JP2011063795A - Polyamide fusion-molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fusion-molded article excellent in heat resistance, flowability, strength, toughness, low water absorbability and heat ageing resistance and excellent in fusibility (fusion strength). <P>SOLUTION: There is provided the fusion-molded article comprising (A) a polyamide prepared by polymerizing (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid with (b) a diamine containing at least 50 mol% of a diamine having a substituent branched from a main chain. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a welded molded article.

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

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

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

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

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

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

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

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

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

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

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

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

The PA6C copolymer polyamides disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity. The polyamides disclosed in Patent Documents 4 and 5 also have welding strength, toughness and strength. And improvement in fluidity is insufficient.

  The problem to be solved by the present invention is to provide a welded molded article having excellent heat resistance, fluidity, strength, toughness, low water absorption, heat aging resistance, and excellent weldability (welding strength). .

  The inventors of the present invention have made extensive studies in order to solve the above problems. As a result, the inventors have found that the above problems can be solved by using a polyamide obtained by polymerizing a specific dicarboxylic acid and a specific diamine as constituents as a material for a weld-molded product, and have completed the present invention.

That is, the present invention is as follows.
[1]
(A) A polyamide obtained by polymerizing (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) at least 50 mol% of a diamine containing a diamine having a substituent branched from the main chain. A welded molded product containing
[2]
The welded molded article according to [1], wherein the diamine having a substituent branched from the main chain is 2-methylpentamethylenediamine.
[3]
The welded molded article according to [1] or [2], wherein the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.
[4]
The welded molded article according to any one of [1] to [3], wherein the dicarboxylic acid (a) further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms.
[5]
The welded molded article according to any one of [1] to [4], wherein the polyamide (A) is a polyamide obtained by further copolymerizing (c) a lactam and / or an aminocarboxylic acid.
[6]
The welding molded product according to any one of [1] to [5], wherein the polyamide (A) has a melting point of 270 to 350 ° C.
[7]
The welded molded article according to any one of [1] to [6], wherein the trans isomer ratio in the polyamide (A) is 50 to 85%.
[8]
(B) The welded molded article according to any one of [1] to [7], further containing an inorganic filler.
[9]
(C) The welded molded article according to any one of [1] to [8], further containing a heat stabilizer.
[10]
The welded molded product according to any one of [1] to [9], wherein the molded product is formed by vibration welding or laser welding.
[11]
[1] A component including the welded molded product according to any one of [10].
[12]
The part according to [11], which is a welded automobile part, pipe, pipe or tube.

  According to the present invention, a welded molded article having excellent heat resistance, fluidity, strength, toughness, low water absorption, heat aging resistance and excellent weldability (welding strength) can be obtained.

The schematic diagram of the state which contacted two types of flat plate test pieces in welding strength measurement is shown.

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

  The welded molded article of the present embodiment has (A) (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid, and (b) at least 50 mol% of a substituent branched from the main chain. It contains a polyamide obtained by polymerizing a diamine containing a diamine.

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

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

<(A-1) Alicyclic dicarboxylic acid>
(A-1) Examples of alicyclic dicarboxylic acids (also referred to as alicyclic dicarboxylic acids) include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentane. Examples thereof include alicyclic dicarboxylic acids having 3 to 10 carbon atoms, preferably 5 to 10 carbon atoms, such as dicarboxylic acid.
The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.
Examples of the substituent include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group.

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

An alicyclic dicarboxylic acid has a trans isomer and a cis geometric isomer.
As the alicyclic dicarboxylic acid as a raw material monomer, either a trans isomer or a cis isomer may be used, or a mixture of various ratios of a trans isomer and a cis isomer may be used.
Since alicyclic dicarboxylic acids are isomerized at a high temperature to a certain ratio, and the cis isomer has higher water solubility in the equivalent salt with the diamine than the trans isomer, the trans isomer / cis cis is used as a raw material monomer. The body ratio in terms of molar ratio is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and still more preferably 35/65 to 15/85.
The trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR). Here, the trans isomer / cis isomer ratio (molar ratio) in the present specification is determined by 1H-NMR.

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

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

Examples of the aromatic dicarboxylic acid include unsubstituted or various terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. And aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with the above substituent.
Examples of the various substituents include, for example, 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 halogen group such as a chloro group and a bromo group, and 1 carbon atom. -6 silyl groups, and sulfonic acid groups and salts thereof such as sodium salts.

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

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

The proportion (mol%) of (a-1) alicyclic dicarboxylic acid in (a) dicarboxylic acid is at least 50 mol%. The ratio of the alicyclic dicarboxylic acid is 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and particularly preferably 100 mol%. When the ratio of the alicyclic dicarboxylic acid is at least 50 mol%, a polyamide having excellent heat resistance, low water absorption, strength, and the like can be obtained.
(A) The ratio (mol%) of dicarboxylic acid other than (a-2) alicyclic dicarboxylic acid in dicarboxylic acid is 0 to 50 mol%, and preferably 0 to 40 mol%.

  When (a) the dicarboxylic acid component contains an aliphatic dicarboxylic acid having 10 or more carbon atoms, (a-1) 50-99.9 mol% of the alicyclic dicarboxylic acid and (a-2) 10 carbon atoms. It is preferable that it is 0.1-50 mol% of the above aliphatic dicarboxylic acid, (a-1) 60-95 mol% of alicyclic dicarboxylic acid, and (a-2) C10 or more aliphatic dicarboxylic acid. More preferably, it is 5-40 mol%, (a-1) alicyclic dicarboxylic acid is 80-95 mol% and (a-2) C10 or more aliphatic dicarboxylic acid is 5-20 mol%. More preferably.

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

<(B) Diamine>
The (b) diamine used in the present embodiment contains at least 50 mol% of a diamine having a substituent branched from the main chain.
<(B-1) Diamine with Substituent Branched from Main Chain>
(B) By containing at least 50 mol% of a diamine having a substituent branched from the main chain as the diamine, a polyamide that simultaneously satisfies fluidity, toughness, strength, and the like can be obtained.
Examples of the substituent branched from the main chain include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. Is mentioned.

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

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

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

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

  The aromatic diamine is an aromatic diamine, such as metaxylylenediamine.

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

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

(B) The ratio (mol%) of the diamine having a substituent branched from the main chain (b-1) in the diamine is at least 50 mol%. The ratio of the diamine having a substituent branched from the main chain is 50 to 100 mol%, and preferably 60 to 100 mol%. More preferably, it is 80-100 mol%, More preferably, it is 85-100 mol%, More preferably, it is 90-100 mol%, Most preferably, it is 100 mol%. When the ratio of the diamine having a substituent branched from the main chain is at least 50 mol%, a polyamide having excellent fluidity, toughness, and strength can be obtained.
(B) The ratio (mol%) of diamines other than the diamine having a substituent branched from the main chain (b-2) in the diamine is 0 to 50 mol%, preferably 0 to 40 mol%. .

  The addition amount of (a) dicarboxylic acid and the addition amount of (b) diamine are preferably around the same molar amount. The amount of (b) diamine escaped out of the reaction system during the polymerization reaction is also considered in terms of the molar ratio, and (a) the molar amount of (b) diamine as a whole is 0 It is preferable that it is 0.9-1.2, More preferably, it is 0.95-1.1, More preferably, it is 0.98-1.05.

<(C) Lactam and / or aminocarboxylic acid>
(A) Polyamide can further copolymerize (c) lactam and / or aminocarboxylic acid from a 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 combined (condensed).
When (A) polyamide is a polyamide obtained by polymerizing (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, (c) lactam and / or aminocarboxylic acid is A lactam having 4 to 14 carbon atoms and / or an aminocarboxylic acid is preferable, and a lactam having 6 to 12 carbon atoms and / or an aminocarboxylic acid is more preferably used.

Examples of the lactam include butyrolactam, pivalolactam, ε-caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like.
Among these, from the viewpoint of toughness, ε-caprolactam and laurolactam are preferable, and ε-caprolactam is more preferable.
Examples of the aminocarboxylic acid include ω-aminocarboxylic acid and α, ω-amino acid that are compounds in which the lactam is ring-opened.
The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ω position, such as 6-aminocaproic acid, 11-aminoundecanoic acid, And 12-aminododecanoic acid and the like, and examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.
As the lactam and / or aminocarboxylic acid, one kind may be used, or two or more kinds may be used in combination.
(C) 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.

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

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

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

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

(A) In polyamide, an alicyclic dicarboxylic acid structure exists as a geometric isomer of a trans isomer and a cis isomer.
(A) In the polyamide, (a-1) the trans isomer ratio in the part derived from the alicyclic dicarboxylic acid represents the ratio of the trans isomer in the entire alicyclic dicarboxylic acid in the polyamide, and the trans isomer The ratio is preferably 50 to 85 mol%, more preferably 50 to 80 mol%, and still more preferably 60 to 80 mol%.
As described above, as the (a-1) alicyclic dicarboxylic acid before polymerization, an alicyclic dicarboxylic acid having a trans isomer / cis isomer ratio (molar ratio) of 50/50 to 0/100 is used. On the other hand, the trans isomer ratio in the part derived from (a-1) alicyclic dicarboxylic acid in (A) polyamide obtained by polymerization of (a) dicarboxylic acid and (b) diamine is preferably 50 to It is preferably 85 mol%.
When the trans isomer ratio is within the above range, the polyamide has a high melting point, toughness and strength, in addition to the characteristics of high heat resistance due to high Tg, and usually fluidity, which is a property contrary to heat resistance. And having a high crystallinity at the same time.
These characteristics of the polyamide consist of a combination of (a) at least 50 mol% or more of 1,4-cyclohexanedicarboxylic acid, (b) at least 50 mol% or more of 2-methylpentamethylenediamine, and the trans isomer ratio is This is particularly noticeable with polyamides of 50 to 85 mol%.
In the present embodiment, the trans isomer ratio can be measured by the method described in the following examples.

[(A) Polyamide production method]
(A) Polyamide is not particularly limited, and (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) at least 50 mol% of a substituent branched from the main chain. It can manufacture with the manufacturing method of polyamide including the process of superposing | polymerizing the diamine containing the aliphatic diamine which has.
(A) As a manufacturing method of polyamide, it is preferable to further include the process of raising the polymerization degree of polyamide.

Examples of the method for producing the polyamide include various methods as exemplified below:
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 a suspension of water of a diamine / dicarboxylate 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 “pre-polymerization”). Abbreviated as “polymer / extrusion polymerization method”).
4) A method of heating an aqueous solution or a suspension of water of a diamine dicarboxylate or a mixture thereof and increasing the degree of polymerization 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 a diamine dicarboxylate or a mixture thereof while maintaining a solid state (hereinafter sometimes abbreviated as “solid phase polymerization method”),
6) A “solution method” in which a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component are used for polymerization.

In the polyamide production method, from the viewpoint of polyamide fluidity, (A) the polyamide is polymerized while maintaining the trans isomer ratio of the portion derived from (a-1) alicyclic dicarboxylic acid at 85% or less. In particular, by maintaining it at 80% or less, it is possible to obtain a polyamide having a further excellent color tone and tensile elongation and a high melting point.
In the production method of polyamide, in order to increase the degree of polymerization and increase the melting point of the polyamide, it is necessary to increase the heating temperature and / or lengthen the heating time. The tensile elongation may decrease due to coloring or thermal deterioration. In addition, the rate at which the molecular weight increases may decrease significantly.
Since it is possible to prevent a decrease in tensile elongation due to polyamide coloring or thermal deterioration, it is preferable to perform polymerization while maintaining the trans isomer ratio at 80% or less.

  As a method for producing polyamide, it is easy to maintain the trans isomer ratio at 85% or less, and because the resulting polyamide has excellent color tone, 1) hot melt polymerization method, and 2) hot melt polymerization. -It is preferable to produce polyamide by a solid phase polymerization method.

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

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

[(A) Physical properties of polyamide]
(Molecular weight)
(A) The molecular weight of the polyamide is specified using the relative viscosity ηr at 25 ° C. as an index.
The molecular weight of the polyamide (A) is preferably 1 in 98% sulfuric acid concentration 1% and 25 ° C. relative viscosity ηr measured according to JIS-K6810 from the viewpoint of mechanical properties such as toughness and strength, and moldability. It is 0.5-7.0, More preferably, it is 1.7-6.0, More preferably, it is 1.9-5.5.
The relative viscosity at 25 ° C. can be measured according to JIS-K6810, as described in [Measurement method] in [Example] described later.

(Melting point)
The melting point (Tm2) of the polyamide (A) measured by [Production Example] described later is preferably 270 to 350 ° C. 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.
Moreover, melting | fusing point Tm2 becomes like this. Preferably it is 350 degrees C or less, More preferably, it is 340 degrees C or less, More preferably, it is 335 degrees C or less, More preferably, it is 330 degrees C or less.
By setting the melting point Tm2 to 270 ° C. or higher, a polyamide having excellent heat resistance can be obtained. By setting the melting point Tm2 to 350 ° C. or lower, the thermal decomposition of the polyamide during melt processing such as extrusion and molding can be suppressed.

(Heat of fusion ΔH)
(A) From the viewpoint of heat resistance, the heat of fusion ΔH of polyamide is preferably 10 J / g or more, more preferably 14 J / g or more, still more preferably 18 J / g or more, and even more preferably 20 J. / G or more.
(A) The measurement of the melting point (Tm1 or Tm2) of polyamide and the heat of fusion ΔH 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.

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

  The welded molded article of the present embodiment preferably contains (B) an inorganic filler from the viewpoint of improving strength and the like.

[(B) Inorganic filler]
The inorganic filler (B) used in the present embodiment is not limited to the following, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, Kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, silicic acid Calcium, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, swellable Containing mica and apatite and the like.

  Among these, glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate, and clay are preferable from the viewpoint of strength and surface appearance. More preferred are glass fiber, carbon fiber, wollastonite, kaolin, mica and talc, still more preferred are glass fiber, wollastonite and mica, and particularly preferred is glass fiber. The above inorganic fillers may be used alone or in combination of two or more.

  First, as a glass fiber or carbon fiber, the cross section may be a perfect circle shape or a flat shape. Examples of such a flat cross section include, but are not limited to, a rectangular shape, an oval shape close to a rectangular shape, an elliptical shape, and a saddle shape with a narrowed central portion in the longitudinal direction. Here, the “flattening ratio” in this specification refers to a value represented by D2 / D1, where D2 is the major axis of the fiber cross section and D1 is the minor axis of the fiber cross section (a perfect circle is a flat shape). The rate is about 1.)

  Among glass fibers and carbon fibers, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 100 to 750 μm, and the weight average fiber length from the viewpoint of imparting excellent mechanical strength to the welded molded product. Those having an aspect ratio (L / D) of 10 to 100 between (L) and the number average fiber diameter (D) are preferably used.

  Here, the number average fiber diameter and the weight average fiber length of the glass fiber and carbon fiber in the present specification are values obtained by the following method. The welded molded product is placed in an electric furnace and the contained organic matter is incinerated. From the residue after the treatment, 100 or more glass fibers and carbon fibers are arbitrarily selected, and these glass fibers are observed with a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-6700F). The number average fiber diameter is measured by measuring the fiber diameter of the carbon fiber. In addition, the weight average fiber length is obtained by measuring the fiber length using SEM photographs of the 100 or more glass fibers and carbon fibers taken at a magnification of 1,000 times.

  You may surface-treat said glass fiber and carbon fiber with a silane coupling agent etc. Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane. Examples include aminosilanes, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxy silanes, and vinyl silanes. Especially, it is preferable that it is 1 or more types selected from the group which consists of said component enumerated, and aminosilanes are more preferable.

  In addition, for the above glass fiber and carbon fiber, as a sizing agent, an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer; Copolymer, epoxy compound, polyurethane resin, homopolymer of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and primary, secondary and tertiary amines thereof And a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among these, from the viewpoint of the mechanical strength of the obtained welded molded article, it comprises a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer. Copolymers, epoxy compounds, polyurethane resins, and combinations thereof as units are preferred. More preferably, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as a structural unit, and a polyurethane resin, And combinations thereof.

  Among the copolymers containing the above carboxylic acid anhydride-containing unsaturated vinyl monomer and unsaturated vinyl monomers excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units, the carboxylic acid anhydride Examples of the product-containing unsaturated vinyl monomer include, but are not limited to, maleic anhydride, itaconic anhydride, and citraconic anhydride, with maleic anhydride being preferred. On the other hand, the unsaturated vinyl monomer excluding the carboxylic anhydride-containing unsaturated vinyl monomer refers to an unsaturated vinyl monomer different from the carboxylic anhydride-containing unsaturated vinyl monomer. Examples of the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer include, but are not limited to, for example, styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2 , 3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate and ethyl methacrylate. Of these, styrene and butadiene are preferred.

  Among these combinations, from the group consisting of a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, and a mixture thereof. More preferably, it is at least one selected.

  Further, the copolymer containing the above-mentioned carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as a constituent unit has a weight average molecular weight. Is preferably 2,000 or more. Moreover, from a viewpoint of improving the fluidity | liquidity of the fusion-molded article obtained, More preferably, it is 2,000-1,000,000, More preferably, it is 2,000-500,000. In addition, the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC).

  Examples of the epoxy compound include, but are not limited to, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecene oxide, dodecene oxide, penta Aliphatic epoxy compounds such as decene oxide and eicosene oxide, glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1 , 4-dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohexene oxide And alicyclic epoxy compounds such as epoxidized cyclohexene methyl alcohol, terpene epoxy compounds such as pinene oxide, aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide, epoxidized soybean oil, And epoxidized linseed oil.

  The polyurethane resin is not particularly limited as long as it is generally used as a sizing agent. Specific examples thereof include isocyanates such as m-xylylene diisocyanate (XDI), 4,4′-methylenebis (cyclohexyl isocyanate) (HMDI), and isophorone diisocyanate (IPDI), and polyester or polyether diols. Those synthesized from can be suitably used.

  The acrylic acid homopolymer (polyacrylic acid) preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.

  The polyacrylic acid may be in a salt form. Examples of the salt form include, but are not limited to, primary, secondary, and tertiary amines. Such polyacrylic acid salts include, but are not limited to, triethylamine, triethanolamine, and glycine. The degree of neutralization is preferably 20 to 90% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor, and is preferably 40 to 60%. % Is more preferable.

  The weight average molecular weight of the polyacrylic acid forming the salt is not particularly limited. Preferably it is the range of 3,000-50,000. That is, it is 3,000 or more from the viewpoint of improving the converging property of glass fiber or carbon fiber, and is 50,000 or less from the viewpoint of improving the mechanical properties of the obtained welded molded product.

  Examples of the monomer that forms a copolymer with acrylic acid include, but are not limited to, for example, acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid and One or more types selected from the group consisting of a hydroxyl group such as mesaconic acid and a monomer having a carboxyl group are included (except for the case of acrylic acid alone). Preferably, it has 1 or more types of ester monomers among the above-mentioned monomers.

  The acrylic acid polymer may be a copolymer of acrylic acid and another copolymerizable monomer. Examples of the monomer that forms a copolymer with acrylic acid include, but are not limited to, for example, among monomers having a hydroxyl group and / or a carboxyl group, acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, and isocrotone. One or more selected from the group consisting of acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid are included (except for the case of acrylic acid only). Preferably, it has 1 or more types of ester monomers among the above-mentioned monomers.

  The polymer of acrylic acid (including both homopolymer and copolymer) may be in a salt form. Examples of the salt form include, but are not limited to, primary, secondary, and tertiary amines. Examples of such acrylic acid polymer salts include triethylamine, triethanolamine and glycine. The degree of neutralization is preferably 20 to 90% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor, and is preferably 40 to 60%. More preferably.

  The weight average molecular weight of the acrylic acid polymer forming the salt is not limited to the following, but is preferably in the range of 3,000 to 50,000. That is, 3,000 or more is preferable from the viewpoint of improving the converging property of glass fiber or carbon fiber, and 50,000 or less is preferable from the viewpoint of improving the mechanical properties of the obtained welded molded product.

  Glass fiber and carbon fiber can be obtained by drying the fiber strand produced by applying the sizing agent to the fiber using a known method such as a roller-type applicator in the known fiber production process. Obtained by continuous reaction. The fiber strand may be used as a roving as it is, or may be used as a chopped glass strand by further obtaining a cutting step. Such a sizing agent preferably imparts (adds) an equivalent of 0.2 to 3% by mass, more preferably an equivalent of 0.3 to 2% by mass, with respect to 100% by mass of glass fiber or carbon fiber. Apply (add). That is, from the viewpoint of maintaining the fiber bundle, the addition amount of the sizing agent is preferably 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber or the carbon fiber. On the other hand, it is preferably 3% by mass or less from the viewpoint of improving the thermal stability of the obtained welded molded product. The strand may be dried after the cutting step, or may be cut after the strand is dried.

Inorganic fillers other than glass fiber and carbon fiber include wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate from the viewpoint of improving the strength and surface appearance of the welded molded product. Clay is preferred. These average particle diameters are preferably 0.01 to 38 μm from the viewpoint of improving toughness and surface appearance. 0.03 to 30 μm is more preferable, 0.05 to 25 μm is further preferable, 0.10 to 20 μm is still more preferable, and 0.15 to 15 μm is particularly preferable.
By setting the average particle size to 38 μm or less, a welded molded article having excellent toughness and surface appearance can be obtained. On the other hand, when the thickness is 0.1 μm or more, a welded molded article having an excellent balance between cost and powder handling surface and mechanical properties (strength, toughness, weldability, etc.) can be obtained.

Here, among inorganic fillers, those having a needle-like shape such as wollastonite have a number average fiber diameter (hereinafter, also simply referred to as “average fiber diameter”) as an average particle diameter. In the case of needles, if the cross section is not a circle, the maximum value of the length is the (number average) fiber diameter.
About the weight average fiber length (hereinafter, also simply referred to as “average fiber length”) of the above-mentioned needle-like shape, the preferred range of the above-mentioned number average fiber diameter, and the following weight average fiber length (L) A numerical range calculated from a preferable range of the aspect ratio (L / D) with the number average fiber diameter (D) is preferable.

  Regarding the aspect ratio (L / D) between the weight average fiber length (L) and the number average fiber diameter (D) of the needle-shaped one, the surface appearance of the welded molded product is improved, and an injection molding machine or the like is used. From the viewpoint of preventing wear of metallic parts, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is more preferable.

  The measurement of needle-like fibers (wollastonite, etc.) in this specification is performed using a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-6700F). A fiber image of a needle-like fiber was taken at a magnification of 1,000 to 50,000 times, and an average particle diameter from 500 arbitrarily selected inorganic fillers (if the cross section was not a circle, the fiber length L and the fiber diameter). D) is measured.

  Inorganic fillers other than glass fibers and carbon fibers may be surface-treated using a silane coupling agent or the like. Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane. Examples include aminosilanes, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxy silanes, and vinyl silanes. Among these, one or more selected from the components listed above are preferable, and aminosilanes are more preferable. Such a surface treating agent may be previously treated on the surface of the (B) inorganic filler, or may be added when (A) the polyamide and (B) the inorganic filler are mixed. Moreover, the addition amount of the surface treatment agent is preferably 0.05 to 1.5% by mass with respect to (B) 100% by mass of the inorganic filler.

The content of the (B) inorganic filler is preferably 1 to 200 parts by weight, more preferably 10 to 150 parts by weight, and further preferably 20 to 120 parts by weight with respect to 100 parts by weight of the (A) polyamide. Part, even more preferably 30 to 100 parts by weight, particularly preferably 40 to 90 parts by weight.
By setting the content to 1 part by mass or more, the effect of improving the strength of the obtained welded molded product is sufficiently exhibited. On the other hand, by setting the content to 200 parts by mass or less, a welded molded product having excellent extrudability, moldability, and surface appearance can be obtained.

  The welded molded article of the present embodiment preferably contains (C) a heat stabilizer from the viewpoint of improving heat aging resistance and the like.

[(C) Heat stabilizer]
The (C) heat stabilizer in the present embodiment is not limited to the following, but includes, for example, phenol-based heat stabilizers, phosphorus-based heat stabilizers, amine-based heat stabilizers, and Group Ib and Group 1b of the periodic table. Examples include metal salts of elements of Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb, and halides of alkali metals and alkaline earth metals.
Among these, from the viewpoint of heat aging resistance, metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table, and alkali metals and alkaline earths Metal halides are preferred. One of the above heat stabilizers may be used alone, or two or more of them may be used in combination.

<Phenolic heat stabilizer>
Although it does not restrict | limit as a phenol type heat stabilizer below, For example, a hindered phenol compound is mentioned. The hindered phenol compound has a property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers.

  Examples of the hindered phenol compound include, but are not limited to, for example, 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, 3,5-di t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1,3 , 5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid. These may be used individually by 1 type and may be used in combination of 2 or more type. 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.

  When using a phenol-based heat stabilizer, the content of the phenol-based heat stabilizer in the welded molded product is preferably 0.01 to 1 part by mass, more preferably 0, with respect to 100 parts by mass of the welded molded product. .1 to 1 part by mass. When it is within the above range, the heat aging resistance can be further improved, and the amount of gas generated can be reduced.

<Phosphorus heat stabilizer>
Examples of the phosphorus-based heat stabilizer include, but are not limited to, 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 (3- Til-6-tert-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, 4,4′-isopropylidenebis (2-tert-butyl) Phenyl) .di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite , Tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, tris (mono , Dimixed nonylphenyl) phosphite, 4,4′-isopropylidenebis (2- -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-tert-butyl) Phenyl)) · 1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) diphosphite, tris (4,4′-isopropyl Redenbis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite, 2, 2 Methylene bis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylene bis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4- And di-t-butyl-5-methylphenyl) -4,4′-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among those listed above, pentaerythritol phosphite compounds and / or tris (2,4-di-t-butylphenyl) phosphite are preferable from the viewpoint of further improving the heat aging resistance and reducing the amount of gas generated. . Examples of the pentaerythritol phosphite compound include, but are not limited to, 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-4 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 pentaerythritol Diphosphite, bis (2,6-di-t- Til-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 Diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos Fight is mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6) is used from the viewpoint of reducing the amount of gas generated. -Di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-) One or more selected from the group consisting of t-octyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is More preferred.

  In the case of using a phosphorus-based heat stabilizer, the content of the phosphorus-based heat stabilizer in the welded molded product is 0.01 to 1 part by mass, more preferably 0.1 to 100 parts by mass of the welded molded product. -1 part by mass. When it is within the above range, the heat aging resistance can be further improved, and the amount of gas generated can be reduced.

<Amine heat stabilizer>
Examples of amine heat stabilizers include, but are not limited to, 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-tetramethyl Piperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethyl Piperidine, 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-tetra Methyl-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-tri Carboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) pro Onyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 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. These may be used individually by 1 type and may be used in combination of 2 or more type.

  When the amine heat stabilizer is used, the content of the amine heat stabilizer in the welded molded product is preferably 0.01 to 1 part by mass, more preferably 0, with respect to 100 parts by mass of the welded molded product. .1 to 1 part by mass. In the above range, the heat aging resistance can be further improved, and the amount of gas generated can be reduced.

<Metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table>
As metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table, any metal salt belonging to these groups is not limited. There is nothing. From the viewpoint of further improving the heat aging resistance, a copper salt is preferable. Examples of such copper salts include, but are not limited to, copper halides (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid. Examples thereof include copper, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the copper salts listed above, preferably one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate, more preferably Copper iodide and / or copper acetate. When the above (more) preferable copper salt is used, it is excellent in heat aging resistance, and can be used to effectively suppress metal corrosion (hereinafter also simply referred to as “metal corrosion”) of screws and cylinders during extrusion. Goods are obtained.

  When using a copper salt, the content of the copper salt in the welded molded product is preferably 0.01 to 0.20 parts by mass, more preferably 0.02 to 0 parts per 100 parts by mass of the welded molded product. 15 parts by mass. Within the above range, the heat aging resistance can be further improved, and copper precipitation and metal corrosion can be effectively suppressed.

  In addition, the content of the copper element derived from the copper salt is preferably 10 to 500 ppm by mass, more preferably 30 to 500, with respect to 100% by mass of the welded molded product, from the viewpoint of improving the heat aging resistance. It is mass ppm, More preferably, it is 50-300 mass ppm.

<Alkali metal and alkaline earth metal halide>
Examples of alkali metal and alkaline earth metal halides include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. Among these, potassium iodide and / or potassium bromide is preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion, and more preferably potassium iodide.

  When using alkali metal and alkaline earth metal halides, the content of alkali metal and alkaline earth metal halides in the welded molded product is preferably 0.05 to 100 parts by mass with respect to 100 parts by mass of the welded molded product. 5 parts by mass, more preferably 0.2-2 parts by mass. When it is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be effectively suppressed.

  The heat stabilizer components described above may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the heat aging resistance, a mixture of a copper salt and a halide of an alkali metal and an alkaline earth metal is preferable.

The ratio of copper salt to alkali metal and alkaline earth metal halide is preferably 2/1 to 40/1, more preferably 5 /, as the molar ratio of halogen to copper (halogen / copper). 1-30 / 1. In the above range, the heat aging resistance can be further improved.
When the above halogen / copper is 2/1 or more, it is preferable because precipitation of copper and metal corrosion can be effectively suppressed. On the other hand, when the halogen / copper is 40/1 or less, corrosion of the screw of the molding machine and the like can be prevented without substantially impairing mechanical properties (toughness and the like).

(A) As a method for producing a welded molded product when other components [(B) inorganic filler, (C) heat stabilizer, etc.] are contained in the polyamide, (A) the polyamide and the other components are mixed. If it is a method to do, it will not be restrict | limited in particular.
(A) As a method of mixing the polyamide and the above-mentioned other components, for example, (A) a method of mixing the polyamide and the other components using a Henschel mixer or the like, supplying the mixture to a melt kneader, and kneading; Examples thereof include a method of blending the other components from the side feeder into the polyamide (A) that has been melted by a screw or twin screw extruder.

In the method of supplying the components constituting the welded molded product to the melt kneader, all the components may be supplied to the same supply port at a time, or the components may be supplied from different supply ports.
The melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
The melt kneading time is preferably about 0.25 to 5 minutes.
The apparatus for performing the melt kneading is not particularly limited, and a known apparatus such as a single or twin screw extruder, a Banbury mixer, a mixing roll, or the like can be used.

The material of the fusion-molded article of the present embodiment includes additives commonly used for polyamides, for example, colorants such as pigments and dyes (colored master batches) within a range that does not impair the purpose of the present embodiment. ), Flame retardant, fibrillating agent, lubricant, fluorescent bleaching agent, plasticizer, antioxidant, stabilizer, UV absorber, antistatic agent, fluidity improver, filler, reinforcing agent, spreading agent, Nucleating agents, rubbers, reinforcing agents, and other polymers can also be included.
When the welded molded product according to the present embodiment contains other materials that can be included in the welded molded product described above, the content of the other materials depends on the type of the welded molded product and the use of the welded molded product. Since it is various, it will not be restrict | limited especially if it is a range which does not impair the objective of this Embodiment.

  The relative viscosity ηr at 25 ° C., the melting point Tm2, the heat of fusion ΔH, and the glass transition temperature Tg of the polyamide composition that can be a material for the welded molded article according to the present embodiment are measured by the same method as that for the polyamide. Can do. Moreover, when the measured value in the weld-molded product is in a range similar to the preferable range as the measured value of the polyamide, a weld-molded product having excellent heat resistance, moldability, and chemical resistance can be obtained.

The welded molded product of the present embodiment is molded in various shapes obtained by using known molding methods such as press molding, injection molding, gas assist injection molding, extrusion molding, and other generally known plastic molding methods. It is obtained by welding the product.
In addition, the said molded article shape | molds the polyamide composition containing (B) inorganic filler, (C) heat stabilizer, etc. in addition to (A) polyamide of this Embodiment mentioned above or (A) polyamide. Can be obtained.

The welding molding is not limited to the following, but for example, vibration welding, laser welding, spin welding, ultrasonic welding, orbital welding, hot plate welding, high frequency welding or injection welding (two-color molding, secondary molding, overlap molding). Is mentioned. Among these, vibration welding or laser welding is preferable from the viewpoints of improving the welding strength and appearance of the welded portion and facilitating welding in various shapes.
These methods are generally methods for forming a hollow body, and can be applied to tubular molded products such as pipes, pipes and tubes, and more complex shaped products. As described above, the welded molded product of the present embodiment can be suitably used particularly for a welded pipe, pipe or tube.
In the welding of a plurality of materials, as long as at least one is the material of the welded molded product of the present embodiment, the other materials (the counterpart material) may be the same or different, and are not particularly limited.
The welded molded article of the present embodiment is excellent in heat resistance, fluidity, strength, toughness, low water absorption, and excellent in weldability. Therefore, the welded molded product of the present embodiment is suitably used as various component materials (members) for automobiles, electrical and electronic products, industrial materials, daily products and household products, and for extrusion applications. be able to.

There is no particular limitation for automobiles, and for example, it is used for intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, and electrical parts.
For example, (air) intake manifold, oil pan, surge tank, power steering oil tank, cooling pipe, turbo intercooler tank, turbo intercooler duct, EGR pipe, oil cooler tank, oil pipe, (fuel) delivery pipe, oil pump, water pump And ATF cooling unit.
For industrial equipment, it is not particularly limited, for example, submarine oil pipes, marine oil pipes, underground oil pipes, pipe liners, marine cable gears, cams, insulating blocks, valves, power tool parts, agricultural equipment parts, Used for engine covers.

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) 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) Sebacic acid (C10DA) Wako Pure Chemical Industries, Ltd. Acid (5) Dodecanedioic acid (C12DA) Wako Pure Chemical Industries, Ltd. Trade name Dodecanedioic acid

{(B) Diamine}
(6) 2-methylpentamethylenediamine (2MPD) manufactured by Tokyo Chemical Industry Co., Ltd. Product name 2-methyl-1,5-diaminopentane (7) hexamethylenediamine (HMD) manufactured by Wako Pure Chemical Industries, Ltd. product name hexamethylenediamine (8) 1,9-nonamethylenediamine (NMD) Aldrich product name 1,9-nonanediamine (9) 2-methyloctamethylenediamine (2MOD) Manufactured with reference to the production method described in JP-A-05-17413 .
{(C) Lactam and / or aminocarboxylic acid}
(10) ε-Caprolactam (CPL) Wako Pure Chemical Industries, Ltd. Trade name ε-Caprolactam

<(B) Inorganic filler>
(11) Glass fiber (GF) manufactured by Nippon Electric Glass Co., Ltd. ECS03T275H Average fiber diameter (average particle diameter) 10 μm (circular shape), cut length 3 mm
<(C) Thermal stabilizer>
(12) Copper iodide (CuI) manufactured by Wako Pure Chemical Industries, Ltd. Trade name Copper iodide (I)
(13) Potassium iodide (KI) 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 substituent branched from the main chain was added as the raw material monomer (b-1) The number of moles of the diamine having the substituent branched from the main chain / the raw material monomer. All (b) moles of diamine) × 100 were obtained by calculation.
Further, (c) mol% of lactam and / or aminocarboxylic acid is ((c) moles of lactam and / or aminocarboxylic acid added as raw material monomer / all (a) dicarboxylic acid added as raw material monomer. (B) mole number of all diamines + (c) mole number of lactam and / or aminocarboxylic acid) × 100.
In addition, when calculating by the above formula, the denominator and the numerator do not include the number of moles of diamine having a substituent branched from the main chain (b-1) added as an additional component.

[Measuring method]
(1) Melting points Tm1, Tm2 (° C.)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER. The measurement condition is that the temperature of an endothermic peak (melting peak) that appears when about 10 mg of a sample is heated to 300 to 350 ° C. according to the melting point of the sample at a heating rate of 20 ° C./min in a nitrogen atmosphere is Tm1 (° C.). After maintaining the temperature in the molten state at the highest temperature rise for 2 minutes, the temperature was lowered to 30 ° C. at a temperature drop rate of 20 ° C./min, held at 30 ° C. for 2 minutes, and the same at the temperature rise rate of 20 ° C./min. The maximum peak temperature of the endothermic peak (melting peak) that appears when the temperature is raised to is melting point Tm2 (° C.), and the total peak area is the heat of fusion ΔH (J / g). When there were a plurality of peaks, those having ΔH of 1 J / g or more were regarded as peaks. For example, when there are two peaks of melting point 295 ° C., ΔH = 20 J / g and melting point 325 ° C., ΔH = 5 J / g, the melting point was 325 ° C. and ΔH = 25 J / g.

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

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

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

(5) Copper concentration, halogen concentration, and molar ratio of halogen and copper (halogen / Cu)
The copper concentration was determined by adding sulfuric acid to the sample (polyamide composition), dropping nitric acid while heating to decompose the organic components, measuring the resulting decomposition solution in pure water, and ICP emission analysis (high-frequency plasma emission) Quantitative analysis. As an ICP emission analyzer, Vista-Pro manufactured by SEIKO ELECTRONIC INDUSTRY CO., LTD. Was used.
Taking iodine as an example, the halogen concentration is combusted in a flask in which a sample (polyamide composition) is replaced with high-purity oxygen, and the generated gas is collected in an absorbing solution. Iodine was quantified using potentiometric titration with 1 / 100N silver nitrate solution.
The molar ratio of halogen and copper (halogen / Cu) was calculated by converting from molecular weight to mole using the above-described quantitative values.
The examples and comparative examples use I / Cu because iodine is used as the halogen.

(6) Melt shear viscosity ηs (Pa · s)
Under the temperature condition of the melting point + 20 ° C. obtained in (1) above, the fluidity was evaluated by the melt shear viscosity ηs at a shear rate of 1000 sec ⁻¹ . The specific measurement method uses a twin capillary rheometer RH7-2 manufactured by ROSAND, UK, and the orifice has a die diameter of 1.0 mm and a die entrance angle of 180 degrees, and L / D is 16 and 0.25. Two orifices were used.

(7) Tensile strength (MPa) and (8) Tensile elongation (%)
Using a dumbbell injection molding test piece (3 mm thickness) for the ASTM tensile test, it was performed according to ASTM D638. The molding test piece is a cylinder with a dumbbell test piece (3 mm thickness) for ASTM tensile test (ASTM D638) (mold temperature = Tg + 20 ° C.) attached to an injection molding machine (PS40E manufactured by Nissei Resin Co., Ltd.). Molding was performed at a temperature of (Tm2 + 10) ° C. to (Tm2 + 30) ° C.

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

(10) Strength half-life (days)
The dumbbell injection molding test piece (3 mm thickness) for ASTM tensile test in the above measurement items (7) and (8) was treated in a hot air oven at 200 ° C. for a predetermined time, and then the tensile strength was measured according to ASTM D638. . The tensile strength after the heat treatment relative to the tensile strength before the heat treatment was calculated as the tensile strength retention, and the heat treatment time at which the tensile strength retention was 50% was defined as the strength half-life.

(11) Weld strength The pellets of the polyamide composition obtained in the examples and comparative examples were formed into flat plate molded pieces (12 cm) having two thicknesses using an injection molding machine [SE130D manufactured by Sumitomo Heavy Industries, Ltd.]. × 8 cm and a molded piece having a thickness of 10 mm, and 12 cm × 8 cm and a molded piece having a thickness of 3 mm). The former molding piece injection conditions (3 mm thickness) were set to an injection pressure of 105 MPa, an injection time of 0.4 seconds, a pressure holding time of 12 seconds, a cooling time of 18 seconds, and a screw rotation speed of 100 rpm. The injection conditions (10 mm thickness) of the latter molded piece were set to an injection pressure of 55 MPa, an injection time of 0.2 seconds, a pressure holding time of 30 seconds, a cooling time of 60 seconds, and a screw rotation speed of 100 rpm. The mold temperature was set to Tg + 20 ° C., the cylinder temperature was set to (Tm2 + 10) ° C. to (Tm2 + 30) ° C., the obtained flat plate was cut, and two types of flat plate test pieces (4 cm × 12 cm, 10 mm thick test) And a test piece having a thickness of 4 mm × 12 cm and a thickness of 3 mm).
The side surfaces (12 cm × 10 mm surface and 12 cm × 3 mm surface) of the obtained two types of flat plate plate test pieces are brought into contact with each other as shown in FIG. 1, and the frequency is measured using a BRANSON MICRO PPL vibration welding machine. Vibration welding was performed under the conditions of 233 Hz, welding pressure 10.2 kgf / cm ² , amplitude 1.5 mm (thickness direction), and welding allowance 2 mm.
The welded flat plate test piece was cut at intervals of 2 cm in the direction perpendicular to the weld surface to prepare a weld test piece having a width of 2 cm.
A tensile test was performed at a tensile speed of 5 mm / min using the welding test piece, and the strength at break was measured to obtain the welding strength.

Hereafter, the manufacture example and comparative manufacture example of polyamide are shown.
[Production Example 1]
Polymerization reaction of polyamide was carried out by “hot melt polymerization method”.
(A) CHDA 896 g (5.20 mol) and (b) 2MPD 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of raw material monomers. To this homogeneous aqueous solution, 15 g (0.13 mol) of 2MPD was added (see Table 1).
The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C. until the pressure in the autoclave tank reached about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank was expressed as gauge pressure). (The liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² , water was removed from the system while heating was continued, and concentrated until the concentration of the aqueous solution reached about 75% (the liquid temperature in this system was about 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (the liquid temperature in this system was about 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm ² , heating was continued until the final temperature (350 ° C. described later) −50 ° C. (here 300 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (350 ° C. described later) −50 ° C. (here, 300 ° C.), the heating continues while the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.
Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 350 ° C. The resin temperature was kept at the final temperature (about 350 ° C.), and the inside of the tank was maintained under a reduced pressure of about 53.3 kPa (400 torr) for 30 minutes 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, the water content was adjusted to about 0.2% by mass, and the measurement results of the items (1) to (4) for the polyamide are shown in Table 2.

[Production Examples 2 to 11]
(A) Dicarboxylic acid, (b) diamine, and (c) Lactam and / or aminocarboxylic acid as shown in Table 1, and the final temperature of the resin temperature, the point of using the compounds and amounts shown in Table 1 Except for the points described above, polyamide was polymerized in the same manner as in the method described in Production Example 1 (“hot melt polymerization method”).
The obtained polyamide was dried in a nitrogen stream, the water content was adjusted to about 0.2% by mass, and the measurement results of the items (1) to (4) for the polyamide are shown in Table 2.

[Comparative Production Example 1]
(A) Dicarboxylic acid, (b) diamine, and (c) Lactam and / or aminocarboxylic acid as shown in Table 1, and the final temperature of the resin temperature, the point of using the compounds and amounts shown in Table 1 Except for the points described above, polyamide was polymerized in the same manner as in the method described in Production Example 1 (“hot melt polymerization method”).
In Comparative Production Example 1, solidification occurred in the autoclave during the polymerization, and thus the strand could not be taken out. Therefore, after cooling, it was taken out as a lump and pulverized using a pulverizer to a size of pellets.
The obtained polyamide was dried in a nitrogen stream, the water content was adjusted to about 0.2% by mass, and the measurement results of the items (1) to (4) for the polyamide are shown in Table 2.

[Comparative Production Examples 2 to 6]
(A) Dicarboxylic acid, (b) diamine, and (c) Lactam and / or aminocarboxylic acid as shown in Table 1, and the final temperature of the resin temperature, the point of using the compounds and amounts shown in Table 1 Except for the points described above, polyamide was polymerized in the same manner as in the method described in Production Example 1 (“hot melt polymerization method”).
The obtained polyamide was dried in a nitrogen stream, the water content was adjusted to about 0.2% by mass, and the measurement results of the items (1) to (4) for the polyamide are shown in Table 2.

[Production Example 12]
85.1 parts by mass of KI and 10 parts by mass of ethylene bisstearylamide were mixed to obtain a mixture of KI and ethylenebisstearylamide. To the obtained mixture, 4.9 parts by mass of CuI was sufficiently mixed, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain heat stabilizer granules.

  Polyamide compositions and molded articles (molded pieces) were produced using the polyamides obtained in the above production examples and comparative production examples, and welded molded articles were produced using the polyamide composition as a material. Polyamide composition obtained [measurement items (5) to (6) above], molded product (molded piece) obtained by molding the polyamide composition [measurement items (7) to (10) above] Since the measurement and evaluation were carried out on the welded molded product [above measurement item (11)] obtained by welding the molded product, this will be described.

[Example 1]
The polyamide produced in Production Example 1 was used. A twin screw extruder [TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature = melting point Tm2 + 20 ° C. (in this case, 327 + 20 = 347 ° C.), and screw rotation speed 300 rpm] The polyamide (100 parts by mass) and the heat stabilizer granules (3.6 parts by mass) produced in Production Example 12 were supplied from the top feed port provided at the most upstream part of the extruder. Furthermore, from the side feed port provided in the downstream side of the extruder (here, the resin supplied from the top feed port was sufficiently melted), (B) GF (inorganic filler) ( 55 mass parts) was supplied, and the melt-kneaded product extruded from the die head was cooled in a strand shape and pelletized to obtain polyamide composition pellets.
Table 2 shows the measurement results of the above items (5) to (11) for the obtained polyamide composition, molded product, and welded molded product.

[Examples 2-11, Comparative Examples 1-6]
A welded molded article was obtained in the same manner as in Example 1 except that each polyamide produced in Production Examples 2 to 11 and Comparative Production Examples 1 to 6 was used in place of the polyamide of Production Example 1.
Table 2 shows the measurement results of the above items (5) to (11) for the obtained polyamide composition, molded product, and welded molded product.
Regarding Comparative Example 1, since the extruded state was very unstable, a polyamide composition could not be obtained.

  From the results in Table 2, (A) (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid, and (b) at least 50 mol% of a diamine containing a diamine having a substituent branched from the main chain. It has been clarified that a weld-molded product containing polyamide, which is obtained by polymerizing the above, is excellent in heat resistance, fluidity, strength, toughness, low water absorption, heat aging resistance, and excellent weldability.

  The present invention provides a welded molded article containing polyamide that has excellent heat resistance, fluidity, strength, toughness, low water absorption, and heat aging resistance, and further has improved weldability (welding strength). it can. The welded molded product of the present invention can be suitably used as a molding material for various parts such as automobiles, electric and electronic, industrial materials, industrial materials, daily products and household products. Have potential.

Claims (12)

  A polyamide obtained by polymerizing (A) (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) at least 50 mol% of a diamine containing a diamine having a substituent branched from the main chain. A welded molded product containing   The welding molded article according to claim 1, wherein the diamine having a substituent branched from the main chain is 2-methylpentamethylenediamine.   The fusion-molded article according to claim 1 or 2, wherein the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.   The fusion-molded article according to any one of claims 1 to 3, wherein the dicarboxylic acid (a) further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms.   The fusion-molded article according to any one of claims 1 to 4, wherein the polyamide (A) is a polyamide obtained by further copolymerizing (c) a lactam and / or an aminocarboxylic acid.   The fusion-molded article according to any one of claims 1 to 5, wherein the polyamide (A) has a melting point of 270 to 350 ° C.   The fusion-molded article according to any one of claims 1 to 6, wherein the trans isomer ratio in the polyamide (A) is 50 to 85%.   (B) The fusion-molded article according to any one of claims 1 to 7, further comprising an inorganic filler.   (C) The fusion-molded article according to any one of claims 1 to 8, further comprising a heat stabilizer.   The welded molded product according to any one of claims 1 to 9, wherein the molded product is formed by vibration welding or laser welding.   A part including the fusion-molded product according to claim 1.   12. A part according to claim 11, which is a welded automobile part, pipe, pipe or tube.

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