JP2000297150A - Polyamide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin or a polyamide resin compsn. suitable for preparing a polyamide film having excellent physical properties and transparency. SOLUTION: This polyamide resin comprises an ε-caprolactam as a main polymer constituting component, and having a low mol.wt. component with a mol.wt. of 1,000-10,000 in a concn. of 10.0 wt.% or less based on 100 wt.% of a polyamide having a mol.wt. of 1,000 or more, the mol.wt. being measured by gel permeation chromatography and being polystyrene-converted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition for producing a polyamide film having excellent transparency, and a polyamide film using the composition.

[0002]

2. Description of the Related Art Polyamide films have an oxygen barrier property,
Although it has excellent properties such as chemical resistance and pinhole resistance, it has a drawback that transparency is deteriorated due to crystallization during molding. In order to overcome this drawback, a method of adding a low molecular weight component such as a fatty acid amide or caprolactam to a polyamide resin (for example, JP-A-64-85315) and a method of reducing crystallinity by copolymerization are known. However, there is a problem that the added low molecular weight component gradually dissolves to the outside during use of the polyamide molded product, causing migration to the outside, and gradually decreasing transparency during use. In addition, in the improvement by copolymerized polyamide, generally, the more copolymerized components, the better the transparency, but at the same time, the physical properties such as strength and chemical resistance also deteriorate, so it is difficult to achieve both required performance and transparency. There are many. On the other hand, a film made of polyamide is known to easily block and impair the workability during packing and packaging, and in order to improve the blocking property, generally, finely divided inorganic substances such as silica, talc, and kaolin are used. Often added,
The addition of finely divided inorganic substances deteriorates the transparency of the molded product and lowers its commercial value, and at the same time, becomes a foreign substance in the film and causes breakage during stretching. Therefore, even if these inorganic substances are added, the transparency is not deteriorated and the stretching is performed. A polyamide that does not break has been desired.

[0003]

SUMMARY OF THE INVENTION Under these circumstances, the present invention has been made to solve the above-mentioned disadvantages of the prior art, and an object of the present invention is to provide a polyamide having improved transparency without impairing the physical properties of the polymer. An object of the present invention is to provide a polyamide resin or a polyamide resin composition suitable for producing a film, and more particularly to provide a stretched film with a resin or a resin composition having a remarkable effect.

[0004]

Means for Solving the Problems As a result of diligent studies on the above-mentioned problems, the present inventors have found that a film using a polyamide resin or a polyamide resin composition in which an oligomer having a specific molecular weight range is a certain amount or less is specifically excellent. The present invention has been found to have excellent physical properties and transparency.
That is, the gist of the present invention is that the molecular weight in terms of polystyrene measured by gel permeation chromatography is 1
When 100% by weight or more of polyamide of 000 or more is
A polyamide resin containing ε-caprolactam as a main polymer component, characterized in that the ratio of low molecular weight compounds having a molecular weight of 1,000 to 10,000 is 10.0% by weight or less.

[0005] The gist of the present invention is to provide a component A: a polyamide resin composition 1 to 8 containing 0.5 to 20% by weight of fine particles.
0 parts by weight and component B: a polyamide resin composition obtained by mixing 99 to 20 parts by weight of the above polyamide resin substantially containing no fine particles. Further, the gist of the present invention resides in a polyamide-based resin film using the polyamide resin or the polyamide resin composition.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The polyamide resin used for producing the polyamide resin or the polyamide resin composition of the present invention is ε
-A polymer having caprolactam as a main polymer component, and containing a small amount of a lactam, amino acid, dicarboxylic acid or diamine having three or more rings as a copolymer component, preferably 3% by weight or less, more preferably 1% by weight or less. Alternatively, the terminal may be modified with a monocarboxylic acid or dicarboxylic acid, a monoamine or a diamine as needed.

In order for a film using the polyamide resin or polyamide resin composition of the present invention to exhibit specifically excellent transparency, a polyamide having a polystyrene equivalent molecular weight of 1,000 or more measured by gel permeation chromatography must be used. When the weight is 100% by weight, the molecular weight is 10
The ratio of low molecular weight substances of from 00 to 10,000 is 10.0
% By weight, preferably 9.5% by weight or less, more preferably 9.0% by weight or less, especially 8.
5% by weight or less is preferred. Molecular weight 1000-1000
If the ratio of the low molecular weight compound of 0 is more than 10.0% by weight, the transparency is deteriorated.

The half-crystallization time of the polyamide resin of the present invention measured at 185 ° C. by an isothermal crystallization method using a differential scanning calorimeter is usually 180 seconds or more, preferably 2 seconds.
It is at least 20 seconds, more preferably at least 250 seconds. Further, the recrystallization temperature after melting once is 155 to 162.
° C, preferably 156 to 162 ° C, particularly preferably 15 ° C.
7-161 ° C. If the ratio of the low molecular weight compound having a molecular weight of 1,000 to 10,000 is more than 10.0% by weight, crystallization is promoted, the half-crystallization time by the isothermal crystallization method is shortened, and the recrystallization temperature is also increased. Deteriorates the transparency of the film.

The method for producing the polyamide resin of the present invention can be selected from among known conditions, but the polyamide having a polystyrene equivalent molecular weight of 1,000 or more measured by gel permeation chromatography was defined as 100% by weight. In order to reduce the ratio of low molecular weight compounds having a molecular weight of 1,000 to 10,000 to 10.0% by weight or less, ε-
It is preferable to promote the so-called polyaddition reaction of caprolactam. In the case of melt polymerization generally performed, water, 6-aminocaproic acid, ε-
The amount of a polyaddition reaction accelerator such as a polyamide oligomer containing caprolactam as a main component is set to 1.0% by weight or more to sufficiently react ε-caprolactam with these to promote ring opening and polyaddition of ε-caprolactam. 22 to do
It is preferable to go through a step of treating at a high temperature of 0 ° C. or higher, preferably 250 ° C. or higher, especially 260 ° C. or higher. Also,
When the polyaddition reaction accelerator to be added is a volatile component such as water, it is preferable to pressurize the inside of the reactor in order to maintain the above-mentioned temperature while preventing such volatilization. The holding pressure is determined by the boiling point of the polyaddition reaction promoter and the temperature inside the reactor. In the case of water, the gauge pressure is usually 0.2 MPa.
Or more, preferably 0.3MPa or more, especially 0.5MPa
a or more is preferable. In general, polyamide having ε-caprolactam as a main component is unreacted ε-caprolactam,
After polymerization to contain oligomers and the like composed of ε-caprolactam, the pellets are usually pelletized and soluble components are removed using boiling water or lower alcohols.The molecular weight in terms of polystyrene measured by gel permeation chromatography is low. Low molecular weight substances having a molecular weight of 1,000 to 10,000 cannot be removed by such an extraction operation.

It is effective to add a known polymerization accelerator in order to promptly carry out the polymerization. In particular, phosphoric acid, phosphorous acid, hypophosphorous acid, or a phosphorus compound such as a salt or ester thereof is used. It is preferably used. Although the molecular weight of the polyamide resin of the present invention is not particularly limited, if the molecular weight is too low, the low molecular weight component increases, and if it is too high, the moldability deteriorates. .5,
Among them, 2.5 to 6.0, particularly 3.0 to 5.0 is preferable.

In order to improve the blocking resistance of the film using the polyamide resin of the present invention, inorganic fine particles such as silica, talc, kaolin, mica, zeolite and the like, and high molecular organic particles such as acrylic and styrene are added. Among them, addition of inorganic fine particles such as silica, talc, kaolin, mica, and zeolite is preferable, and silica is particularly preferably used from the viewpoint of transparency. Further, these inorganic fine particles may be subjected to a surface treatment with a silane coupling agent, a titanate coupling agent, or the like.

Since the addition of fine particles increases the blocking resistance of the film while deteriorating the transparency, the amount added depends on the required performance of the product.
To 1% by weight, particularly preferably 0.05 to 0.5% by weight. If the average particle size of the fine particles is too large, fish eyes are formed in the film, which causes a reduction in commercial value. If the average particle size is too small, the blocking resistance is impaired.In particular, the average particle size measured by the Coulter counter method is 0.1 to 20.
μm, preferably 0.3 to 15 μm,
Further, the thickness is preferably 1.0 to 5.0 μm.

As a method for adding these fine particles, a method of adding at the time of polymerization, a method of kneading with an extruder or the like, and a method of kneading at the time of molding can be applied, but from the viewpoint of transparency, they are added at the time of polymerization. The method is preferred. Also, ε-
Masterbatch containing a high concentration of fine particles in a polymer mainly composed of caprolactam (component A)
Is mixed with a polyamide resin or a polyamide resin composition (component B) substantially free of fine particles of the present invention to obtain a resin composition, which is formed into a film, which is particularly preferable since the transparency is greatly improved. The concentration of the fine particles in the masterbatch is not particularly limited, but is usually 0.5 to 20% by weight, preferably 0.8 to 5% by weight, particularly preferably 1 to 2% by weight. As for the production method of the master batch, there are a method of adding fine particles when polymerizing the polyamide resin, a method of dry-blending the polyamide resin and the fine particles, and then melt-kneading with a single-screw or twin-screw extruder. When added sometimes, the effect of improving transparency is great. The master batch also has a molecular weight of 1000 to 1 when a polyamide having a molecular weight of 1000 or more in terms of polystyrene measured by gel permeation chromatography is defined as 100% by weight.
The ratio of the low molecular weight substance of 0000 is 10.0% by weight or less, preferably 9.5% by weight or less, more preferably 9.
It is preferably 0% by weight or less, particularly preferably 8.5% by weight or less.

The blending ratio of the masterbatch and the polyamide resin or polyamide resin composition of the present invention is not particularly limited, but is generally 1 to 80 parts by weight to 99 to 20 parts by weight, and especially 3 to 20 parts by weight to 97 parts by weight. The amount is preferably from 80 to 80 parts by weight, more preferably from 3 to 10 parts by weight to 97 to 90 parts by weight. The method of blending the masterbatch with the polyamide resin or the polyamide resin composition of the present invention includes a method of blending at the time of polymerization, a method of kneading with a single-screw or twin-screw extruder, and a method of kneading and molding in a molding machine at the time of molding. And the like can be applied at the same time. Among them, a method of simultaneously performing kneading and molding in a molding machine during molding is preferable because it is simple.

Further, in order to improve flexibility and pinhole resistance, other resins, for example, ionomer resin, acid-modified polyethylene, acrylic rubber, polyester elastomer and the like can be added. . The polyamide or polyamide resin composition of the present invention may contain other conventional components such as heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, preservatives, adhesion promoters, coloring agents, and foaming agents. , Anti-blocking agents, crystallization accelerators, lubricants, spreading agents, fungicides,
It may contain a plasticizer, a release agent, a thickener, a drip-proofing agent, an impact modifier, etc., but especially when a bisamide compound represented by the following general formula is added, it is possible to give the film a better transparency. It is preferable because it is possible.

[0016]

Embedded image

Or

[0018]

Embedded image

(Wherein R¹Is a divalent hydrocarbon residue, R^Two
And R^ThreeIs a monovalent hydrocarbon residue, R ^FourAnd R^FiveIs water
Represents an atom or a monovalent hydrocarbon residue)

Examples of the bisamide compound represented by the above general formula (1) include alkylene diamines such as diaminomethane, diaminoethane, diaminopropane, diaminobutane, diaminohexane, diaminododecane, and arylenes such as phenylenediamine and naphthylenediamine. Diamine,
Obtained by the reaction of diamines such as arylenedialkyldiamines such as xylylenediamine with fatty acids such as stearic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, palmitic acid, arachidic acid, behenic acid, oleic acid and montanic acid. Alkylene bis fatty acid amide,
Examples include arylene bisfatty acid amides and arylenedialkylene bisfatty acid amides, among which N, N'-
Methylene bisstearic acid amide and N, N'-ethylenebisstearic acid amide are preferably used.

Examples of the bisamide compound represented by the general formula (2) include alkylamines such as methylamine, ethylamine, butylamine, hexylamine, decylamine, octadecylamine and dodecylamine; arylamines such as aniline and naphthylamine; Aralkylamines such as benzylamine, cycloalkylamines such as cyclohexylamine, and monoamines such as adipic acid;
Examples thereof include those obtained by reacting with dicarboxylic acids such as sebacic acid, terephthalic acid, isophthalic acid, and p-phenylenedipropionic acid. Among them, dioctadecyl dibasic amides such as N, N'-dioctadecyl terephthalamide Is preferred. These bisamide compounds can be used alone or as a mixture.

The addition of such a bisamide is particularly preferable because the effect of improving the transparency is great when a water cooling system is employed at the time of molding the film. In the case of a film, the addition amount of these bisamides is preferably 0.01 to 0.5 part by weight, particularly preferably 0.05 to 0.3 part by weight, based on 100 parts by weight of the polyamide resin or the polyamide resin composition of the present invention. If the added amount of the bisamide is too large, agglomeration occurs in the packaging material or the filament and the appearance is impaired. If the amount is too small, the effect of improving transparency is small.

A known method can be used for the addition of such a bisamide. Specifically, a method of adding at the time of polymerization of a polyamide resin, a dry blend with a polyamide resin or a polyamide resin composition, and a single or twin screw extruder. A method of melt-kneading, a method of dry-blending at the time of molding a film or a filament, and the like are mentioned. From the viewpoint of simplicity, a method of dry-blending at the time of molding a package is preferable. The film referred to in the present invention is formed by a known method such as a T-die method and an inflation method, but a film stretched uniaxially or biaxially is particularly preferable. Although there is no particular limitation on the stretching ratio, a film which is stretched usually from 1.2 to 6 times, particularly from 2 to 4 times, has a large effect of improving transparency. The film may have a single-layer structure or a multilayer structure using a technique such as coextrusion or lamination with another resin.
The film using the polyamide resin or the polyamide resin composition of the present invention has excellent transparency as compared with conventionally known films, and thus has a large utility value.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist. In the examples, “parts” indicates “parts by weight”. The measurement was performed by the following method.

(1) Measurement of Gel Permeation Chromatography (GPC) The dried polyamide resin pellets were treated with trifluoroacetic acid and trifluoroacetylated to obtain a tetrahydrofuran (THF) -soluble sample, and then THF was eluted. Liquid (flow rate: 1.0 ml / min), TOSOH TSK
GEL G2000H, G3000H, G4000H,
G5000H was measured using a total of four columns and a differential refractometer as a detector. The molecular weight and the molecular weight distribution were determined in terms of polystyrene from the elution time of commercially available monodispersed standard polystyrene. Molecular weight 1000-1000
The ratio of the low-molecular-weight product, which is 0, was determined by cutting out a GPC chart and determining the weight ratio.

(2) Relative viscosity of polyamide Measured using 98% sulfuric acid according to JIS K6810- 1970. (3) Time to semi-crystallization of polyamide Using DSC2 manufactured by PerkinElmer, 5 ± 0.5 mg of polyamide resin is weighed into an aluminum pan, and the temperature is raised from room temperature to 260 ° C at 20 ° C / min under a nitrogen atmosphere. After that, it is kept at this temperature for 3 minutes, and then at 100 ° C./min.
The temperature was cooled to 185 ° C. at the above rate, and the temperature was maintained as it was, and the time until the peak of the crystallization peak appeared was measured.

(4) Recrystallization temperature of polyamide 5 ± 0.5 mg of polyamide resin was weighed into an aluminum pan using SEIKO SSC-5000, and the temperature was raised from room temperature to 260 ° C. at a rate of 20 ° C./min under a nitrogen atmosphere. After that, the temperature was held for 3 minutes, and the temperature of the crystallization peak that appeared when the temperature was lowered to 80 ° C. at 20 ° C./min was measured.

(5) Stretching and Breaking The number of broken pieces when the film was simultaneously biaxially stretched 3 × 3 times at 80 ° C. was examined. (6) Amount of Silica in Pellet The pellet was incinerated and determined from the ash weight. (7) Blocking resistance (slipperiness) of film AS was measured using a friction measuring device TR type manufactured by Toyo Seiki Seisaku-sho, Ltd.
The static friction coefficient was evaluated at 23 ° C. and 65% RH according to TM D1894. (8) Haze value of film The haze value was evaluated using a haze meter manufactured by Tokyo Denshoku Co., Ltd.

Example 1 60 kg of ε-caprolactam, 1.8 kg of H ₂ O,
0.1 L of a 5% aqueous solution of Na ₂ HPO ₃ was charged into a 200 L autoclave, and after purging with nitrogen, the jacket was heated while stirring at 16 rpm while the reactor was sealed, and the internal temperature was increased to 270 ° C. and the gauge pressure to 0.7 MPa. When the pressure reached, the pressure was released to atmospheric pressure, and then reduced to 400 torr. When a predetermined stirring power was reached, the stirring was stopped, and after double-pressing with N ₂ , the contents were drawn out in a strand shape and pelletized with a rotary cutter. Subsequently, the operation of extracting the pellet with 150 L of boiling pure water is repeated 5 times to remove unreacted monomers and low molecular weight substances, and then dried at 120 ° C. and 1 torr until the water content becomes 0.1% or less. did. The resulting polyamide resin has a relative viscosity of 3.7 and a molecular weight of 1,000 to 10.
The ratio of low molecular weight substances, which was 000, was 8.0% by weight. Relative viscosity of the resin obtained in Example 5 and Comparative Example 1,
Table 1 shows the ratios of the low molecular weight substances together.

After 0.08 parts of ethylenebisstearic acid was dry-blended with 100 parts of this polyamide resin, a single-layer film having a thickness of 135 μm was formed at a resin temperature of 240 ° C. using a water-cooled inflation molding machine manufactured by Placo. . Subsequently, the film was simultaneously biaxially stretched 3 × 3 times at 80 ° C. using a long biaxial stretching machine,
Heat setting was performed at 210 ° C. to obtain a biaxially stretched polyamide film having a thickness of 15 μm. The stretch rupture, static friction coefficient, and haze value of the obtained film were determined, and the results are shown in Table 2 together with the results of the films obtained in other Examples and Comparative Examples.

Example 2 To 100 parts of the polyamide resin obtained in Example 1, 0.03 part of fine talc (trade name: Mistron Vapor, manufactured by Sipes Mines) and 0.1 part of ethylene bisstearylamide were dried. Blend, cylinder diameter 40mm, L /
Melted at a resin temperature of 240 ° C. using a single screw extruder of D22,
It was continuously extruded from a T-die and was taken out on a metal roll having a surface temperature of 80 ° C. to form a 30 μm thick single layer film.

Example 3 0.9 kg of silica fine particles (manufactured by Fuji Silysia Ltd., trade name: Sylysia 310) having an average particle size of 1.4 μm was dispersed in an 80% aqueous solution of caprolactam with a high-speed stirrer so as to have a 5% concentration. _It was charged in a 200 L autoclave together with 0.1 L of a 5% aqueous solution of ₂ HPO ₃ . Next, additional caprolactam was charged so that the total caprolactam amount became 60 kg, and polymerization was carried out in the same manner as in Example 1. When a predetermined stirring power was reached, the stirring was stopped, and after double-pressing with N2, the contents were extracted in a strand shape and pelletized with a rotary cutter. Then, put the pellet into 15
The operation of extracting with 0 L of boiling pure water is repeated 5 times,
After removing unreacted monomers and low molecular weight substances, 120
It dried at 0.1 degreeC and 1 torr until the water content became 0.1% or less. The relative viscosity of the obtained polyamide was 3.7, and the ash content was 1.6% by weight. After dry blending 6 parts of this master batch, 94 parts of the polyamide resin of Example 1 and 0.08 part of ethylenebisstearic acid amide, using a water-cooled inflation molding machine made by Placo Co., Ltd., the resin temperature was 240 ° C. and the thickness was 135 μm. A layer film was formed.
Subsequently, this film was subjected to 8
After simultaneously biaxially stretching 3 × 3 times at 0 ° C., heat setting was performed at 210 ° C. to obtain a 15 μm-thick biaxially stretched polyamide film.

Example 4 A biaxially stretched polyamide film having a thickness of 15 μm was obtained in the same manner as in Example 3 except that the blend ratio of the master batch of Example 3 and the polyamide resin of Example 1 was changed to 8 parts to 92 parts. . Example 5 60 kg of ε-caprolactam, 0.6 kg of H ₂ O,
0.1 L of a 5% aqueous solution of Na ₂ HPO ₃ was charged into a 200 L autoclave, and after purging with nitrogen, the jacket was heated while stirring at 16 rpm while the reactor was sealed, and the internal temperature was increased to 240 ° C. and the gauge pressure to 0.3 MPa. When the pressure reached, the pressure was released to atmospheric pressure, and then reduced to 400 torr. When a predetermined stirring power was reached, the stirring was stopped, and after double-pressing with N ₂ , the contents were drawn out in a strand shape and pelletized with a rotary cutter. Subsequently, the operation of extracting the pellet with 150 L of boiling pure water is repeated 5 times to remove unreacted monomers and low molecular weight substances, and then dried at 120 ° C. and 1 torr until the water content becomes 0.1% or less. did. The resulting polyamide has a relative viscosity of 3.8 and a molecular weight of 1,000 to 1,000.
The ratio of low molecular weight substances, which was 0, was 9.6% by weight. After 94 parts of this polyamide resin, 6 parts of the masterbatch described in Example 3, and 0.08 part of ethylene bisstearic acid amide were dry-blended, a water-cooled inflation molding machine made by Placo was used.
Was formed. Subsequently, the film was simultaneously biaxially stretched 3 × 3 times at 80 ° C. using a long-axis biaxial stretching machine, and then heat-set at 210 ° C. to a thickness of 15 μm.
Was obtained.

Comparative Example 1 60 kg of ε-caprolactam and 0.24 k of H ₂ O
g, 0.1 L of a 5% aqueous solution of Na ₂ HPO ₃ was charged into a 200 L autoclave, and after the atmosphere was replaced with nitrogen, the jacket was heated without stirring, and the internal temperature was 150 ° C. and the gauge pressure was 0.1 M.
When the pressure reached Pa, the internal temperature was further increased while releasing the pressure so as to maintain 0.1 MPa. When the internal temperature reached 210 ° C., the pressure was released to atmospheric pressure, and then reduced to 400 torr. When a predetermined stirring power was reached, the stirring was stopped, and after double-pressing with N ₂ , the contents were drawn out in a strand shape and pelletized with a rotary cutter. Then, put the pellet into 15
The operation of extracting with 0 L of boiling pure water is repeated 5 times,
After removing unreacted monomers and low molecular weight substances, 120
It dried at 0.1 degreeC and 1 torr until the water content became 0.1% or less. The relative viscosity of the obtained polyamide is 3.7, and the ratio of low molecular weight compounds having a molecular weight of 1,000 to 10,000 is 11.1.
It was 0% by weight. Example 1 using this polyamide resin
A biaxially stretched polyamide film was obtained in the same manner as described above. As described in Table 2, transparency was worse than that of Example 1.

Comparative Example 2 Using the polyamide resin obtained in Comparative Example 1, a single-layer film having a thickness of 30 μm was obtained in the same manner as in Example 2. Table-2
As described, the slipperiness was equal to that of Example 2, but the transparency was deteriorated. Comparative Example 3 A 15-μm-thick biaxially stretched polyamide film was obtained in the same manner as in Example 3, except that the polyamide resin obtained in Comparative Example 1 was used instead of the polyamide resin of Example 1. As described in Table 2, the slipperiness was almost the same as that of Example 3, but the transparency was deteriorated and the stretch fracture was observed.

Comparative Example 4 A biaxially stretched polyamide film having a thickness of 15 μm was obtained in the same manner as in Example 4 except that the polyamide resin obtained in Comparative Example 1 was used instead of the polyamide resin of Example 1.
As described in Table 2, the slipperiness was almost the same as that of Example 4, but the transparency was deteriorated, and a break in stretching was also observed.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

Industrial Applicability The polyamide resin or polyamide resin composition of the present invention has high utility value because it is excellent in transparency when processed into a film. In particular, since transparency and lubricity are simultaneously satisfied and there is no stretching breakage, the present invention can be applied to packaging and the like that requires a beautiful appearance without lowering the productivity, and the effect is remarkable.

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Claims (5)

[Claims] When a polyamide having a molecular weight of 1,000 or more in terms of polystyrene measured by gel permeation chromatography is defined as 100% by weight, a molecular weight of 10
A polyamide resin containing .epsilon.-caprolactam as a main polymer component, wherein the ratio of low molecular weight substances having a molecular weight of from 00 to 10,000 is 10.0% by weight or less. 2. The polyamide resin composition according to claim 1, wherein the polyamide resin contains 0.01 to 1% by weight of fine particles. 3. The polyamide resin composition according to claim 1, wherein component A: 1 to 80 parts by weight of a polyamide resin composition containing 0.5 to 20% by weight of fine particles, and component B: substantially no fine particles. Parts by weight of a polyamide resin composition. 4. A polyamide resin film using the polyamide resin or the polyamide resin composition according to claim 1. 5. The polyamide resin film according to claim 4, wherein the film is uniaxially or biaxially stretched.