreover, when the melting point Tm2 of the polyamide is 350 ° C. or less, the thermal decomposition of the polyamide in the melt processing such as extrusion and molding can be suppressed.

(A) The measurement of the melting point (Tm1 or Tm2) and heat of fusion ΔH of polyamide 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.

((B) Reinforcing fiber)
The (B) reinforcing fiber contained in the long fiber reinforced polyamide resin composition in this embodiment will be described.
The content of the (B) reinforcing fiber in the long fiber reinforced polyamide resin composition of the present embodiment is 20 to 80% by mass, preferably 25 in terms of strength, hot strength, durability, and moldability. It is -75 mass%, More preferably, it is 30-70 mass%.
The weight average fiber length of the (B) reinforcing fiber in the long fiber reinforced polyamide resin composition is 1 to 15 mm, preferably 3 to 12 mm from the viewpoint of improving mechanical strength, rigidity and moldability.

The weight average fiber length of the (B) reinforcing fiber is removed by burning or dissolving only the polyamide resin of the long fiber reinforced polyamide resin composition, then observed with an optical microscope, and arbitrarily with an image analyzer. It is obtained by measuring the length of 400 selected reinforcing fibers and calculating the average value.
Here, when the length of each of the (B) reinforcing fibers is L1, L2,. In the following formula, “i” is an integer from 1 to 400.
Weight average fiber length = Σ (Li ² ) / ΣLi
In addition, the said weight average fiber length is a value applied with respect to the (B) reinforced fiber of the state contained in the long fiber reinforced polyamide resin composition of this embodiment.
That is, the weight average fiber length of the reinforcing fiber (B) before blending with the (A) polyamide resin is not limited to the above.

(B) The material of the reinforcing fiber is not particularly limited as long as it is a reinforcing fiber generally used for a polyamide resin.
For example, inorganic fiber such as glass fiber, carbon fiber, boron fiber, metal fiber (eg, stainless fiber, aluminum fiber, copper fiber), polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaffin Organic materials such as phenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, wholly aromatic polyamide fiber such as fiber obtained from condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid, or wholly aromatic liquid crystal polyester fiber Is mentioned.
(B) As reinforcing fiber, the said material may be used independently and 2 or more types may be used together.
Especially, it is preferable that it is 1 or more types chosen from a glass fiber, a carbon fiber, a boron fiber, and a metal fiber from a viewpoint of an improvement of mechanical strength and rigidity, and a glass fiber and / or a carbon fiber are more preferable.

The (B) reinforcing fiber is not particularly limited with respect to the average fiber diameter of the single fiber, but, for example, one having a diameter of 5 to 25 μm is generally used.
The average fiber diameter of single fibers is obtained by observing the reinforcing fibers to be used under an optical microscope and calculating the average value when measuring 400 fiber diameters arbitrarily selected using an image analyzer. It is done.
In addition, as the reinforcing fiber (B), it is preferable to use roving which is a continuous fiber obtained by focusing single fibers.

(B) From the viewpoint of improving the adhesion between the (A) polyamide resin and the reinforcing fiber, it is preferable to perform a surface treatment with a treatment agent such as a coupling agent.
The treatment agent for surface treatment is not particularly limited, and a conventionally known surface treatment agent is used.
For example, for glass fibers, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, vinyltriethoxysilane and γ-glycid A silane coupling agent such as xylpropyltrimethoxysilane can be applied.

For reinforced fibers, copolymers, epoxy compounds, polyurethane resins, and homopolymers of acrylic acid containing carboxylic acid anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers as constituent units as sizing agents , Copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, or tertiary amines. In particular, from the viewpoint of mechanical properties (particularly strength) of the polyamide resin composition, a copolymer (carboxylic anhydride) containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as constituent units. Also referred to as a copolymer containing as a constituent unit an unsaturated vinyl monomer containing and an unsaturated vinyl monomer excluding the unsaturated vinyl monomer containing a carboxylic acid anhydride), an epoxy compound, and a polyurethane resin A copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units, and a polyurethane resin are more preferable.
The unsaturated vinyl monomer in the copolymer does not include a carboxylic acid anhydride-containing unsaturated vinyl monomer.
As the sizing agent, one kind may be used, or two or more kinds may be used in combination.
The sizing agent preferably imparts (adds) 0.2 to 3% by mass, more preferably 0.3 to 2% by mass, (adds) the solid content of 100% by mass of the reinforcing fiber. .
From the viewpoint of maintaining the bunching of the reinforcing fibers, it is preferable that the addition amount of the sizing agent is 0.2% by mass or more as a solid content with respect to 100% by mass of the reinforcing fibers. From the viewpoint of improving the thermal stability of the long fiber reinforced polyamide resin composition, the addition amount of the sizing agent is preferably 3% by mass or less as the solid content.

[Method for Producing Long Fiber Reinforced Polyamide Resin Composition]
The production method of the long fiber reinforced polyamide resin composition in the present embodiment is not particularly limited. For example, (A) polyamide resin obtained by melting and kneading (A) polyamide resin with a twin screw extruder is melted. (B) A pulverization method in which rovings of reinforcing fibers are impregnated to obtain a resin-impregnated strand, and a resin-impregnated strand is spirally twisted as described in JP-A-2008-221574. The method of fully impregnating is mentioned.

[Other additives]
The long fiber reinforced polyamide resin composition in the present embodiment may contain a predetermined additive depending on desired characteristics.
In the long fiber reinforced polyamide resin composition, additives commonly used for polyamide, for example, colorants such as pigments and dyes (including colored master batches), flame retardants, and the like, within a range that does not impair the purpose of the present embodiment. Fibrilizing agent, lubricant, fluorescent bleaching agent, plasticizer, antioxidant, stabilizer (including heat stabilizer and light stabilizer), UV absorber, antistatic agent, fluidity improver, filler, reinforcement Agents, spreading agents, nucleating agents, rubber, reinforcing agents and other polymers can also be contained.

  Further, in the long fiber reinforced polyamide resin composition, as a stabilizer, a phenol stabilizer, a phosphorus stabilizer, an amine stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb of the periodic table , One or more selected from the group consisting of metal salts of elements of Group IVa and Group IVb, and halides of alkali metals and alkaline earth metals.

The phenol-based stabilizer is not particularly limited, and examples thereof include hindered phenol compounds.
The phenol-based stabilizer has a property of imparting heat resistance and light resistance to resins and fibers such as polyamide.
The hindered phenol compound is not particularly limited, and examples thereof include N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide). ), Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4- Hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3, -Di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid and the like. Among these, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.
As a phenol type stabilizer, you may use by 1 type and may be used in combination of 2 or more types.
When using a phenol stabilizer, the blending amount of the phenol stabilizer in the long fiber reinforced polyamide resin composition is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the long fiber reinforced polyamide resin composition. Yes, more preferably 0.1 to 1 part by mass. When the blending amount is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

  The phosphorus stabilizer is not particularly limited, for example, pentaerythritol type phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, Phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4- Di-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene-bis ( -Methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, 4,4'-isopropylidenebis (2-t- Butylphenyl) ・ di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphos Phyto, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidenediphenyl diphosphite, tris ( Mono, di-mixed nonylphenyl) phosphite, 4,4′-isopropylidenebis ( -T-butylphenyl) .di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di -T-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenyl polyphosphite, bis (octylphenyl) bis (4,4'-butylidenebis (3-methyl-6-t) -Butylphenyl)), 1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) diphosphite, tris (4,4 ' -Isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite, 2 2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2, 4-di-t-butyl-5-methylphenyl) -4,4′-biphenylene diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite, etc. Can be mentioned. Of these, pentaerythritol phosphite compounds and tris (2,4-di-t-butylphenyl) phosphite are preferable from the viewpoint of further improving the heat aging resistance and reducing the generated gas.

  The pentaerythritol type phosphite compound is not particularly limited. For example, 2,6-di-t-butyl-4-methylphenyl phenyl pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl methyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2-ethylhexyl pentaerythritol diphosphite, 2,6-di-t-butyl- 4-methylphenyl isodecyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl lauryl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl Isotridecyl pentaerythritol diphosphite, 2,6-di-t-butyl -Methylphenyl stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl Benzyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl ethyl cellosolve pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl butyl carbitol Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl nonylphenyl penta Erythritol diphosphite, bis (2,6-di-t Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2,6-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl, 2,4-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2,4-di-t-octylphenyl · pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2-cyclohexyl Phenyl pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl phenyl pentaerythritol Tall diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos Fight etc. are mentioned. Among them, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite are preferred, and bis (2 , 6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

As a phosphorus stabilizer, you may use by 1 type and may be used in combination of 2 or more types.
When using a phosphorus stabilizer, the compounding quantity of the phosphorus stabilizer in a long fiber reinforced polyamide resin composition is 0.01-1 mass part with respect to 100 mass parts of a long fiber reinforced polyamide resin composition, More preferably, it is 0.1-1 mass part. When the blending amount is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

The amine stabilizer is not particularly limited, and examples thereof include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetra Methylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetra Methylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy)- 2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl)- Oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6 6-tetramethyl-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6) -Tetramethyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2 , 6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4 -Tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl) -4-hydroxyphenyl) Lopionyloxy] 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 and the like.
As the amine stabilizer, one kind may be used, or two or more kinds may be used in combination.
When the amine stabilizer is used, the compounding amount of the amine stabilizer in the long fiber reinforced polyamide resin composition is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the long fiber reinforced polyamide resin composition. Yes, more preferably 0.1 to 1 part by mass. When the amount is within the above range, light resistance and heat aging resistance can be further improved, and the amount of generated gas can be further reduced.

The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table is not particularly limited and is preferably a heat stabilizer. Copper salt.
The copper salt is not particularly limited. For example, copper halide (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid Examples thereof include copper oxide, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex salt in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. Especially, it is preferable that it is 1 or more types selected from the group which consists of copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate. Copper iodide and / or copper acetate Is more preferable. When using the above metal salts, especially copper salts, long fiber reinforced polyamide resin that has excellent heat aging resistance and can suppress metal corrosion of the screw and cylinder during extrusion (hereinafter also simply referred to as “metal corrosion”). A composition can be obtained.
As said metal salt, you may use by 1 type and may be used in combination of 2 or more types.
When using a copper salt, the blending amount of the copper salt in the long fiber reinforced polyamide resin composition is preferably 0.01 to 0.2 parts by mass with respect to 100 parts by mass of the long fiber reinforced polyamide resin composition, More preferably, it is 0.02-0.15 mass part. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.
Further, from the viewpoint of improving the heat aging resistance, the copper element content is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, and even more preferably 50, based on the total amount of the long fiber reinforced polyamide resin composition. ~ 300 ppm.

Alkali metal and alkaline earth metal halides are not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. Among these, potassium iodide and potassium bromide, and a mixture thereof are preferable, and potassium iodide is more preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion.
As the halide, one kind may be used, or two or more kinds may be used in combination.
When using alkali metal and alkaline earth metal halides, the blending amount of alkali and alkaline earth metal halides in the long fiber reinforced polyamide resin composition is 100 parts by mass of the long fiber reinforced polyamide resin composition. , Preferably it is 0.05-5 mass parts, More preferably, it is 0.2-2 mass parts. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

In the long fiber reinforced polyamide resin composition of the present embodiment, a mixture of a copper salt and a halide of an alkali or alkaline earth metal can be suitably used as a heat stabilizer. The ratio of the copper salt to the alkali and alkaline earth metal halide is such that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. It is preferable to contain, More preferably, it is 5/1-30/1.
When the molar ratio (halogen / copper) is within the above range, the heat aging resistance of the long fiber reinforced polyamide resin composition can be further improved. Moreover, when the molar ratio (halogen / copper) is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed. When the molar ratio (halogen / copper) is 40/1 or less, corrosion of the screws of the molding machine can be prevented without substantially impairing mechanical properties such as toughness, which is preferable.

[Physical properties of long fiber reinforced polyamide resin composition]
The sulfuric acid relative viscosity ηr, melting point Tm2, and heat of fusion ΔH at 25 ° C. of the long fiber reinforced polyamide resin composition of the present embodiment can be measured by the same method as that for the polyamide. The long fiber reinforced polyamide resin composition is excellent in heat resistance, moldability, and chemical resistance because the measured value in the long fiber reinforced polyamide resin composition is in a range similar to the preferable range as the measured value of the polyamide. Can be obtained.

[Molded product of long fiber reinforced polyamide resin composition]
The molded body of the long fiber reinforced polyamide resin composition can be obtained by melting and molding the long fiber reinforced polyamide resin composition or pellets thereof.
As a molding method, a known method can be applied. For example, known molding methods such as injection molding, extrusion molding, press molding, blow molding, calendar molding, casting molding, and the like can be mentioned.
Moreover, you may combine the said shaping | molding method arbitrarily.
In the molded article of the long fiber reinforced polyamide resin composition of the present embodiment, it is preferable that the (B) reinforcing fiber is dispersed in a range of weight average fiber length: 1 mm to 10 mm, preferably 2 mm to 9 mm. More preferably, it is dispersed within a range.
The method for achieving the weight average fiber length of the (B) reinforcing fiber in the molded body is not limited to the following, but examples include the following technique for suppressing fiber breakage during injection molding.
That is, for example, 1) A method using a deep groove / low compression ratio and a screw having a large backflow prevention ring or a screw head clearance. 2) A method using a mold having a large gate cross-sectional area. 3) As a molding condition, a method of molding at a resin temperature slightly higher than that of a normal polyamide resin by minimizing screw rotation speed and back pressure.
The weight average fiber length of the (B) reinforcing fiber in the molded product was removed by burning or dissolving the polyamide resin contained in the molded product, and then the reinforcing fiber was transferred onto a slide glass and observed under an optical microscope. It can be calculated by the following formula from a value obtained by measuring the length of 400 arbitrarily selected reinforcing fibers using an analyzer.
Weight average fiber length = Σ (L _i ² ) / ΣL _i
(The length of each reinforcing fiber is L ₁ , L ₂ ,..., L _400. )

[Use of long fiber reinforced polyamide resin composition and molded article]
The molded product obtained from the long fiber reinforced polyamide resin composition of the present embodiment is excellent in strength, strength during heat, durability, low water absorption, and heat stability. Therefore, the long fiber reinforced polyamide resin composition of the present embodiment is suitably used as various parts materials for automobiles, electric and electronic, industrial materials, daily use and household goods, and for extrusion applications. be able to.
It is not particularly limited for automobiles, and is used for, for example, intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, and electrical parts.
The automobile intake system parts are not particularly limited, and examples include an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body.
The automobile cooling system component is not particularly limited, and examples thereof include a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.
The automobile fuel system parts are not particularly limited, and examples thereof include a fuel delivery pipe and a gasoline tank case.
The interior part is not particularly limited, and examples thereof include an instrument panel, a console box, a glove box, a steering wheel, and a trim.
The exterior parts are not particularly limited, and examples include a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, and a roof rail.
The electrical component is not particularly limited, and examples thereof include a connector, a wire harness connector, a motor component, a lamp socket, a sensor on-vehicle switch, and a combination switch.
The electric and electronic devices are not particularly limited, and are used for connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, motor end caps, and the like.
The industrial material is not particularly limited. For example, it is used for gears, cams, insulating blocks, valves, electric tool parts, agricultural equipment parts, engine covers, and the like.
It is not specifically limited as for daily use and household goods, for example, it is used for buttons, food containers, office furniture and the like.
The extrusion application is not particularly limited, and is used for, for example, a film, a sheet, a filament, a tube, a rod, and a hollow molded article.

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) Raw material of polyamide]
<(A) Dicarboxylic acid>
(1) 1,4-cyclohexanedicarboxylic acid (CHDA) manufactured by Eastman Chemical Co., Ltd., trade name 1,4-CHDA HP grade (trans isomer / cis isomer (molar ratio) = 25/75)
(2) Terephthalic acid (TPA) Wako Pure Chemical Industries, Ltd. Trade name Terephthalic acid (3) Adipic acid (ADA) Wako Pure Chemical Industries, Ltd. Trade name Adipic acid (4) Dodecanedioic acid (C12DA) Wako Pure Chemical Industries, Ltd. Dodecanedioic acid

<(B) Diamine>
(5) 2-methylpentamethylenediamine (2MPD) manufactured by Tokyo Chemical Industry Co., Ltd. Product name 2-methyl-1,5-diaminopentane (6) pentamethylenediamine (PMD) manufactured by Wako Pure Chemical Industries, Ltd. Product name 1,5-diaminopentane (7) Hexamethylenediamine (HMD) Wako Pure Chemical Industries, Ltd. Trade name Hexamethylenediamine

<(C) Lactam and / or aminocarboxylic acid>
(8) ε-Caprolactam (CPL) Wako Pure Chemical Industries, Ltd. Trade name ε-Caprolactam

[(B) Reinforcing fiber]
(9) Glass fiber roving Made of PPG glass fiber Product name TufRov 4510, average fiber diameter 17 μm, 2400TEX
(10) Glass fiber chopped strand Product name T-275H (average fiber diameter 10.5 μmφ, fiber cut length 3 mm) manufactured by Nippon Electric Glass

[(C) Additive]
(11) Thermal stabilizer Ciba product name Irganox 1098
(12) Heat stabilizer Wako Pure Chemical Industries, Ltd. Product name Copper iodide (13) Heat stabilizer Wako Pure Chemical Industries, Ltd. Product name Potassium iodide

[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 pentamethylenediamine skeleton is ((b-1) moles of diamine having a pentamethylenediamine skeleton added as a raw material monomer / all (b) diamines added as a raw material monomer. The number of moles of x) was determined by calculation as 100.
The mole% of (c) lactam and / or aminocarboxylic acid is: (c) moles of lactam and / or aminocarboxylic acid added as raw monomer / moles of all (a) dicarboxylic acid added as raw monomer Number + (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 the diamine having the (b-1) pentamethylenediamine skeleton which is the additive.

[Measurement method of physical properties]
<(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 is raised to is the melting point Tm2 (° C.).

<(2) Sulfuric acid relative viscosity ηr at 25 ° C.>
It carried out according to JIS-K6920. Specifically, a polymer solution (a ratio of (polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid and measured under a temperature condition of 25 ° C.

<(3) Cyclic amino terminal amount (μ equivalent / g)>
The amount of cyclic amino terminal was measured using 1H-NMR.
Signal of hydrogen bonded to carbon adjacent to nitrogen atom of nitrogen heterocycle (chemical shift value 3.5 to 4.0 ppm) and signal of hydrogen bonded to carbon adjacent to nitrogen atom of amide bond of polyamide main chain ( The cyclic amino terminal amount was calculated using an integral ratio of chemical shift value of 3.0 to 3.5 ppm. The total number of polymer terminals used at that time is 2 /, using MPC measured with GPC (converted by Tosoh Corporation, HLC-8020, hexafluoropropanol solvent, PMMA standard sample (manufactured by Polymer Laboratories)). Calculated as Mn × 1,000,000.

<(4) Amino terminal amount (μ equivalent / g)>
The amino terminal amount was measured by neutralization titration.
3.0 g of polyamide was dissolved in 100 mL of 90% aqueous phenol and titrated with 0.025 N hydrochloric acid to determine the amino terminal amount. The end point was determined from the indicated value of the pH meter.

<(5) Tensile strength (MPa)>
From the polyamide resin composition pellets obtained in Examples and Comparative Examples, the cylinder temperature is shown in Table 1 using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.). A multi-purpose test piece (A type) according to ISO 3167 was obtained as molding conditions of melting point Tm2 + 25 ° C., mold temperature 120 ° C., injection pressure 65 MPa, injection time 5 seconds, cooling time 25 seconds, screw rotation speed 200 rpm. .
The obtained multipurpose test piece (A type) was subjected to a tensile test at a tensile speed of 5 mm / min in accordance with ISO 527, and the tensile strength was measured.

<(6) Tensile strength during heating (MPa)>
Under the condition of an ambient temperature of 130 ° C., a tensile test was performed at a tensile speed of 5 mm / min using the above-mentioned multipurpose test piece (A type), and the hot tensile strength was measured.

<(7) Tensile strength after heat aging (MPa)>
The multi-purpose test piece (A type) was heat-aged in a hot air circulation oven at 210 ° C. for 700 hours.
After cooling at 23 ° C. for 24 hours or more, a tensile test was performed according to ISO 527 at a tensile speed of 5 mm / min to measure the tensile strength. The higher the tensile strength after heat aging, the better the heat resistance stability.
Moreover, the intensity | strength retention rate by heat aging was computed from the ratio of (7) with respect to said (5).

<(8) Creep rupture stress (MPa)>
Using the polyamide resin composition pellets obtained in the examples and comparative examples, the flat molding pieces (150 × 150 × 4 mm) were molded under the same injection molding conditions as in (5) above.
A test piece according to ASTM D1822 was cut out from the obtained flat plate-shaped piece so that the resin filling direction and the test piece evaluation direction were at right angles, and used as a measurement sample.
In a 6-creep test machine (model 145-PC) manufactured by Yasuda Seiki Seisakusho, a load was arbitrarily applied in a range of 60 to 90% with respect to the tensile strength of the measurement sample in an atmosphere at 130 ° C. The measurement points tabulated from the time required until the fracture with respect to the load stress at that time were logarithmically approximated, and the stress value at which the fracture occurred at the stress load time of 24 hours was determined. The higher the creep rupture stress value, the better the durability.

<(9) Water absorption rate (%)>
The mass before test (mass before water absorption) was measured in the dry as mold of the multipurpose test piece (A type).
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 (%).

<(10) Weight average fiber length in the molded body>
The multipurpose specimen A type produced by the above method was put in a porcelain crucible, and the polyamide resin was burned using an electric muffle furnace (FP-31 type, manufactured by Yamato Kagaku, set temperature 600 ° C.).
The glass fiber after combustion was transferred onto a slide glass, observed under an optical microscope, and calculated from the following formula using a value obtained by measuring the length of 400 arbitrarily selected glass fibers using an image analyzer.
Weight average fiber length = Σ (Li ² ) / ΣLi
(The length of each reinforcing fiber is L1, L2,..., L400, respectively.)

[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 distilled water 1500 g to prepare a 50% by mass aqueous solution containing equimolar raw material monomers.
As an additive to be added in consideration of the obtained aqueous solution and the escape during melt polymerization, 21 MP (0.18 mol) of 2MPD was charged into an autoclave (made by Nitto Koatsu) with an internal volume of 5.4 L, and the liquid temperature (internal temperature) Was maintained until the temperature reached 50 ° C., and the atmosphere in the autoclave was replaced with nitrogen. From the liquid temperature of about 50 ° C., heating was continued until the pressure in the tank of the autoclave reached about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank was expressed as gauge pressure). . In order to keep the pressure in the tank at about 2.5 kg / cm ² , heating was continued while removing water out of the system, and the aqueous solution was concentrated to a concentration of about 85%. The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² . In order to keep the pressure in the tank at 30 kg / cm ² , heating was continued until the final temperature of the liquid temperature reached −50 ° C. while removing water out of the system. Further, while the heating was continued, the pressure in the tank was reduced from 30 kg / cm ² to atmospheric pressure (gauge pressure was 0 kg / cm ² ) over 60 minutes. The heater temperature was adjusted so that the final temperature of the liquid temperature was 345 ° C. The liquid temperature was maintained in that state for 10 minutes under a reduced pressure of 100 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 obtained polyamide was dried in a nitrogen stream and the moisture content was adjusted to be less than about 0.2% by mass, and then the measurements (1) to (4) were performed. The measurement results are shown in Table 1.

[Production Example 2]
Polyamide was polymerized by the hot melt polymerization method described in Production Example 1 except that the amount of the additive during melt polymerization was the amount described in Table 1 below.
Further, “solid phase polymerization” was performed.
10 kg of polyamide pellets obtained by melt polymerization were placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.) and sufficiently substituted with nitrogen. While flowing nitrogen at 1 L / min, heating was performed at 260 ° C. for 6 hours while stirring. Thereafter, the temperature was lowered while flowing nitrogen, and when the temperature reached about 50 ° C., the pellets were taken out from the apparatus to obtain polyamide.
Table 1 below shows the measurement results of the obtained polyamide based on the above-described measurement method.

[Production Example 3]
Polyamide was polymerized by the hot melt polymerization method described in Production Example 1 except that the time taken to lower the pressure in the tank from 30 kg / cm ² to atmospheric pressure was 90 minutes. Table 1 below shows the measurement results of the obtained polyamide based on the above-described measurement method.

[Production Examples 4 to 9]
The compounds and amounts shown in Table 1 were used as (a) dicarboxylic acid, (b) diamine, (c) lactam and / or aminocarboxylic acid, and additives during melt polymerization. Moreover, the polyamide was polymerized by the hot melt polymerization method described in Production Example 1 except that the final temperature of the melt polymerization was set to the temperature described in Table 1 below.
Furthermore, the solid phase polymerization described in Production Example 2 was carried out except that the temperature and time described in Table 1 below were applied as the solid phase polymerization temperature and time.
Table 1 below shows the measurement results of the obtained polyamide based on the above-described measurement method.

[Comparative Production Example 1]
The hot melt polymerization method described in Production Example 1 except that the time taken to lower the pressure in the tank from 30 kg / cm ² to atmospheric pressure was 120 minutes and the final temperature of the melt polymerization was 350 ° C. Polymerization of polyamide was carried out.
The measurement results of the obtained polyamide based on the above measurement method are shown in Table 2 below.

[Comparative Production Example 2]
As the (a) dicarboxylic acid, (b) diamine, and additives during melt polymerization, the compounds and amounts shown in Table 2 below were used. Further, the polyamide was polymerized by the hot melt polymerization method described in Production Example 1 except that the final temperature of the melt polymerization was set to the temperature described in Table 2 below. Furthermore, the solid phase polymerization described in Production Example 2 was performed except that the temperature and time described in Table 2 below were applied as the solid phase polymerization temperature and time.
The measurement results of the obtained polyamide based on the above measurement method are shown in Table 2 below.

[Comparative Production Examples 3 to 7]
As the (a) dicarboxylic acid, (b) diamine, and additives during melt polymerization, the compounds and amounts shown in Table 2 below were used. Further, the polyamide was polymerized by the hot melt polymerization method described in Production Example 1 except that the final temperature of the melt polymerization was set to the temperature described in Table 2 below.
The measurement results of the obtained polyamide based on the above measurement method are shown in Table 2 below.

[Example 1]
Using a twin screw extruder (trade name “ZSK25”, manufactured by Coperion), the barrel temperature is Tm2 + 25 ° C. of the polyamide resin (A) shown in Table 1 above, and the screw rotation speed is 300 rpm. Thus, the polyamide resin of Production Example 1 was fed and melt-kneaded.
The melted polyamide resin was supplied and filled in an impregnation die equipped with a resin impregnation roller of a long fiber reinforced resin composition manufacturing apparatus (trade name “KOSLFP-212”, manufactured by Kobe Steel, Ltd.).
Two glass fiber rovings are introduced into this impregnation die, and the glass fiber bundle impregnated with the above-mentioned molten polyamide resin is continuously drawn out from the nozzle (nozzle diameter 2.9 mm) in the impregnation die, and one resin strand shape And a pellet of a long fiber reinforced polyamide resin composition was obtained by cutting with a pelletizer. The strand take-up speed was 30 m / min.
The obtained pellet had a pellet length of 10 mm, a pellet diameter of 2.9 mm, a weight average fiber length of 10 mm as a reinforcing fiber, and a glass fiber content of 50% by mass.
The evaluation results of the obtained long fiber reinforced polyamide resin composition are shown in Table 3 below.

[Examples 2 to 9]
A long fiber reinforced polyamide resin composition was obtained in the same manner as in Example 1 except that the amounts of the raw material components were adjusted to the ratios shown in Table 3 below. Table 3 below shows the measurement results of the long fiber reinforced polyamide resin composition based on the above measurement method.

[Comparative Examples 1-7]
A long fiber reinforced polyamide resin composition was obtained in the same manner as in Example 1 except that the amounts of the raw material components were adjusted to the ratios shown in Table 4 below. Table 4 below shows the measurement results of the long fiber reinforced polyamide resin composition based on the above measurement method.

Example 10
Using a twin screw extruder (trade name “ZSK25”, manufactured by Coperion), the barrel temperature is Tm2 + 25 ° C. of the polyamide resin (A) shown in Table 1 above, and the screw rotation speed is 300 rpm. Thus, the polyamide resin and heat stabilizer of Production Example 1 were fed so as to have the ratios shown in Table 5 below, and melt-kneaded.
The melted polyamide resin was supplied and filled in an impregnation die equipped with a resin impregnation roller of a long fiber reinforced resin composition manufacturing apparatus (trade name “KOSLFP-212”, manufactured by Kobe Steel, Ltd.).
Two glass fiber rovings are introduced into this impregnation die, and the glass fiber bundle impregnated with the above-mentioned molten polyamide resin is continuously drawn out from the nozzle (nozzle diameter 2.9 mm) in the impregnation die, and one resin strand shape And a pellet of a long fiber reinforced polyamide resin composition was obtained by cutting with a pelletizer. The strand take-up speed was 30 m / min.
The obtained pellet had a pellet length of 10 mm, a pellet diameter of 2.9 mm, a weight average fiber length of 10 mm as a reinforcing fiber, and a glass fiber content of 50% by mass.
The evaluation results of the obtained long fiber reinforced polyamide resin composition are shown in Table 5 below.

[Comparative Example 8]
A long fiber reinforced polyamide resin composition was obtained in the same manner as in Example 10 except that the amounts of the raw material components were adjusted to the ratios shown in Table 5 below. Table 5 below shows the measurement results of the long fiber reinforced polyamide resin composition based on the above measurement method.

[Comparative Example 9]
Using a twin-screw extruder (trade name “ZSK25”, manufactured by Coperion, L / D = 48), the barrel temperature was extruded under the conditions of Tm2 + 25 ° C. of polyamide resin (A) shown in Table 1 and a screw rotation speed of 300 rpm. From the most upstream part of the machine, the polyamide resin of Example 1 and the heat stabilizer are fed so as to have the ratios shown in Table 5 below, and the glass fiber chopped strands are fed from the side feed port installed on the downstream side of the extruder. Pellets of polyamide resin composition were obtained by supplying the mixture shown in Table 5 and cooling the melt-kneaded product extruded from the die head in a strand shape and cutting with a pelletizer.
The obtained pellet had a pellet length of 3.0 mm, a pellet diameter of 2.0 mm, and a glass fiber content of 50 mass%.
The evaluation results of the obtained polyamide resin composition are shown in Table 5 below.

Example 11
A long fiber reinforced polyamide resin composition was obtained in the same manner as in Example 10 except that the nozzle diameter was changed to 2.3 mm. Table 5 below shows the measurement results of the long fiber reinforced polyamide resin composition based on the above measurement method.

[Comparative Example 10]
A polyamide resin composition was produced in the same manner as in Comparative Example 9 except that the amounts of the raw material components were adjusted to the ratios shown in Table 5 below. However, since the internal pressure of the die of the extruder increased and fluffing of the strands occurred, it was not possible to produce stably.

As is apparent from the results in Table 3, the long fiber reinforced polyamide resin compositions of Examples 1 to 9 had excellent characteristics in all points of strength, hot strength, and durability. In particular, the long fiber reinforced polyamide resin compositions of Examples 1, 2 and 4 to 9 having a sulfuric acid relative viscosity ηr of 2.3 or more had excellent characteristics.
On the other hand, Comparative Examples 1 and 4 in which the amount of cyclic amino terminal exceeds 60 μequivalent / g was insufficient in terms of heat strength and durability. Further, Comparative Examples 2 and 5 to 7 having a cyclic amino terminal amount of less than 30 μeq / g were also insufficient in terms of hot strength and durability.
In Comparative Example 3 in which the content of the pentamethylenediamine skeleton of the diamine used for the polymerization of the polyamide is less than 50 mol%, the strength during heating and the durability were insufficient.
As is apparent from the results in Table 5, the long fiber reinforced polyamide resin compositions of Examples 10 and 11 had excellent properties in terms of strength, hot strength, heat stability, and low water absorption. . On the other hand, the polyamide resin compositions of Comparative Examples 8 to 10 were insufficient in these respects.

  The long fiber reinforced polyamide resin composition of the present invention has industrial applicability as a molding material for various parts such as automobiles, electric and electronic, industrial materials, and daily and household products.

Claims (8)

A pellet of a long fiber reinforced polyamide resin composition,
(A) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid;
(B) a diamine containing a diamine having a pentamethylenediamine skeleton of at least 50 mol%;
A polyamide obtained by polymerizing
The amount of cyclic amino terminals of the polyamide is 30 to 60 μequivalent / g, and (A) the polyamide is 20 to 80% by mass in the long fiber reinforced polyamide resin composition ,
(B) Reinforcing fiber having a weight average fiber length of 1 to 15 mm in the long fiber reinforced polyamide resin composition, 20 to 80% by mass,
A pellet of a long fiber reinforced polyamide resin composition. The pellet of the long fiber reinforced polyamide resin composition according to claim 1, wherein the (A) polyamide has a sulfuric acid relative viscosity ηr at 25 ° C of 2.3 or more. The pellet of the long fiber reinforced polyamide resin composition according to claim 1 or 2, wherein the amino terminal amount of the (A) polyamide is 20 µeq / g or more. The pellet of the long fiber reinforced polyamide resin composition according to any one of claims 1 to 3, wherein the polyamide (A) is a polyamide polymerized at a reaction temperature higher than 300 ° C. The long-fiber reinforced polyamide resin composition according to any one of claims 1 to 4, wherein the cyclic amino terminal of the polyamide (A) is formed by a cyclization reaction of a diamine having a pentamethylenediamine skeleton. Pellets . The pellet of the long fiber reinforced polyamide resin composition according to any one of claims 1 to 5, wherein the polyamide (A) is a polyamide obtained through a solid phase polymerization step in at least a part of the polymerization step. The long fiber reinforced polyamide resin composition according to any one of claims 1 to 6, wherein the (B) reinforcing fiber is at least one selected from the group consisting of glass fiber, carbon fiber, boron fiber, and metal fiber. Pellets . A molded body using pellets of the long fiber reinforced polyamide resin composition according to any one of claims 1 to 7, wherein the (B) reinforcing fiber is dispersed with a weight average fiber length of 1 mm to 10 mm. Molded body.