JP5524538B2 - Polyamide sheet - Google Patents

Description

  The present invention relates to a polyamide sheet.

  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, and chemical resistance. Widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily products and household products.

In the automobile industry, as an environmental measure, there is a demand for reducing the weight of the vehicle body by replacing metal in order to reduce exhaust gas. In order to meet these requirements, polyamides are increasingly used for exterior materials and interior materials, and the level of required properties such as heat resistance, strength, and appearance for polyamide materials is further improved. Above all, since the temperature in the engine room is also increasing, there is an increasing demand for higher heat resistance for the polyamide material.
Further, in the electrical and electronic industries such as home appliances, in order to cope with the lead-free surface mount (SMT) solder, it is required to increase the heat resistance of the polyamide material that can withstand the rise in 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., it is difficult to obtain a molded product having sufficient characteristics due to severe pyrolysis of the polyamide even if a molded product is obtained by melt molding.

  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

However, although the 6T copolymer polyamide certainly has the characteristics of low water absorption, high heat resistance, and high chemical resistance, the fluidity is low, the moldability and the surface appearance of the molded product are insufficient, and the toughness and Inferior in light resistance.
Therefore, the appearance of a molded product such as an exterior part is required, and improvement is desired for applications exposed to sunlight or the like. In addition, the specific gravity is large and improvement is desired in terms of weight reduction.

  The PA6T / 2MPDT disclosed in Patent Document 1 can partially improve the problems of the conventional PA6T copolymer polyamide, but it has fluidity, moldability, toughness, surface appearance of molded product, color tone and light resistance. On the other hand, the improvement level 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. May not meet the requirements.

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 are also insufficiently improved in terms of toughness, strength, and fluidity.

  Accordingly, there is a need for a polyamide sheet having improved heat resistance, strength, toughness, low water absorption and color tone in a well-balanced manner.

  The problem to be solved by the present invention is to provide a polyamide sheet which is excellent in heat resistance, strength, toughness and low water absorption, and further excellent in moldability and color tone.

As a result of intensive studies to solve the above problems, the present inventors have obtained a polyamide sheet obtained by polymerizing alicyclic dicarboxylic acid and a diamine having a substituent branched from the main chain as main components. The present inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention is as follows.

[1]
(A): (a) at least 50 mol% of a dicarboxylic acid containing an alicyclic dicarboxylic acid,
(B) a diamine containing at least 50 mol% of a branched saturated aliphatic diamine having 3 to 20 carbon atoms ;
And a relative viscosity ηr at 25 ° C. of 1.9 to 5.5.
There is provided a polyamide sheet comprising the polyamide.

[2]
(B) The polyamide sheet according to [1], wherein the branched saturated aliphatic diamine having 3 to 20 carbon atoms contained in the diamine is 2-methylpentamethylenediamine.

[3]
(A) The polyamide sheet according to [1] or [2], wherein the alicyclic dicarboxylic acid contained in the dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.

[4]
The polyamide sheet according to any one of [1] to [3], wherein the (a) dicarboxylic acid further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms.

[5]
The (A) polyamide provides the polyamide sheet according to any one of [1] to [4], wherein (c) a lactam and / or aminocarboxylic acid is further copolymerized.

[6]
The polyamide sheet according to any one of [1] to [5], wherein the polyamide (A) has a melting point Tm2 of 270 to 350 ° C.

[7]
The polyamide sheet according to any one of [1] to [6], wherein the trans isomer ratio in the polyamide (A) is 50 to 85%.

  According to the present invention, it is possible to provide a polyamide sheet which is excellent in heat resistance, strength, toughness and low water absorption, and further excellent in moldability and color tone.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.

  The material of the sheet (sometimes referred to as a film) of the present embodiment includes (A) polyamide.

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

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

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

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

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

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

Examples of the aromatic dicarboxylic acid include unsubstituted or various terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. And aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with the above substituent.
Examples of the various substituents include, 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 proportion of the alicyclic dicarboxylic acid is 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and most 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 (b) The diamine used in the present embodiment contains at least 50 mol% of a diamine having a substituent branched from the main chain.
(B) By containing at least 50 mol% of a diamine having a substituent branched from the main chain as the diamine, a polyamide that simultaneously satisfies fluidity, toughness, 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.

  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%, Especially 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 from 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 be further copolymerized with (c) lactam and / or aminocarboxylic acid from the viewpoint of toughness.
The (c) lactam and / or aminocarboxylic acid used in the present embodiment means a lactam and / or aminocarboxylic acid that can be 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.
The trans isomer ratio of the alicyclic dicarboxylic acid structure in the polyamide represents the ratio of the trans isomer in the entire alicyclic dicarboxylic acid in the polyamide, and the trans isomer ratio is preferably 50 to 85 mol%. More preferably, it is 50-80 mol%, More preferably, it is 60-80 mol%.
(A-1) As the alicyclic dicarboxylic acid, it is preferable to use an alicyclic dicarboxylic acid having a trans isomer / cis isomer ratio (molar ratio) of 50/50 to 0/100. And (b) the polyamide obtained by polymerization of the diamine preferably has a trans isomer ratio of 50 to 85 mol%.
When the trans isomer ratio is within the above range, the polyamide has a high melting point, toughness and strength, as well as high thermal rigidity due to a high Tg, and fluidity, which is usually opposite 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 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”). It may be 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, (It 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 the fluidity of the polyamide, it is preferable to carry out the polymerization while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid at 85% or less, and particularly by maintaining at 80% or less, A polyamide having excellent color tone and tensile elongation and having a high melting point can be obtained.
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 a continuous hot melt polymerization method, for example, a solution of about 40 to 60% by mass containing water and a polyamide component as a solvent is preheated to about 40 to 100 ° C. in a container of a preliminary apparatus, and then a concentrated layer / Concentrated to about 70-90% at a pressure of about 0.1-0.5 MPa (gauge pressure) and a temperature of about 200-270 ° C. to obtain a concentrated solution. The concentrated solution is discharged into a flasher maintained at a temperature of about 200 to 350 ° C., and then the pressure is reduced to atmospheric pressure (gauge pressure is 0 MPa). After reducing the pressure to atmospheric pressure, reduce the pressure as necessary. The polyamide melt is then extruded into strands, cooled and cut into pellets.

As a molecular weight of the polyamide (A) in the present embodiment, a relative viscosity ηr at 25 ° C. was used as an index.
The molecular weight of the polyamide (A) in the present embodiment is as follows: mechanical properties such as toughness and strength; moldability, etc .; 98% sulfuric acid concentration 1%, relative viscosity ηr at 25 ° C. measured according to JIS-K6810, Preferably it is 1.5-7.0, 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 the following examples.

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

The heat of fusion ΔH of the polyamide (A) in the present embodiment is preferably 10 J / g or more, more preferably 14 J / g or more, further preferably 18 J / g or more, from the viewpoint of heat resistance. More preferably, it is 20 J / g or more.
The measurement of the melting point (Tm1 or Tm2) of polyamide (A) and the heat of fusion ΔH in the present embodiment can be performed according to JIS-K7121 as described in the following examples.
Examples of the measuring device for the melting point and the heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER.

The glass transition temperature Tg of the (A) polyamide in the present embodiment is preferably 90 to 170 ° C. The glass transition temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 110 ° C. or higher. Further, the glass transition temperature is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
(A) By setting the glass transition temperature of polyamide to 90 ° C. or higher, a polyamide having excellent heat resistance and chemical resistance can be obtained. Moreover, the molded article with a good external appearance can be obtained by setting the glass transition temperature of (A) polyamide to 170 ° C. or lower.
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 material of the sheet (film) of the present embodiment includes additives commonly used for polyamides, for example, colorants such as pigments and dyes (colored master batches), as long as the object of the present embodiment is not impaired. ), Flame retardant, fibrillating agent, lubricant, fluorescent bleaching agent, plasticizer, antioxidant, stabilizer, UV absorber, antistatic agent, fluidity improver, filler, reinforcing agent, spreading agent, It can also contain nucleating agents, rubber, reinforcing agents as well as other polymers.
The sheet (film) of the present embodiment contains polyamide, but the content of polyamide in the sheet is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, and further 95 to 100% by mass. Preferably, 98 to 100% by mass is even more preferable.

[Inorganic filler]
For example, the inorganic filler 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, calcium silicate, sodium aluminosilicate, silicic acid Magnesium, Ketjen Black, Acetylene Black, Furnace Black, Carbon Nanotube, Graphite, Brass, Copper, Silver, Aluminum, Nickel, Iron, Calcium Fluoride, Mica, Montmorillonite, Swelling Fluorine Mica and Apatite Etc., and the like.
The inorganic filler may be surface treated with a silane coupling agent or the like. Although it does not restrict | limit especially as said silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyl triethoxysilane, (gamma) -aminopropyl trimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane. And the like; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. Especially, it is preferable that it is 1 or more types selected from said enumeration component, and aminosilanes are more preferable.

[Thermal stabilizer]
For example, as the heat stabilizer, for example, phenol heat stabilizer, phosphorus heat stabilizer, amine heat stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table And metal salts of group IVb and group IVb elements, and alkali and alkaline earth metal halides.
Among these, from the viewpoint of thermal aging properties, metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table, and alkali and alkaline earth metals The halides are preferred. The above-mentioned heat stabilizers may be used alone or in combination of two or more.

[Phenolic heat stabilizer]
Although it does not restrict | limit as a phenol type heat stabilizer below, For example, a hindered phenol compound is mentioned. Phenol-based heat stabilizers, particularly hindered phenol compounds, have the property of imparting 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. In this Embodiment, 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 blending amount of the phenol-based heat stabilizer in the polyamide is preferably 0.01 to 1 part by weight, more preferably 0.1 to 1 part with respect to 100 parts by weight of the polyamide. Part by mass. When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further 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. In this Embodiment, 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 tris (2,4-di-t-butylphenyl) phosphite are preferable from the viewpoint of further improving the heat aging resistance and reducing the generated gas. 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. In this Embodiment, 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-di-t-butyl-4-) Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) Pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

  When using a phosphorus heat stabilizer, the compounding quantity of the phosphorus heat stabilizer in polyamide is 0.01-1 mass part with respect to 100 mass parts of polyamides, More preferably, it is 0.1-1 mass part. It is. When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further 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. In this Embodiment, these may be used individually by 1 type and may be used in combination of 2 or more type.

  When using an amine heat stabilizer, the compounding amount of the amine heat stabilizer in the polyamide is preferably 0.01 to 1 part by mass, more preferably 0.1 to 1 part per 100 parts by mass of the polyamide. Part by mass. When it is within the above range, the heat aging resistance can be further improved, and the amount of generated gas can be further reduced.

[Metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table]
The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table is not particularly limited, but is preferably a copper salt. is there. 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 alone or in combination of two or more.

Among the copper salts listed above, one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate are preferred, and copper iodide is more preferred. And / or copper acetate.
When such a preferable copper salt is used, a polyamide having excellent heat aging resistance and capable of suppressing metal corrosion (hereinafter also simply referred to as “metal corrosion”) of a screw or a cylinder during extrusion is obtained.
When using a copper salt, the compounding amount of the copper salt in the polyamide is preferably 0.01 to 0.2 parts by mass, more preferably 0.02 to 0.15 parts by mass with respect to 100 parts by mass of the polyamide. It is.
When it is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.
Moreover, from the viewpoint of improving the heat aging resistance, the content of copper element is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, and still more preferably 50 to 300 ppm with respect to the total amount of polyamide.

[Alkali metal and alkaline earth metal halides]
Alkali metal and alkaline earth metal halides are not limited to the following examples, but examples include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. Can be mentioned.
In particular, from the viewpoint of improvement in heat aging resistance and suppression of metal corrosion, potassium iodide and potassium bromide, and a mixture thereof are preferable, and potassium iodide is more preferable.
When the alkali metal and alkaline earth metal halide is used, the blending amount of the alkali metal and alkaline earth metal halide in the polyamide is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyamide. Yes, more preferably 0.2 to 2 parts by mass. Within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

The component of the heat stabilizer mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type. Particularly preferred are mixtures of copper salts with alkali metal and alkaline earth metal halides.
The ratio of the copper salt to the alkali metal and alkaline earth metal halide is preferably included in the polyamide so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. More preferably, it is 5/1 to 30/1. In the above range, the heat aging resistance can be further improved.
When the halogen / copper is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be 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 such as toughness.

(A) As a manufacturing method of the material of the sheet | seat (film) of this Embodiment in the case of making a polyamide contain another component, if (A) polyamide and the other component are mixed, it will be specifically limited. It is not a thing.
As a method for mixing the polyamide and the inorganic filler, for example, a method in which the polyamide and other components are mixed using a Henschel mixer, and supplied to a melt kneader and kneaded, or in a molten state with a single or twin screw extruder. The method of mix | blending other components with polyamide from a side feeder is mentioned. Moreover, the method of pellet-blending the thing which made the other component the masterbatch and / or a raw material is mention | raise | lifted.

In the method of supplying polyamide and other components to the melt-kneader, all the components may be supplied to the same supply port at once, 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 polyamide sheet of the present embodiment has a thickness of 0.01 to 2.0 mm, preferably 0.01 to 0.5 mm, and more preferably 0.01 to 0.2 mm.
The polyamide sheet of the present embodiment can be manufactured by a conventionally known method using the above-mentioned (A) polyamide, mixing with the above-mentioned other materials, and using this as a raw material.

The polyamide sheet of the present embodiment can be prepared by mixing constituent materials in advance and molding the extruded sheet. In addition, the constituent components are directly fed into an extruded sheet molding machine, and blending and sheet molding are performed simultaneously. It can also be made.
Moreover, you may manufacture the polyamide sheet of this Embodiment by the extrusion tubular method (method also called the inflation method).
Furthermore, the polyamide sheet of the present embodiment can also be manufactured by a T-die extrusion method. In this case, it may be used without stretching, may be uniaxially stretched, or may be biaxially stretched.
When it is desired to increase the strength of the sheet, it can be achieved by stretching.

  The polyamide sheet of the present embodiment may have a surface laminated with a paint, a metal layer, various polymers, or the like.

[Use]
The polyamide sheet of the present embodiment is excellent in heat resistance, strength, toughness, low water absorption, moldability, and has an excellent color tone, so it is for automobiles, electric and electronic, industrial materials It can be suitably used as various parts materials for daily use and household goods.
There are no particular limitations on the electrical and electronic use, and for example, it is used for electrical insulating materials such as motors, transformers, and cables, dielectric materials such as capacitors, printed circuit boards, and electronic board materials such as flat cables.
There is no particular limitation for industrial equipment, and for example, it is used for magnetic materials such as sheet magnets.
It is not specifically limited as for daily use and household goods, for example, it is used for buttons, food containers, office furniture and the like.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.
First, the raw material of the polyamide sheet, the calculation method of the amount of the polyamide component, the physical property value measuring method, and the evaluation method applied in the following examples and comparative examples are shown.
In this specification, 1 kg / cm ² is 0.098 MPa.

[Raw material of polyamide sheet]
(A) Polyamide is shown below as a raw material for the polyamide sheet.
(A) Polyamide (a) Dicarboxylic acid (1) 1,4-cyclohexanedicarboxylic acid (CHDA) Product name 1,4-CHDA HP grade (trans isomer / cis isomer (molar ratio) = 25/75) manufactured by Eastman Chemical
(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) Product name 2-methyl-1,5-diaminopentane (7) Hexamethylenediamine (HMD) Product name Hexamethylene Diamine (8) 1,9-nonamethylenediamine (NMD) Aldrich product name 1,9-nonanediamine (9) 2-methyloctamethylenediamine (2MOD) Refer to the production method described in JP-A No. 05-17413 Manufactured.

(C) Lactam and / or aminocarboxylic acid (10) ε-caprolactam (CPL) Wako Pure Chemical Industries, Ltd. Product name ε-caprolactam

[Calculation method of polyamide component amount]
(A) mol% of (a-1) alicyclic dicarboxylic acid contained in dicarboxylic acid is (number of moles of (a-1) alicyclic dicarboxylic acid added as raw material monomer / all of raw material monomers added (A) Number of moles of dicarboxylic acid) × 100.
(B) The mol% of the diamine having a substituent branched from the main chain contained in the diamine is (b-1) the mole of the diamine having a substituent branched from the main chain added as a raw material monomer. Number / number of moles of (b) diamine added as raw material monomer) × 100.
In addition, (C) mol% of the lactam and / or aminocarboxylic acid contained in the polyamide is ((c) moles of lactam and / or aminocarboxylic acid added as raw material monomer / added as raw material monomer, All (a) moles of dicarboxylic acid + (b) moles of all diamines + (c) moles 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.

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

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

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

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

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

(6) Tensile elongation (%)
Further, the tensile elongation (%) was defined as the ratio of the amount of displacement between chucks when ruptured to the initial chuck distance before the test by the tensile test. The tensile elongation (%) was calculated by the following formula.
Tensile elongation (%) = 100 × displacement at break / distance between initial chucks

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

(8) Sheet Formability “Formability” when a sheet-like molded body shown below was produced was evaluated by thickness unevenness.
The thickness of the central part of the sheet was measured at 30 points every 30 seconds in the flow direction, and evaluated based on the occurrence of thickness unevenness.
A: The thickness unevenness measured at 20 points is less than 10% of the set thickness, and the thickness of the sheet is fairly stable.
Δ: The thickness unevenness of the 20-point measurement is less than 20% of the set thickness, but the sheet feels slightly wavy, but the thickness is stable.
X: Thickness unevenness measured at 20 points, there are 20% or more of the set thickness, and the sheet is considerably wavy. Or, a film having a stable thickness cannot be obtained.

(9) Sheet color tone b value Using a color difference meter ND-300A manufactured by Nippon Denshoku Co., Ltd., the b value of the roll sheet surface was measured to evaluate the color tone.
If the b value was 11 or less, it was judged that the yellowness was small and the color tone was excellent.

[Production example of polyamide]
<Production Example 1>
A polyamide polymerization reaction was carried out by the “hot melt polymerization method”.
(A) Dicarboxylic acid: CHDA 896 g (5.20 mol) and (b) diamine: 2MPD 604 g (5.20 mol) were dissolved in distilled water 1500 g to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomer.
To this homogeneous aqueous solution, 15 g (0.13 mol) of (b) diamine: 2MPD was added.
The aqueous solution thus obtained was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept at a liquid temperature (internal temperature) of 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 until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It 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.).
Heating was continued until the final temperature reached −50 ° C. while removing water out of the system in order to keep the pressure in the tank at about 30 kg / cm ² . After the liquid temperature rose to the final temperature of −50 ° C. (here, 300 ° C.), while continuing heating, the pressure in the tank was decreased while taking about 120 minutes until the pressure in the tank reached atmospheric pressure (gauge pressure was 0 kg / cm ² ). .
Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 350 ° C. With the resin temperature kept in this state, the inside of the tank was maintained for 30 minutes under a reduced pressure of 400 torr with a vacuum apparatus. Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain a polyamide.
The polyamide thus obtained was dried in a nitrogen stream and the moisture content was adjusted to about 0.1% by mass, and then the above measurements (1) to (7) were performed on the polyamide.
The composition of the polyamide is shown in Table 1 below, and the physical properties and evaluation are shown in Table 2 below.

<Production Examples 2 to 11>
(A) Dicarboxylic acid, (b) diamine, (c) lactam and / or aminocarboxylic acid were used according to the compounds and amounts shown in Table 1 below, and the final temperature of the resin temperature was set to the temperature shown in Table 1 below.
For other conditions, the polyamide was polymerized by the same method as in Production Example 1 (“hot melt polymerization method”).
The polyamide thus obtained was dried in a nitrogen stream, and the moisture content was adjusted to about 0.1% by mass. With respect to this polyamide, the above measurements (1) to (7) were performed.
The measurement results are shown in Table 2 below.

<Comparative Production Example 1>
(A) Dicarboxylic acid, (b) diamine, (c) lactam and / or aminocarboxylic acid were used according to the compounds and amounts shown in Table 1 below, and the final temperature of the resin temperature was set to the temperature shown in Table 1 below.
For other conditions, the polyamide was polymerized by the same method as in Production Example 1 (“hot melt polymerization method”).
In Comparative Production Example 1, since it was solidified in the autoclave during the polymerization, it could not be taken out as a strand. Therefore, after cooling, it was taken out as a lump, pulverized with a pulverizer, and adjusted to the size of a pellet.
The polyamide thus obtained was dried in a nitrogen stream, and the moisture content was adjusted to about 0.1% by mass.
Measurements (1) to (4) above were performed on this polyamide. The measurement results are shown in Table 2 below.
Since the polyamide of Comparative Production Example 1 could not mold the test pieces for measuring the tensile strength, tensile elongation, and water absorption rate, the measurements (5) to (7) were not performed.
In addition, the sheet could not be molded.

<Comparative Production Examples 2-6>
(A) Dicarboxylic acid, (b) diamine, (c) lactam and / or aminocarboxylic acid were used according to the compounds and amounts shown in Table 1 below, and the final temperature of the resin temperature was set to the temperature shown in Table 1 below.
For other conditions, the polyamide was polymerized by the same method as in Production Example 1 (“hot melt polymerization method”).
The polyamide thus obtained was dried in a nitrogen stream, and the moisture content was adjusted to about 0.1% by mass. With respect to this polyamide, the above measurements (1) to (7) were performed. The measurement results are shown in Table 2 below.

[Production example of polyamide sheet]
<Examples 1-11, Comparative Examples 1-6>
The polyamides of Production Examples 1 to 11 and Comparative Production Examples 1 to 6 were further dried in a nitrogen stream, and the moisture content was adjusted to 0.05% by mass or less.
Extrusion sheet molding was performed at a screw rotation speed of 30 rpm and a discharge rate of 6 kg / h using a single-screw extruder with a screw diameter of 40 mm, in which the temperature of the cylinder and the temperature of the T dice (width: 40 cm) were set to melting point Tm2 + 20 ° C. .
At this time, the clearance of the T dice and the sheet take-up speed were adjusted so that the sheet had a thickness of 0.10 mm.
Using the produced sheet, the above (8) sheet formability was evaluated, and (9) the sheet b value was measured. The evaluation and measurement results are shown in Table 2 below.

  As shown in Table 2 above, (A): (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid, and (b) a diamine having a substituent branched from at least 50 mol% of the main chain. It was found that the polyamide obtained by polymerizing the diamine containing was excellent in heat resistance, strength, toughness and low water absorption, and the polyamide sheet was excellent in moldability and color tone.

  The polyamide sheet of the present invention has industrial applicability as a molding material for various parts for automobiles, electric and electronic use, industrial materials, industrial materials, daily use and household goods.

Claims (7)

(A): (a) at least 50 mol% of a dicarboxylic acid containing an alicyclic dicarboxylic acid,
(B) a diamine containing at least 50 mol% of a branched saturated aliphatic diamine having 3 to 20 carbon atoms;
And a relative viscosity ηr at 25 ° C. of 1.9 to 5.5.
A polyamide sheet containing the polyamide. The polyamide sheet according to claim 1, wherein the branched saturated aliphatic diamine having 3 to 20 carbon atoms contained in (b) diamine is 2-methylpentamethylenediamine. The polyamide sheet according to claim 1 or 2, wherein the (a) the alicyclic dicarboxylic acid contained in the dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid. The polyamide sheet according to any one of claims 1 to 3, wherein the (a) dicarboxylic acid further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms. The polyamide sheet according to any one of claims 1 to 4, wherein the (A) polyamide is a polyamide in which (c) a lactam and / or an aminocarboxylic acid is further copolymerized. The polyamide sheet according to any one of claims 1 to 5, wherein the polyamide (A) has a melting point Tm2 of 270 to 350 ° C. The polyamide sheet according to any one of claims 1 to 6, wherein the (A) polyamide has a trans isomer ratio of 50 to 85%.