JP2003138012A - Polyamide with excellent stretchability - Google Patents

Abstract

(57) Abstract: Provided is a polyamide excellent in stretchability, particularly suitable for sequential biaxial stretchability. A unit containing (A) a unit composed of a lactam and / or an aminocarboxylic acid, (B) a unit composed of a diamine, and (C) a unit composed of a dicarboxylic acid including an alicyclic dicarboxylic acid having a bridged structure. It is characterized by the following. As the alicyclic dicarboxylic acid having a bridged structure,
Examples include dicarboxylic acids represented by the following general formulas [A-1] and [A-2]. Embedded image Embedded image (However, in the general formulas [A-1] and [A-2], R
_{1 to} R ₄ each independently represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and m represents either 1 or 2. )

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyamide having excellent stretchability. More specifically, the present invention relates to a polyamide having a unit of a dicarboxylic acid as a structural unit of an alicyclic dicarboxylic acid having a cross-linked structure, and relates to a polyamide suitable for a stretched film, particularly a sequentially biaxially stretched film.

[0002]

BACKGROUND OF THE INVENTION Polyamides are used as food packaging materials such as retort foods because of their excellent heat resistance and gas barrier properties. In recent years, the required characteristics have diversified with the expansion of these food packaging applications. For example, there is a demand for a polyamide film which is thin and has excellent practical mechanical strength and gas barrier properties, and particularly a polyamide film which is suitable for a sequential biaxial stretching method with good productivity.

It is generally known that when a film obtained from a crystalline polymer is stretched, the film becomes thin and the mechanical strength per unit is improved. By applying this stretching technique, a thin film having excellent mechanical strength is produced from many crystalline polymers. However, nylon 6 and nylon 66
It is known that films, monofilaments, fibers and the like obtained from such crystalline polyamides are likely to cause stretching unevenness or break at a relatively low stretching ratio unless the stretching conditions are controlled within a certain narrow range. In particular, when a nylon film is produced by a sequential biaxial stretching method which is advantageous for mass production of the film, the first stage stretching (hereinafter referred to as “primary stretching”) of stretching in the film extrusion direction is performed. After that, it is known that the second stage stretching (hereinafter, referred to as “secondary stretching”) in which the stretching is performed in the direction perpendicular to the stretching direction of the primary stretching becomes difficult. The reason for this is that during the primary stretching, the polyamide molecules are oriented parallel to the film surface, and hydrogen bonds are formed between the molecules, which promotes crystallization, making the film hard and making the secondary stretching difficult. It is thought to be. Therefore, it is desired to develop a polyamide having excellent stretchability that can be applied to the sequential biaxial stretching method.

Therefore, many polyamide copolymers and polyamide compositions have been conventionally proposed for improving the stretchability of polyamide. As the polyamide copolymer having improved stretchability, for example, JP-A-53-5250 discloses a polyamide copolymer composed of ε-caprolactam, hexamethylenediamine, isophthalic acid and terephthalic acid.
JP-A-60-104312 proposes a polyamide copolymer comprising at least a dicarboxylic acid and an alicyclic diamine. Further, as the polyamide composition,
For example, JP-A-52-104565 proposes a composition in which an aliphatic polyamide is blended with a polyamide containing xylylenediamine and an α, ω-aliphatic dicarboxylic acid as a constituent unit. JP-A-53-88053
The publication discloses an aliphatic polyamide and 2,2,4- and / or
Alternatively, a method for producing a sequential biaxially stretched film from a composition in which 2,4,4-trimethylhexamethylenediamine and a polyamide composed of an aromatic and / or alicyclic dicarboxylic acid are blended in a specific ratio has been proposed. . Japanese Patent Publication No. 43552/1994 discloses a blend of a copolyamide obtained from an aliphatic polyamide and a semiaromatic polyamide, and an aliphatic diamine and a semiaromatic polyamide obtained from isophthalic acid and / or terephthalic acid. Polyamide compositions have been proposed. In addition, JP-A-6-
No. 263895 discloses a crystalline aliphatic polyamide and a specific alicyclic diamine, aliphatic diamine, terephthalic acid,
A composition in which an amorphous polyamide made of isophthalic acid is blended has been proposed.

The above-mentioned proposed polyamide copolymer and polyamide composition have a
Stretchability is improved. However, when the stretching ratio of the film is 3 times or more, stretching unevenness may occur, and thus the stretching ratio capable of being uniformly stretched may be limited. Further, in the secondary stretching in the sequential biaxial stretching method, stretching unevenness is likely to occur, and breakage may occur at a low stretching ratio, so that improvement in stretchability cannot be said to be sufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide having excellent stretchability, particularly suitable for successive biaxial stretchability.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have aimed to obtain a polyamide which is excellent in stretchability, particularly in sequential biaxial stretchability,
As a result of studying the relationship between the molecular structure of polyamide and the stretchability, the inventors have found that a polyamide having a unit composed of an alicyclic dicarboxylic acid having a crosslinked structure in the molecular chain has excellent stretchability, and arrived at the present invention.

That is, according to the present invention, (A) a unit composed of a lactam and / or an aminocarboxylic acid, (B) a unit composed of a diamine, and (C) a dicarboxylic acid containing an alicyclic dicarboxylic acid having a bridge structure The present invention relates to a polyamide having excellent stretchability, which comprises the following units.

Although it is not clear why a polyamide having a cross-linked alicyclic dicarboxylic acid as a constituent unit is excellent in stretchability, particularly in successive biaxial stretchability, which has been difficult to achieve in the past, it has a cross-linking structure. Since the alicyclic dicarboxylic acid has a bulky molecular structure as compared with an aliphatic polyamide such as nylon 6, the alicyclic structure having a cross-linking structure introduced into the polyamide causes It is presumed that the hydrogen bonding interaction is weakened, the orientation of the polyamide molecules in the film plane is suppressed, and the crystallization is suppressed. This means that when the films of the same draw ratio obtained from the polyamide of the present invention having a cross-linked alicyclic dicarboxylic acid as a constitutional unit and nylon 6 are compared with each other in terms of the total molecular plane orientation, It is presumed as described above also from the fact that the total degree of molecular orientation of polyamide is low.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polyamide of the present invention comprises a unit composed of (A) a lactam and / or an aminocarboxylic acid, a unit composed of (B) a diamine, and a unit composed of (C) a dicarboxylic acid containing an alicyclic dicarboxylic acid having a bridge structure. contains.

The lactam used in the present invention is ε
-Caprolactam, ω-enanthlactam, ω-undecalactam, ω-dodecalactam, 2-pyrrolidone and the like. Examples of the aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. These lactams and amino acids may be used alone, or
You may use it in combination of 2 or more types as appropriate. When laclam and aminocarboxylic acid are used in combination, they can be mixed and used at an arbitrary ratio. A polyamide copolymer composed of a polyamide derived from a lactam and / or an aminocarboxylic acid and a polyamide having a bridged alicyclic dicarboxylic acid as a constituent component is stretched even if the content of the latter is small. Sex is improved.

The diamine used in the present invention includes ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecadiamine. Methylenediamine, tridecanediamine,
Linear aliphatic diamines such as tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1 , 4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-
1,4-butanediamine, 1,4-dimethyl-1,4-
Butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-
Methyl-1,5-pentanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,5-dimethyl-1,
6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4 4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2-methyl-1,7-heptanediamine, 2,2-
Dimethyl-1,7-diaminoheptane, 2,3-dimethyl-1,7-diaminoheptane, 2,4-dimethyl-
1,7-heptanediamine, 2,5-dimethyl-1,7
-Heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-
Methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,
8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl- 1,8-octanediamine,
3,3-dimethyl-1,8-octanediamine, 4,4
-Dimethyl-1,8-octanediamine, 5-methyl-
Branched aliphatic diamines such as 1,9-nonanediamine,
Cyclopropanediamine, cyclopropyldiaminomethyl, cyclobutyldiaminomethyl, cyclopentyldiaminomethyl, 5-amino-2,2,4-trimethyl-1
-Cyclopentanemethylamine, cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane,
1,4- (bisaminomethyl) cyclohexane, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (4-amino-) 3-methylcyclohexyl) methane, bis (4-
Amino-3-methylcyclohexyl) propane, bis (4-amino-3-ethylcyclohexyl) methane,
Bis (4-amino-3,5-dimethylcyclohexyl)
Methane, bis (4-amino-3,5-dimethylcyclohexyl) propane, bis (4-amino-3-ethylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) propane, bis (4-amino-3) , 5-
Diethylcyclohexyl) methane, bis (4-amino-
3,5-diethylcyclohexyl) propane, bis (4
-Amino-3-methyl-5-ethylcyclohexyl) methane, bis (4-amino-3-methyl-5-ethylcyclohexyl) propane, bis (aminoethyl) piperazine, bis (aminopropyl) piperazine, bisaminomethylnorbornane, etc. Alicyclic diamine, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, 1,4-diaminonaphthalene 1,8-diaminonaphthalene, 2,3-
Diaminonaphthalene, 2,6-diaminonaphthalene,
3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3 ' -Diethyldiphenylmethane, 4,4'-diamino-3,3 ', 5
5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'
-Diethyldiphenylmethane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (4-amino-3)
-Methylphenyl) propane, 2,2'-bis (4-amino-3-ethylphenyl) propane, 2,2'-bis (4-amino-3,5-dimethylphenyl) propane,
Examples of the aromatic diamine such as 2,2′-bis (4-amino-3,5-diethylphenyl) propane and 2,2′-bis (4-amino-3-methyl-5-ethylphenyl) propane. These diamines may be used alone or in combination of two or more kinds.

Examples of the alicyclic dicarboxylic acid having a bridge structure, which is an essential component of the dicarboxylic acid used in the present invention, include those having the structures represented by the following general formulas [A-1] and [A-2]. To be

[0014]

[Chemical 3]

[Chemical 4] (However, in the general formulas [A-1] and [A-2], R
_{1 to} R ₄ each independently represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and m represents either 1 or 2. )

Here, as typical examples of the alkyl group having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, etc. Is mentioned. Among these, R ₁
It is preferable that R ₄ is a hydrogen atom because it is easily available. Specific examples of the alicyclic dicarboxylic acid having a bridged structure represented by the general formula [A-1] include bicyclo [2.2.1] heptanedicarboxylic acid and the general formula [A-
As specific examples of the alicyclic dicarboxylic acid represented by 2],
When m is 1, tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid, when m is 2, pentacyclo [6.
5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] Pentadecanedicarboxylic acid may be mentioned. These may be used alone or in combination of two or more.
Among these, bicyclo [2.2.1] heptanedicarboxylic acid and tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid are preferable. Furthermore, the dicarboxylic acid is a substituted isomer in which the substitution position of the carboxyl group is different,
Although stereoisomers exist depending on the conformation, any of them can be used in the present invention.

The alicyclic dicarboxylic acid having a crosslinked structure used in the present invention can be obtained by a known method. For example, bicyclo [2.2.1] heptanedicarboxylic acid can be obtained by hydrogen cyanide addition of bicyclo [2.2.1] heptenecarbonitrile.
2.1] A method is known in which heptenedicyano is hydrolyzed in an alkaline aqueous solution. The starting material, bicyclo [2.2.1] heptenecarbonitrile, can be easily obtained by a Diels-Alder reaction using dicyclopentadiene and acrylonitrile, which are industrially easily available, as raw materials. . In addition, tricyclo [5.2.1.0]
^2,6 ] decanedicarboxylic acid is hydroformylated in the presence of a catalyst containing a dicyclopentadiene with a metal compound or an organic phosphorus compound to give tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid. Carbaldehyde is produced and can be obtained by oxidizing this.
Alternatively, tetracyclo [4.4.0.1 ^2,5 .1
^[7,10 ] dodecene in the presence of an oxidant or a metal catalyst,
Obtained by oxidation. Pentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . [ ^9,13 ] pentadecanedicarboxylic acid also hydroformylates tricyclopentadiene in the presence of a catalyst containing a metal compound and an organic phosphorus compound to form pentacyclo [6.5.1.
1 ^3,6 . 0 ^2,7 . [ ^09,13 ] pentadecane dicarbaldehyde is produced and can be obtained by oxidizing this. The starting material tricyclopentadiene can be easily obtained by thermally depolymerizing dicyclopentadiene and causing polymerization, and distilling the resulting mixture. Alternatively, hexacyclo [6.6.
1.0 ^{2,5.1 3,6} . 0 ^9,14 .1 ^10,13] oxidizing agent heptadecene or metal catalysts presence, obtained by oxidation.

Examples of the dicarboxylic acid other than the alicyclic dicarboxylic acid having a cross-linking structure used in the present invention include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and tridecane. Linear aliphatic dicarboxylic acids such as candionic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosandioic acid, dimethylmalonic acid, 3,3-dimethylsuccinic acid,
2,2-dimethylglutaric acid, 2-methyladipic acid,
3-methyl adipic acid, trimethyl adipic acid, 2-butyl octadioic acid, 2,3-dibutyl butanedioic acid, 8-ethyl octadecanedioic acid, 8,13-dimethyl eicosadionic acid, 2-octyl undecanedioic acid, Branched aliphatic carboxylic acids such as 2-nonyldecanedioic acid, 1,3-cyclopentanedicarboxylic acid, 1,3
-Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dicyclohexylmethane-4,4'-
Alicyclic dicarboxylic acid such as dicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid,
1,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,
4'-biphenyldicarboxylic acid, diphenylmethane-
2,4'-dicarboxylic acid, diphenylmethane-3,3'-
Aromatic dicarboxylic acids such as aromatic dicarboxylic acids such as dicarboxylic acid, diphenylmethane-3,4'-dicarboxylic acid and diphenylmethane-4,4'-dicarboxylic acid. These dicarboxylic acids may be used alone or in appropriate combination of two or more kinds. The proportion of the alicyclic dicarboxylic acid having a crosslinked structure in the dicarboxylic acid is 10 to 100 mol%, preferably 2
It is 0 to 100 mol%. If the proportion of the alicyclic dicarboxylic acid having a crosslinked structure used is less than the above lower limit, the effect of improving the stretchability will be reduced. The diamine and the dicarboxylic acid containing the alicyclic carboxylic acid having a crosslinked structure are used in approximately equimolar ratios. The diamine and dicarboxylic acid may be used as they are, or a nylon salt obtained from the diamine and dicarboxylic acid by a known method may be used.

The polyamide of the present invention comprises (A) a unit composed of lactam and / or aminocarboxylic acid, (B) a unit composed of diamine, and (C) a dicarboxylic acid containing an alicyclic dicarboxylic acid having a bridge structure. The unit consisting of (A) lactam and / or aminocaproic acid is 50 to 99.8 mo.
1%, preferably 70-99.5 mol%,
(B) the unit consisting of diamine is 0.1 to 25 mol%,
It is preferably 0.25 to 15 mol%, and the unit composed of (C) dicarboxylic acid is 0.1 to 25 mol%, preferably 0.25 to 15 mol%. In addition, 10 to 100 mol% of the dicarboxylic acid, preferably 20 to 100
A mol%, more preferably 50 to 100 mol%, is an alicyclic dicarboxylic acid having a crosslinked structure. If the amount of lactam and / or aminocarboxylic acid used is less than the above lower limit, the mechanical strength may decrease. Also,
If it exceeds the upper limit, the stretchability may decrease.
If the amount of the alicyclic dicarboxylic acid having a crosslinked structure in the dicarboxylic acid is less than the above lower limit, the stretchability will decrease. If it exceeds the upper limit, the stretchability is good, but practical properties such as mechanical strength are deteriorated.

The production of the polyamide of the present invention can be carried out batchwise,
It can also be carried out in a continuous manner, such as a batch reaction kettle, a one-tank type or multi-tank layer continuous reaction apparatus, a tubular continuous reaction apparatus, a kneading reaction extruder such as a single-screw kneading extruder or a twin-screw kneading extruder,
A known polyamide manufacturing apparatus can be used. As the polymerization method, known methods such as melt polymerization, solution polymerization and solid phase polymerization can be used. These polymerization methods can be used alone or in an appropriate combination.

For example, a dicarboxylic acid containing lactam and / or aminocarboxylic acid, diamine, and alicyclic dicarboxylic acid having a crosslinked structure and water are charged into a pressure vessel and heated in a sealed state at a temperature range of 200 to 350 ° C. After polycondensation under pressure, the pressure is reduced, and the polycondensation reaction is continued under atmospheric pressure or reduced pressure in the temperature range of 200 to 350 ° C. to increase the molecular weight, whereby the target polyamide can be produced. At this time, the diamine and the dicarboxylic acid may be charged as they are in a pressure resistant container, or the diamine and the dicarboxylic acid in approximately equimolar amounts are mixed and dissolved in water or alcohol to form a nylon salt, and then the solution is left as it is. Alternatively, it may be charged in the state of or a concentrated solution state, or in the form of a solid nylon salt obtained by recrystallization. still,
Loss of diamine during polymerization can be prevented by adding a slight excess of diamine. As the water used in the present invention, it is desirable to use ion-exchanged water or distilled water from which oxygen has been removed.
It is generally 1 to 150 parts by weight with respect to 0 parts by weight.

The high molecular weight polyamide is usually taken out from the reaction vessel in a molten state, cooled with water or the like, and then pelletized. In the case of a pellet containing a polyamide containing a large amount of unreacted monomer such as nylon 6, the unreacted monomer and the like are further removed by washing with hot water, and then the pellet is used for producing a film, a monofilament, a fiber or the like. The polyamide of the present invention has a molecular weight of JI
Relative viscosity measured by the method described in S K6810 (η
r) is in the range of 1.5 to 5.0, preferably 2.0 to 4.
5 of them. There are no particular restrictions on the type of the terminal group of the polyamide, its concentration or the molecular weight distribution.

When polymerizing the polyamide of the present invention, phosphoric acid, phosphorous acid,
Phosphorus compounds such as hypophosphorous acid, polyphosphoric acid and their alkali metal salts can be added. The addition amount of these phosphorus compounds is usually 50 to 3,000 ppm with respect to the polyamide to be obtained. Further, in order to adjust the molecular weight and stabilize the melt viscosity during molding, one kind or two or more kinds of monoamine, diamine, monocarboxylic acid and dicarboxylic acid can be added in an arbitrary combination. Examples thereof include amines such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine, and carboxylic acids such as acetic acid, stearic acid, benzoic acid, adipic acid, isophthalic acid, and terephthalic acid. The amount of these molecular weight regulators used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the final polyamide has a relative viscosity of 1.5 to 5.0. .

The film production from the polyamide of the present invention is a known film production method, for example, a T-die method using a melt extruder, an inflation method, a tuber method, a solvent casting method, a hot pressing method and the like. It can be manufactured by the method of. Further, monofilaments and fibers can be produced by a known melt spinning method. The melting temperature of the polyamide in the method using the melt extruder or the melt spinning method is from the melting point of the polyamide used to 320 ° C.

The unstretched film obtained by the above method is
The film can be stretched uniaxially or biaxially, and as the biaxial stretching method, a tenter simultaneous biaxial stretching method, a sequential biaxial stretching method and a tuber stretching method can be used. When a film is produced by the sequential biaxial stretching method, the polyamide of the present invention is melt-extruded by an extruder equipped with a T die to form an unstretched film. The unstretched film may be subsequently stretched in a continuous process, or may be once wound and then stretched. Stretching is carried out at a temperature equal to or higher than the glass transition temperature (hereinafter, referred to as “Tg”) of the polyamide used, and the primary stretching is performed at a stretching ratio of 2 to 5 times, preferably in a temperature range of Tg to (Tg + 50) ° C. , 2.5 to 4 times, and then the secondary stretching is performed at the same temperature as or slightly higher than the primary stretching at a stretching ratio of 2 to 5 times, preferably,
After being stretched 2.5 to 4 times, the film is heat-set at a temperature of 150 ° C. or higher to successively produce a biaxially stretched film.

To the extent that the effects of the present invention are not impaired, the polyamide of the present invention can be added with a heat stabilizer, an ultraviolet absorber, a light stabilizer,
Antioxidants, lubricants, fillers, antiblocking agents, antistatic agents, tackifiers, sealability improving agents, antifog agents, release agents, impact resistance improving agents, plasticizers, pigments, dyes, Fragrances, reinforcing materials, etc. can be added.

The polyamide of the present invention is preferable as a material for a stretched film, particularly as a material for a sequentially biaxially stretched film. Moreover, it is used not only for films but also for monofilaments and fibers.
The stretchability of the fibers is also good. Further, the polyamide of the present invention can also be used for producing a molded product by injection molding, compression molding, vacuum molding or the like.

[0027]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. The measured values shown in Examples and Comparative Examples were measured by the following methods.

Measurement of ηr (Relative Viscosity) of Polyamide According to JIS K6810, 98% by weight of concentrated sulfuric acid was used as a solvent at a polyamide concentration of 1% by weight / volume, and a Ubero-
It measured at the temperature of 25 degreeC using the de viscosity meter.

Measurement of Degree of Orientation of All Molecular Surfaces of Film Stretched in Extrusion Direction A biaxial stretching machine type BIX-703 (manufactured by Iwamoto Seisakusho Co., Ltd.) temperature-controlled at a predetermined atmospheric temperature (50 ° C., 60 ° C., 70 ° C.) An unstretched sample film having a length of 92 mm and a width of 92 mm was attached to a stretching tank, preheated at an ambient temperature (also referred to as “stretching temperature”) for 20 seconds, and then 35 mm / sec in the film extrusion direction. Stretched 3 times at deformation speed
The film obtained by heat setting at ° C was used for measuring the degree of orientation of all molecular planes. Refractive index (Nx) in the stretching direction, refractive index (Ny) in the width direction and refractive index (Nz) in the thickness direction of this film
Was measured with an automatic birefringence meter KOBRA-21ADH type (manufactured by Oji Scientific Instruments), and the total molecular plane orientation degree (P) was determined from the following formula (1). P = {(Nx + Ny) / 2} -Nz (1) (where P is the degree of orientation of all molecular planes of the stretched film, Nx is the refractive index in the stretching direction of the film, Ny is the refractive index in the width direction of the film, Nz Indicates the refractive index in the thickness direction). The smaller the value of P, the smaller the orientation of polyamide molecules and the better the stretchability.

Measurement of Stretch Magnification at Break of Secondary Stretching by Sequential Biaxial Stretching Method Biaxial Stretching Machine IX-7 adjusted to an ambient temperature of 60 ° C.
An unstretched sample film was attached to a 03-type (made by Iwamoto Seisakusho) stretching tank, preheated for 20 seconds at ambient temperature (stretching temperature), and then 3.0 times at a deformation rate of 35 mm / sec in the extrusion direction of the film. Primary stretching is performed, and then secondary stretching is performed at a deformation rate of 35 mm / sec until the film breaks,
The draw ratio at break was measured.

Example 1 Stirrer, thermometer, pressure gauge, pressure controller, nitrogen inlet,
Into a 70 liter pressure vessel equipped with a pressure release port and a polymer outlet, 22000 g of ε-caprolactam, 478 g of bicyclo [2.2.1] heptanedicarboxylic acid, 301 g of hexamethylenediamine and 1140 g of distilled water were charged, and nitrogen pressure was applied. The pressure was released several times to replace the pressure in the pressure vessel with nitrogen, and then the temperature was raised to 250 ° C. Polymerize at 250 ° C under stirring for 4 hours, then raise the temperature to 270 ° C and then
The pressure was released to 0 MPa over a period of time, and the polymerization was continued for 4 hours with stirring at 270 ° C. while continuously flowing nitrogen gas at 150 ml / min. Next, the stirring was stopped, the molten polyamide was extracted from the polymer outlet in the form of a string, cooled with water, and pelletized to obtain pellets. The pellets were washed under hot water flow at 95 ° C for 12 hours to obtain an unreacted monomer.
After removing the residue, it was vacuum dried at 80 ° C. for 24 hours. The obtained polyamide had an ηr of 3.48. The pellets were mixed with 300 ppm of calcium stearate and supplied to a single screw extruder (GT-40-A-400 manufactured by Plastic Engineering Laboratory Co., Ltd.) equipped with a coat hanger type T die.
Melt kneading at 260 ° C and cooling roll controlled at 40 ° C.
And extruded onto a roll to produce an unstretched film having a thickness of 150 μm. This unstretched film was stored in an aluminum bag at 0 ° C. or lower so as not to absorb moisture until the stretchability was evaluated. 92 mm in length and 9 in width cut out from this unstretched film at the time of measurement
A 2 mm sample was attached to a biaxial stretching machine BIX-703 (manufactured by Iwamoto Seisakusho) and preheated at 50 ° C., 60 ° C., and 70 ° C. ambient temperature (stretching temperature) for about 20 seconds, respectively, and then deformed at the same temperature. 3 in the film extrusion direction at a speed of 35 mm / sec.
It was stretched twice and then heat set at 180 ° C. The degree of orientation of all molecular planes of the obtained stretched film was measured, and the results are shown in Table 1. A sample of 92 mm in length and 92 mm in width cut out from this unstretched film was used as a biaxial stretching machine IX-7.
Attached to 03 type (made by Iwamoto Seisakusho), ambient temperature 60 ℃,
Primary stretching was performed at a deformation rate of 35 mm / sec in the extrusion direction of the film by 3.0 times, and then secondary stretching was performed at the same temperature and the same deformation rate as the primary stretching until the film was broken. The stretching ratio at the time of the secondary stretching break was 4.0 times.

Example 2 The charged amounts of ε-caprolactam, bicyclo [2.2.1] heptanedicarboxylic acid, hexamethylenediamine and distilled water were 22000 g, 235 g and 148 g, respectively.
A polyamide was obtained in the same manner as in Example 1 except that the amount was 1120 g. The ηr of this polyamide was 3.58. The degree of orientation of all molecular planes of a stretched film obtained from this polyamide in the same manner as in Example 1 was measured, and the results are shown in Table 1. In addition, an unstretched film was used, and biaxial stretching was sequentially performed in the same manner as in Example 1 to measure the stretching ratio at the time of the secondary stretching breakage. The stretching ratio at the time of the secondary stretching break was 3.5 times.

Example 3 A method similar to that of Example 1 except that 582 g of tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid was used in place of bicyclo [2.2.1] heptanedicarboxylic acid. To obtain polyamide. The ηr of this polyamide was 3.45. Using this polyamide, the degree of orientation of all molecular planes of the stretched film obtained in the same manner as in Example 1 was measured, and the results are shown in Table 1. In addition, an unstretched film was used, and biaxial stretching was sequentially performed in the same manner as in Example 1 to measure the stretching ratio at the time of the secondary stretching breakage. The stretching ratio at the time of the secondary stretching break was 4.2 times.

Example 4 Instead of bicyclo [2.2.1] heptanedicarboxylic acid, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^A polyamide was obtained in the same manner as in Example 1, except that 753 g of [9,13] pentadecanedicarboxylic acid was used.
The ηr of this polyamide was 3.35. Using this polyamide, the degree of orientation of all molecular planes of the stretched film obtained in the same manner as in Example 1 was measured, and the results are shown in Table 1. In addition, an unstretched film was used, and biaxial stretching was sequentially performed in the same manner as in Example 1 to measure the stretching ratio at the time of the secondary stretching breakage. The stretch ratio at the time of the secondary stretch break was 4.3 times.

Comparative Example 1 22000 g of ε-caprolactam and 1100 of distilled water
Polyamide (nylon 6) was obtained in the same manner as in Example 1 except that g was charged and bicyclo [2.2.1] heptanedicarboxylic acid and hexamethylenediamine were not used. The ηr of this polyamide was 3.57. Using this polyamide, the degree of orientation of all molecular planes of the stretched film obtained in the same manner as in Example 1 was measured, and the results are shown in Table 1. Also, using an unstretched film,
Biaxial stretching was sequentially performed in the same manner as in Example 1, and the stretching ratio at the time of the secondary stretching break was measured. The stretching ratio at the time of the secondary stretching break was 1.3 times.

Comparative Example 2 Using adipic acid instead of bicyclo [2.2.1] heptanedicarboxylic acid, 22000 g of ε-caprolactam,
Hexamethylenediamine 301g, adipic acid 379g
And the same procedure as in Example 1 except that 1140 g of distilled water was charged.
Copolymer) was obtained. The ηr of this polyamide is 3.60.
Met. Using this polyamide, the degree of orientation of all molecular planes of the stretched film obtained in the same manner as in Example 1 was measured,
The results are shown in Table 1. Further, using this unstretched film, sequential biaxial stretching was performed in the same manner as in Example 1,
The stretch ratio at the time of the secondary stretch break was measured. The stretching ratio at the time of the secondary stretching break was 2.4 times.

[0037]

[Table 1]

Example 5 Using a polyamide obtained in the same manner as in Example 1 and using a CS-40-26N type melt extruder manufactured by Uniplus Co., a cylinder temperature of 280 ° C. and a screw rotation speed of 60 r.
The monofilament having a diameter of 2 mm was obtained by spinning at pm. Attach this monofilament to a hand-drawing machine,
After preheating for 5 minutes in a heating furnace having an ambient temperature of ° C, stretching was performed at the same temperature at a deformation rate of 1 mm / sec up to 5.5 times. As a result of repeating this operation 5 times, it was possible to stretch without breaking 5 times.

Comparative Example 3 A polyamide obtained by the same method as in Comparative Example 1 was used and stretched by the same method as in Example 7. As a result of carrying out the stretching operation 5 times, the stretching ratio was broken in the range of 3.3 to 4.6 times in all of the 5 times, and it could not be stretched to 5 times or more.

Example 6 Stirrer, thermometer, pressure gauge, pressure controller, nitrogen inlet,
A 70 liter pressure vessel equipped with a pressure release port and a polymer outlet was charged with 20000 g of 6-aminocaproic acid, 375 g of bicyclo [2.2.1] heptanedicarboxylic acid, 236 g of hexamethylenediamine and 1030 g of distilled water, and pressurized with nitrogen. After that, the pressure inside the pressure vessel was replaced with nitrogen, and the temperature was raised to 270 ° C. The mixture was reacted at 270 ° C. for 6 hours with stirring while flowing nitrogen gas. next,
The stirring was stopped, and the molten polyamide was extracted from the polymer outlet in the form of a string, cooled with water, and pelletized by pelletizing. The pellets were washed under hot water flow at 95 ° C for 12 hours to remove unreacted monomers, and then at 80 ° C for 2 hours.
It was vacuum dried for 4 hours. Ηr of the obtained polyamide is 3.
It was 38. An unstretched film was produced from this polyamide in the same manner as in Example 1. Using this unstretched film, biaxial stretching was sequentially performed in the same manner as in Example 1, and the stretching ratio at the time of the secondary stretching break was measured. The stretching ratio at the time of the secondary stretching break was 3.8 times.

[0041]

The present invention comprises (A) a unit composed of a lactam and / or an aminocarboxylic acid, (B) a unit composed of a diamine, and (C) a dicarboxylic acid containing an alicyclic dicarboxylic acid having a bridge structure. A polyamide containing a unit is excellent in stretchability and is suitable as a material for a polyamide film for sequential biaxial stretching.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 13, 2003 (2003.2.1
3)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

The diamine used in the present invention includes ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecadiamine. Linear aliphatic diamines such as methylenediamine, tridecamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, heptadecamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine. , 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butane Njiamin, 1,3-dimethyl -
1,4-butanediamine, 1,4-dimethyl-1,4-
Butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-
Methyl-1,5-pentanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,5-dimethyl-1,
6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4 4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2-methyl-1,7-heptanediamine, 2,2-
Dimethyl-1,7-diaminoheptane, 2,3-dimethyl-1,7-diaminoheptane, 2,4-dimethyl-
1,7-heptanediamine, 2,5-dimethyl-1,7
-Heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-
Methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,
8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl- 1,8-octanediamine,
3,3-dimethyl-1,8-octanediamine, 4,4
-Dimethyl-1,8-octanediamine, 5-methyl-
Branched aliphatic diamines such as 1,9-nonanediamine,
Cyclopropanediamine, cyclopropyldiaminomethyl, cyclobutyldiaminomethyl, cyclopentyldiaminomethyl, 5-amino-2,2,4-trimethyl-1
-Cyclopentanemethylamine, cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane,
1,4- (bisaminomethyl) cyclohexane, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (4-amino-) 3-methylcyclohexyl) methane, bis (4-
Amino-3-methylcyclohexyl) propane, bis (4-amino-3-ethylcyclohexyl) methane,
Bis (4-amino-3,5-dimethylcyclohexyl)
Methane, bis (4-amino-3,5-dimethylcyclohexyl) propane, bis (4-amino-3-ethylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) propane, bis (4-amino-3) , 5-
Diethylcyclohexyl) methane, bis (4-amino-
3,5-diethylcyclohexyl) propane, bis (4
-Amino-3-methyl-5-ethylcyclohexyl) methane, bis (4-amino-3-methyl-5-ethylcyclohexyl) propane, bis (aminoethyl) piperazine, bis (aminopropyl) piperazine, bisaminomethylnorbornane, etc. Alicyclic diamine, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, 1,4-diaminonaphthalene 1,8-diaminonaphthalene, 2,3-
Diaminonaphthalene, 2,6-diaminonaphthalene,
3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3 ' -Diethyldiphenylmethane, 4,4'-diamino-3,3 ',
5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-
5,5'-diethyldiphenylmethane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (4
-Aminophenyl) propane, 2,2'-bis (4-amino-3-methylphenyl) propane, 2,2'-bis (4-amino-3-ethylphenyl) propane, 2,
2'-bis (4-amino-3,5-dimethylphenyl) propane, 2,2'-bis (4-amino-3,5-diethylphenyl) propane, 2,2'-bis (4-amino-3)
Examples thereof include aromatic diamines such as -methyl-5-ethylphenyl) propane, and these diamines may be used alone or in combination of two or more kinds.

Continued front page    F term (reference) 4F071 AA54 AA88 AH04 BB08 BC01                 4J001 DA01 DB04 DC13 DC14 EA06                       EA07 EA08 EA15 EA16 EA17                       EB08 EB09 EB10 EB13 EB15                       EB16 EB36 EB37 EB46 EB56                       EC05 EC07 EC08 EC09 EC10                       EC13 EC14 EC16 EC45 EC46                       EC47 EC48 EC54 FA05 FB05                       FC05 GA03 GA12 GB03 JA13                       JB02                 4L035 BB31 DD14 GG01

Claims (7)

[Claims] 1. A unit comprising (A) a lactam and / or an aminocarboxylic acid unit, (B) a diamine unit, and (C) a dicarboxylic acid unit containing a bridged alicyclic dicarboxylic acid. A polyamide having excellent stretchability, which is characterized by: 2. The polyamide having excellent stretchability according to claim 1, wherein 10 to 100 mol% of the dicarboxylic acid is an alicyclic dicarboxylic acid having a crosslinked structure. 3. A unit of 50 to 99.8 mol% consisting of (A) lactam and / or aminocarboxylic acid, 0.1 to 25 mol% of unit consisting of (B) diamine, and 0.1 unit of (C) dicarboxylic acid. Polyamide consisting of ˜25 mol%, wherein the dicarboxylic acid is from 10 to 100 mo
A polyamide having excellent stretchability, wherein 1% is an alicyclic dicarboxylic acid having a crosslinked structure. 4. The alicyclic dicarboxylic acid having a crosslinked structure is at least one dicarboxylic acid represented by the following general formulas [A-1] and [A-2]. The polyamide having excellent stretchability according to any one of 3 to 3. [Chemical 1] [Chemical 2] (However, in the general formulas [A-1] and [A-2], R
_{1 to} R ₄ each independently represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and m represents either 1 or 2. ) 5. The alicyclic dicarboxylic acid having a crosslinked structure is derived from bicyclo [2.2.1] heptanedicarboxylic acid, tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid or a mixture thereof. The polyamide having excellent stretchability according to any one of claims 1 to 3, which is a dicarboxylic acid selected. 6. A film, monofilament or fiber produced from the polyamide according to claim 1. 7. A sequential biaxially stretched film produced from the polyamide according to claim 1.