JP2002121380A - Polyamide film, fiber and monofilament - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide film, a fiber and a monofilament obtained from a polyamide resin composition excellent in thermal stability in melt molding and improved in hot water resistance. SOLUTION: The polyamide film is obtained from a polyamide resin composition comprising a polyamide resin, a hydroxyphenylpropionate represented by general formula (1) and a cyclic phosphite containing a hydroxyl group in the same molecule represented by general formula (2), where the total amount of the hydroxyphenylpropionate represented by general formula (1) and the cyclic phosphite containing a hydroxyl group in the same molecule represented by general formula (2) is 0.005-1 pt.wt. based on 100 pts.wt. of the polyamide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyamide film, a fiber and a monofilament obtained from a polyamide resin composition containing specific amounts of two specific antioxidants. Specifically, the present invention relates to a polyamide film, a fiber, and a monofilament obtained from a polyamide resin composition containing specific amounts of two kinds of antioxidants, a specific hydroxyphenylpropionate and a cyclic phosphite.

[0002]

2. Description of the Related Art Polyamide resins have excellent mechanical properties, heat resistance, toughness, chemical resistance, abrasion resistance, oil resistance, transparency,
Because it has gas barrier properties, pinhole resistance, etc.
Melt molding produces automobile parts, electric equipment parts, films, fibers, monofilaments, sheets, tubular molded products, blow molded products, and the like, and their fields of use are expanding.

[0003]

The polyamide resin is usually melt-molded in a temperature range of 250 to 320 ° C. With the expansion of application fields, there is an increasing demand for production of a molded article having a complicated shape and high productivity, and the melting temperature during molding tends to increase. However, when the melting temperature of the polyamide resin is high or when it is held in a molten state for a long time, the polyamide resin may deteriorate or partially cross-link to form a gel-like material, and the melt fluidity changes, It is known that undesired phenomena such as a decrease in surface properties of the product and a decrease in mechanical strength due to the formation of a gel-like substance are liable to occur. Specifically, in the case of film forming, due to a change in melt fluidity or generation of a gel-like material, a granular defect called fisheye gel or a streak-like appearance defect called a die line occurs, In the case of forming a monofilament, there are phenomena such as easy breakage (yarn breakage) during spinning.

[0004] Also, with the increasing demand for polyamides, molded articles are often used under more severe conditions. For example, it is also known that when a polyamide molded article is treated with hot water or steam at 100 ° C. or higher, the mechanical properties of the polyamide molded article, particularly the tensile strength, are greatly reduced. Therefore, there is a need for polyamide films, fibers, and monofilaments having both improved thermal stability and hot water resistance during melt molding.

Conventionally, there have been many proposals for improving the thermal stability of polyamide resins. For example, regarding the thermal stability of a polyamide resin, JP-A-59-25826 and JP-A-59-231089 disclose a polyamide resin containing a polyamide resin and a hydroxyphenylpropionate ester having improved thermal stability. A composition is disclosed. These documents also describe that a phosphorus-based antioxidant can be used in combination. However, these prior arts include:
There is no specific data on the thermal stability of the polyamide resin composition, and no description on films, fibers, or monofilaments.

JP-A-6-16928 discloses a polyamide resin composition containing a polyamide resin, a hydroxyphenylpropionate ester and a phosphorus-based antioxidant and having improved heat stability. However, there is no description about the thermal stability of the polyamide resin at the time of melting,
Further, there is no description about films, fibers, and monofilaments.

JP-A-11-222493 discloses a polyamide resin composition containing a polyamide resin and a specific cyclic phosphite and having improved thermal stability. It also describes that various phenolic antioxidants can be used in combination. However, there is no disclosure of specific data on the thermal stability of the polyamide resin during melting, and there is no description of data on films, fibers, and monofilaments.

An object of the present invention is to provide a polyamide film, a fiber, and a monofilament obtained from a polyamide resin composition having good heat stability during melt molding and improved hot water resistance.

[0009]

The present inventors have conducted intensive studies and as a result, have found that polyamide films, fibers, and monofilaments obtained from a polyamide resin composition in which two specific antioxidants are mixed in specific amounts. The present inventors have found that heat stability during melt molding is good and hot water resistance is also good, and the present invention has been achieved.

That is, the present invention relates to a polyamide resin, a hydroxyphenylpropionate represented by the general formula (1) and a cyclic phosphite having a hydroxy group in the same molecule represented by the general formula (2). A polyamide resin composition comprising: 100 parts by weight of a polyamide resin;
When the total amount of the hydroxyphenylpropionate represented by the general formula (1) and the cyclic phosphite having a hydroxy group in the same molecule represented by the general formula (2) is 0.0
The present invention relates to a polyamide film, a fiber and a monofilament obtained from a polyamide resin composition in an amount of from 0.5 to 1 part by weight.

[0011]

Embedded image (In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms.)

[0012]

Embedded image(Where R¹, R², R³, R⁴, R⁵, R⁶Haso
Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
You. X is a mere bond, a sulfur atom or -CHR ⁷-Group
 (R⁷ Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms)
 Represents A is an alkylene group having 2 to 8 carbon atoms or * -C
OR⁸-Group (R⁸ Is a mere bond or an atom having 1 to 8 carbon atoms.
* Indicates that the alkylene group is bonded to the oxygen side
You. ). ).

Hereinafter, the present invention will be described in detail. The polyamide resin used in the present invention can be obtained by polymerizing or copolymerizing a nylon salt comprising a lactam, aminocarboxylic acid, or diamine having three or more ring members and dicarboxylic acid. These polymerizations or copolymerizations can be carried out by known polymerization methods such as melt polymerization, solution polymerization and solid phase polymerization. Known polyamide production, such as kneading reaction extruders such as batch type reaction vessels, single-tank type or multi-type continuous reaction devices, tubular continuous reaction devices, single-screw kneading extruders, and twin-screw kneading extruders. An apparatus can be used.

As a lactam having three or more rings, for example,
ε-caprolactam, ω-enantholactam, ω-laurolactam, α-pyrrolidone, α-piperidone and the like. Examples of the aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9
-Aminononanoic acid, 11-aminoundecanoic acid, 12-
Aminododecanoic acid and the like can be mentioned.

As the diamine constituting the nylon salt,
For example, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine,
Aliphatic amines such as 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 1,3- / 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, piperazine, bis (4-aminocyclohexyl) ) Methane, 2,2-bis- (4'-aminocyclohexyl)
Examples thereof include alicyclic diamines such as propane, and aromatic diamines such as meta-xylylenediamine and para-xylylenediamine.

The dicarboxylic acids constituting the nylon salt include, for example, aliphatic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sepatinic acid, nonandioic acid, decanedioic acid, undecandioic acid and dodecandioic acid. Alicyclic carboxylic acids such as dicarboxylic acid, hexahydroterephthalic acid and hexahydroisophthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid (1,2-form, 1,3-form, 1,4-form, 1, 5
-Body, 1,6-body, 1,7-body, 1,8-body, 2,3-
, 2,6-body and 2,7-body). In the polyamide resin composition of the present invention, a homopolymer or a copolymer derived from the above-mentioned three- or more-membered lactam, amine carboxylic acid, or nylon salt composed of diamine and dicarboxylic acid is used alone or in the form of a mixture. Can be.

Specific examples of the polyamide resin used include nylon 4, nylon 6, nylon 7, nylon 1
1, nylon 12, nylon 46, nylon 66, nylon 69, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD
6, nylon 6/66 (copolymer of nylon 6 and nylon 66, hereinafter the copolymer is similarly described), nylon 6/69, nylon 6/610, nylon 6/611,
Nylon 6/12, Nylon 6/612, Nylon 6 /
6T, nylon 6 / 6I, nylon 6/66/610,
Nylon 6/66/12, nylon 6/66/612,
Nylon 66 / 6T, Nylon 66 / 6I, Nylon 6
T / 6I, nylon 66 / 6T / 6I and the like. Preferred polyamide resins include nylon 6, nylon 12, nylon 66, nylon MXD6, and nylon 6/66 in consideration of heat resistance, mechanical strength, transparency and economy, availability of molded articles, and the like. Copolymer,
Nylon 6/12 copolymer and nylon 6/66/12 terpolymer.

The polyamide resin used in the present invention is J
According to IS K6810, the relative viscosity (ηr) measured under the conditions of 98% sulfuric acid concentration 1% and temperature 25 ° C. is 2 to 2.
6, preferably in the range of 2-5. If the relative viscosity is too low, the resulting molded article may have insufficient mechanical strength, and if it is too high, molding may be difficult. Further, the terminal group structure of the polyamide resin may be any of an amino group, a carboxyl group, or an alkyl group,
From the viewpoint of hot water resistance, a polyamide resin having a low terminal carboxyl group concentration, in which a part of the carboxyl groups is sealed with a monoamine or diamine, is preferred.

The general formula (1) used in the present invention
(Hereinafter referred to simply as hydroxyphenylpropionate), 3- (3-alkyl-5-tert-butyl-4-hydroxyphenyl) propionic acid, or an acid thereof Reactive derivatives such as chlorides and acid anhydrides and 3,9-bis (1,1-dimethyl-2-hydroxyethyl) 2
It can be produced by reacting 4,8,10-tetraoxaspiro [5.5] undecane with a known method.

In the hydroxyphenylpropionic acid ester represented by the general formula (1), R ¹ represents a methyl group, an ethyl group or a propyl group, and a methyl group is preferable in view of heat and oxidation stability. Specific examples of hydroxyphenylpropionate include 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [2- [3- (3
-T-butyl-4-hydroxy-5-ethylphenyl)
Propionyloxy] -1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [2- [2- (3-t-butyl-
4-hydroxy-5-isopropylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4.
There are 8,10-tetraoxaspiro [5.5] undecane and the like, and among these, 3,9-bis [2- [3
-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.
5] Undecane is preferably used.

The cyclic phosphite having a hydroxy group in the same molecule represented by the general formula (2) used in the present invention (hereinafter simply referred to as cyclic phosphite) is exemplified by the following: Equation (3)

[0022]

Embedded image

(Wherein R ¹ , R ² , R ³ and X have the same meaning as described above), a phosphorus trihalide and a general formula (4)

[0024]

Embedded image

(Wherein R ⁴ , R ⁵ , R ⁶ , and A have the same meaning as described above) by a known method.

The phosphorus trihalide used here includes, for example, phosphorus trichloride, phosphorus tribromide and the like.
In particular, phosphorus trichloride is preferably used.

In the cyclic phosphite having a hydroxy group in the same molecule represented by the general formula (2), the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, typical examples of the alkyl group having 1 to 8 carbon atoms include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl and t-butyl.
Examples include pentyl, i-octyl, t-octyl, 2-ethylhexyl and the like. R ¹ and R ⁴ are t-alkyl groups such as t-butyl, t-pentyl and t-octyl; R ² is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl;
It is preferably an alkyl group having 1 to 5 carbon atoms, such as sec-butyl, t-butyl, t-pentyl, etc.
Butyl and t-pentyl are preferred. R ³ , R
⁶ is the same alkyl group as described above, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom or a methyl group. R ⁵ represents a hydrogen atom, methyl, ethyl, n-propyl,
It is preferably an alkyl group having 1 to 5 carbon atoms such as i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, t-pentyl and the like.

The substituent X is a mere bond, a sulfur atom or -C
An HR ⁷ group (R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), that is, a methylene group which may be substituted by an alkyl having 1 to 8 carbon atoms. Here, examples of the alkyl having 1 to 8 carbon atoms that is substituted on the methylene group include the same alkyl groups as described above.
X is a mere bond, a methylene group or methyl, ethyl, n-
Preferably, propyl, i-propyl, n-butyl, i-butyl, t-butyl and the like are substituted methylene groups.

The substituent A is an alkylene group having 2 to 8 carbon atoms or a * -COR ⁸ -group (R ⁸ is a mere bond or an alkylene group having 1 to 8 carbon atoms, and * is a bond to the oxygen side. Is shown). Here, typical examples of the alkylene group having 2 to 8 carbon atoms include ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propylene and the like. Propylene is preferably used. Also, * -CO
R 8 ^- * in group indicates that the carbonyl is bonded to oxygen of the phosphite. A carbon number of 1 in R ⁸
Representative examples of the alkylene group of ~ 8 include, for example, methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl-
1,3-propylene and the like. As R ⁸ , a simple bond, ethylene or the like is preferably used.

As the cyclic phosphite having a hydroxy group in the same molecule represented by the general formula (2), 6-
[3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-
Particularly preferred is t-butyldibenz [df] [1.3.2] dioxaphosphebin.

In the polyamide resin composition used in the present invention, the total amount of hydroxyphenylpropionate and cyclic phosphite is 0.005 to 1 part by weight based on 100 parts by weight of the polyamide resin. Things. The mixing ratio of the hydroxyphenylpropionate and the cyclic phosphite can be used in any ratio as long as it is within the range of the amount used, but usually the hydroxyphenylpropionate is 0.0025 to 0.5% by weight. Parts, from 0.0025 to 0.5 parts by weight of the cyclic phosphite. When the total amount of the hydroxyphenylpropionate and the cyclic phosphite is less than the lower limit, the improvement effect is not always sufficiently exhibited, and when the total amount is more than the upper limit, not only the improvement of the effect corresponding thereto cannot be expected, but also Bleed out on the surface of the polyamide molded article.

The polyamide resin composition used in the present invention may contain other known phenol-based, phosphorus-based, sulfur-based, and hindered amine-based oxidizing agents as long as the properties of the resulting product are not significantly impaired. Inhibitors, weathering agents,
Lubricants such as metal soaps and bisamide compounds, fillers such as silica, talc, and kaolin; antistatic agents such as alkyl sulfate compounds and quaternary ammonium salt compounds; antiblocking agents; clouding agents; dyes; and pigments Agents, other thermoplastic resins, and the like.
Known modified polyolefins, ionomers, elastomers and the like can be added in order to improve the flex resistance and the like within a range that does not significantly change the thermal stability of the polyamide composition.

The polyamide resin composition used in the present invention is prepared by mixing a polyamide resin, a hydroxyphenylpropionate ester, a cyclic phosphite ester, and various additives as required in predetermined amounts, and mixing them by a known method. Manufactured by For example, a method of dry blending a polyamide resin, a hydroxyphenylpropionate ester and a cyclic phosphite ester using a tumbler or a mixer, and a method in which the hydroxyphenylpropionate ester and the cyclic phosphite are preliminarily prepared at a concentration used for molding. A kneading method in which the resin is melt-kneaded using a single-screw or twin-screw extruder, or contains a high-concentration hydroxyphenylpropionate and a cyclic phosphite in advance using a single-screw or a twin-screw extruder. A masterbatch method of producing a polyamide resin and diluting it during molding is used. The hydroxyphenyl propionate and the cyclic phosphite may be separately mixed with the polyamide resin, or both may be mixed with the polyamide resin together.

As a method for producing the polyamide film of the present invention, a known polyamide film production method can be applied. For example, the raw polyamide resin composition is melt-kneaded with an extruder, extruded into a flat film by a T-die or a coat hanger die, cast on a casting roll surface, cooled to produce a film, a casting method, a ring-shaped die. A tubular method or the like in which a film extruded into a cylindrical shape is air-cooled or water-cooled to produce a film is applied. The produced film can be used in an unstretched state, but is usually used as a stretched film in many cases. As a stretched film,
There are uniaxially stretched films, simultaneous biaxially stretched films, sequential biaxially stretched films, and the like. These include roll type uniaxial stretching method, tenter sequential biaxial stretching method, tenter type simultaneous biaxial stretching method, tubular stretching method and the like. Can also be manufactured. The stretching process follows the production of the polyamide film,
It may be carried out continuously, or the polyamide film may be once wound up and stretched as a separate step. These films can be used by laminating them with a known resin by a known method such as a coextrusion method or a laminating method. In addition, the thickness of the polyamide film of the present invention is not particularly limited and is selected depending on the application.
m, preferably 5 to 100 μm.

As the method for producing a fiber or monofilament of the present invention, a known method for producing a polyamide fiber or monofilament can be applied. For example, the raw polyamide resin composition is melt-kneaded in an extruder,
After cooling the extruded filamentous material, it is subsequently introduced into an atmosphere such as hot water or heated air, stretched to a desired stretching ratio, and further subjected to post-processing such as heat fixing or dyeing, if necessary, to form fibers and monofilaments. Obtainable. The fiber diameter of the monofilament of the present invention is not particularly limited, but is selected depending on the application, usually ^10-2 to ⁵ denier, preferably 10 ^-1 to 10 ⁴ denier.

[0036]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but it is needless to say that the present invention is not limited to these Examples. Hereinafter, the polyamide resins, antioxidants, and evaluation methods used in Examples and Comparative Examples are described.

1. Polyamide (nylon) resin used A-1: nylon 6 (UBE NY manufactured by Ube Industries, Ltd.)
LON 1022B, relative viscosity 3.6) A-2: Nylon 6 (UBE NY manufactured by Ube Industries, Ltd.)
LON SF1018A, relative viscosity 3.2)

2. Antioxidants used B-1: 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,1
0-tetra-t-butyldibenz [df] [1.3
2] Dioxaphosphefin (manufactured by Sumitomo Chemical Co., Ltd.)
Trade name Sumilizer GP) B-2: 3,9-bis [2- [3- (3-t-butyl-4)
-Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-
Tetraoxaspiro [5,5] undecane (Sumitomo Chemical Co., Ltd. product name Sumilyzer GA-80) B-3: Tris (2,4-di-t-butylphenyl) phosphite (Ciba Specialty Chemicals Co., Ltd.) Product name Irgafos 168) B-4: Pentaerythrityl-tetrakis [3- (3,3)
5-Di-t-butyl-4-hydroxyphenyl) propionate] (trade name Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.)

3. Evaluation Method of Thermal Stability in Melted State A polyamide resin and an antioxidant were supplied to a twin-screw extruder (TEX30, manufactured by Nippon Steel Works), and the extruder set temperature was set to 250 ° C.
The mixture was melt-kneaded under conditions of a screw rotation speed of 100 rpm, granulated, and then dried to obtain pellets. The pellets are supplied to Labo Plast Mill (2D25-S, manufactured by Toyo Seiki Seisaku-sho, Ltd.), and the kneading set temperature is 280 ° C. and the screw rotation speed is 80 rpm.
and kneaded under the conditions of m. The torque was continuously measured, and the rate of change of the torque was determined from the values of the torque values after 3 minutes and 30 minutes from the start of rotation of the screw by the following equation. The smaller the rate of change of the torque, the better the thermal stability in the molten state. Change rate of torque = [(torque value after 30 minutes) / (torque value after 3 minutes)] × 100 (%)

4. Evaluation method of heat discoloration resistance (1) Preparation of evaluation film A polyamide resin and an antioxidant were supplied to a twin-screw extruder (manufactured by Nippon Steel Works, TEX30 type) and the extruder set temperature was set to 250.
° C, melt kneading under the condition of screw rotation speed 100 rpm,
After granulation, it was dried to obtain pellets. This pellet was extruded into a single screw extruder equipped with a T die (40 m
mφEx), the extruder temperature was set at 250 ° C., the number of revolutions of the screw was set at 40 rpm, and the cooling roll temperature was set at 40 ° C. to produce a 150 μm-thick polyamide film for evaluation. (2) Evaluation of Yellowness YI The evaluation film obtained above was placed in an oven at 180 ° C. for 5 minutes.
After holding for a time, an aging treatment was performed. 5.0 cm long from the film for evaluation before and after the aging treatment,
A sample of 5.0 cm in width was cut out, and each yellowness Y
I to a color computer (manufactured by Suga Test Instruments Co., Ltd.)
SM-5-IS-2B). As an index value of the heat discoloration resistance, a change value ΔYI of the yellowness YI of the film before and after the aging treatment was obtained. The smaller the change value ΔYI, the better the heat discoloration resistance. ΔYI = (YI after aging processing) − (YI before aging processing)

5. Evaluation method of hot water resistance (1) Preparation of evaluation film A polyamide resin and an antioxidant were supplied to a twin-screw extruder (TEX30, manufactured by Nippon Steel Works), and the extruder was set at a temperature of 250 ° C.
The mixture was melt-kneaded at a screw rotation speed of 100 rpm, granulated, and dried to obtain pellets. This pellet was extruded into a single screw extruder equipped with a T die (40 mmφ manufactured by Plastic Engineering Laboratory).
Ex), and the conditions were set at an extruder set temperature of 250 ° C., a screw rotation speed of 40 rpm, and a cooling roll temperature of 40 ° C. to produce a polyamide film having a thickness of 100 μm.
A sample having a length of 90 mm and a width of 90 mm was cut out from this film, attached to a biaxial stretching machine (BIX-703, manufactured by Iwamoto Seisakusho), and simultaneously biaxially stretched at a stretching temperature of 70 ° C. to obtain a film having a length of 2.8.
After stretching 2.8 times and 2.8 times the width, heat-setting at 210 ° C,
A biaxially stretched film for evaluation of hot water resistance was obtained. (2) Evaluation of hot water resistance A film of 150 mm in length and 150 mm in width cut out from the biaxially stretched film for evaluation obtained above was put into a retort food autoclave (manufactured by Tommy Seiko, SR-240) at 135 ° C. The treatment was performed under the conditions of a total pressure of 3.2 kg / cm 2 (gauge pressure) and a partial pressure of air of 1.0 kg / cm ² (gauge pressure) for 30 minutes. The tensile strength of the film before and after the treatment was measured according to ASTM D-882, and the tensile strength retention was determined by the following equation. The higher the value of the retention of tensile strength, the smaller the effect of the retort treatment, indicating that the hot water resistance is excellent. Tensile strength retention = [(tensile strength after retort treatment) / (tensile strength before retort treatment)] × 100 (%)

6. Evaluation of spinnability A polyamide resin and an antioxidant were supplied to a twin-screw extruder (TEX30, manufactured by Nippon Steel Works), and the extruder set temperature was set to 250 ° C.
The mixture was melt-kneaded at a screw rotation speed of 100 rpm, granulated, and dried to obtain pellets. The pellets were supplied to a Capillograph manufactured by Toyo Seiki Seisaku-sho, and at a test temperature of 260 ° C,
After holding for 5 minutes, spinning was started. The initial speed of the take-up speed was set to 10 mm / min. Thereafter, the take-up speed was increased at a constant speed (10 mm / min), and the take-up speed and the tension at the time when the yarn breakage (yarn breakage) occurred were measured. The higher the take-up speed at the time of thread breakage and the greater the tensile tension,
This indicates that yarn breakage (breakage) hardly occurs, that is, the spinning property is good.

Examples 1 and 2 and Comparative Examples 1 to 5 Antioxidants of the types and amounts shown in Table 1 were mixed with 100 parts by weight of polyamide resin A-1. The heat stability, heat discoloration resistance, and hot water resistance during melting were evaluated. Table 1 shows the results.

Example 3 and Comparative Examples 6 and 7 Antioxidants of the types and amounts shown in Table 2 were mixed with 100 parts by weight of the polyamide resin A-2. Each spinnability was evaluated. Table 2 shows the results.
Shown in

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

According to the present invention, the polyamide film, fiber,
Monofila has features such as small change in torque during melt molding, little coloring even when used at high temperature, little decrease in tensile strength after hot water or steam treatment, good spinnability, etc. It has good heat and oxidation stability during melt molding and has excellent hot water resistance.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F071 AA54 AC06 AC11 AC15 AC19 AE05 AF03 BC01 BC06 4J002 CL001 CL011 CL031 CL051 CL061 EJ026 EL107 EW037 EW067 FD01 FD07 FD076 FD077 FD10 FD17 GF00 GG00 GG01 4

Claims (4)

[Claims] 1. A polyamide resin represented by the general formula (1)
Hydroxyphenylpropionate and general formula
Cyclic having a hydroxy group in the same molecule represented by (2)
A polyamide resin composition containing a phosphite
And 100 parts by weight of a polyamide resin represented by the general formula (1).
Hydroxyphenylpropionate and general formula
Cyclic having a hydroxy group in the same molecule represented by (2)
When the total amount with the phosphite is 0.005 to 1 part by weight
Polyamide filler obtained from a certain polyamide resin composition
Lum. Embedded image(Where R¹Represents an alkyl group having 1 to 3 carbon atoms. )(Where R¹, R², R³, R⁴, R⁵, R⁶Haso
Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
You. X is a mere bond, a sulfur atom or -CHR ⁷-Group
 (R⁷ Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms)
 Represents A is an alkylene group having 2 to 8 carbon atoms or * -C
OR⁸-Group (R⁸ Is a mere bond or an atom having 1 to 8 carbon atoms.
* Indicates that the alkylene group is bonded to the oxygen side
You. ). ) 2. The method of claim 1, wherein the hydroxyphenylpropionic acid ester represented by the general formula (1) is 3,9-bis [2- [3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl]
-2,4,8,10-tetraoxaspiro [5.5] undecane, wherein the cyclic phosphite having a hydroxy group in the same molecule represented by the general formula (2) is 6- [3
-(3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-
The polyamide film according to claim 1, which is butyldibenz [df] [1.3.2] dioxaphosphebin. 3. A fiber obtained from the polyamide resin composition according to claim 1. 4. A monofilament obtained from the polyamide resin composition according to claim 1.