JP7026965B2 - Semi-aromatic polyamide film - Google Patents

Description

The present invention relates to a semi-aromatic polyamide film.

Polyamide 9T films composed of aliphatic diamines having 9 carbon atoms and terephthalic acid have good heat resistance and dimensional stability, and are being studied for application to electronic and electrical parts. As a more practical composition suitable for use in a substrate for a flexible printed circuit or the like, it has been proposed to add a thermoplastic elastomer to the polyamide 9T (Patent Document 1). In the above applications, it is required that physical properties such as strength be maintained in a high temperature environment for a long period of time (long-term heat resistance).

As a method for imparting long-term heat resistance to a semi-aromatic polyamide such as polyamide 9T, for example, Patent Document 2 describes polyhydric alcohols (for example, dipentaerythritol) having more than two hydroxyl groups in the semi-aromatic polyamide. It is disclosed to add. However, simply adding polyhydric alcohols to the polyamide bleeds out and spoils the appearance, and the long-term heat resistance is not sufficient (Patent Document 3). Further, Patent Document 3 discloses that long-term heat aging resistance is improved by adding a compound having a specific amount of a carboxyl group and a hydroxyl group. However, the method of Patent Document 3 needs to heat-treat polyhydric alcohols in advance to adjust the content of carboxyl groups within an appropriate range, and is not a simple method in terms of time and cost. Met.

International Publication No. 2014/057828 Pamphlet Japanese Patent Publication No. 2011-529993 International Publication 2014/041804 Pamphlet

In recent years, as a long-term heat resistance evaluation method for polymer materials, a method of evaluating by the relative temperature index (RTI) defined by UL746B, that is, the time when the tensile strength becomes 50% of that before the treatment at several treatment temperatures. Is calculated, the inverse of each absolute temperature and the log of the strength half time at each temperature are plotted, and the method of evaluating the temperature at which the tensile strength becomes 50% in 100,000 hours is used [ThreeBond Technical]. News 13 (issued on December 1, 1985) by Shimizu Ota].

According to the research by the present inventors, conventionally, a semi-aromatic polyamide film having a relative temperature index of 100 ° C. or higher is not known.

In view of the prior art, an object of the present invention is to provide a semi-aromatic polyamide film having better long-term heat resistance than a conventional semi-aromatic polyamide film.

The present inventors have found that the above object can be achieved by mixing a semi-aromatic polyamide with a specific thermoplastic elastomer by a specific method and further stretching the mixture, and have completed the present invention. ..

That is, the gist of the present invention is as follows.
(1) A semi-aromatic polyamide (A) 97 to 90% by mass consisting of a dicarboxylic acid containing terephthalic acid as a main component and a diamine containing an aliphatic diamine having 9 carbon atoms as a main component.
A thermoplastic elastomer (B) having at least one functional group selected from a carboxyl group or an anhydride thereof, an amino group, a hydroxyl group, an epoxy group, an amide group and an isocyanate group, and 3 to 10% by mass of the thermoplastic elastomer (B).
Consists of heat stabilizers ,
The total of (A) and (B) is 100% by mass,
The heat stabilizer consists of only one or more heat stabilizers selected from hindered phenolic heat stabilizers, phosphorus heat stabilizers and bifunctional heat stabilizers.
A semi-aromatic polyamide stretched film having a relative temperature index of 100 ° C. or higher at which the tensile strength of MD becomes 50% in 100,000 hours.

According to the present invention, it is possible to provide a semi-aromatic polyamide film which is superior in long-term heat resistance to a conventional semi-aromatic polyamide film and has a relative temperature index of 100 ° C. or higher. The semi-aromatic polyamide film of the present invention can be suitably used as a substrate for flexible flat cable wiring, a coverlay film, a heat resistant tape, and an insulating tape.

The semi-aromatic polyamide film of the present invention comprises a semi-aromatic polyamide (A) composed of a dicarboxylic acid containing terephthalic acid as a main component and a diamine containing an aliphatic diamine having 9 carbon atoms as a main component, and a functional group. It is composed of the thermoplastic elastomer (B) having.

First, the semi-aromatic polyamide (A) used in the present invention will be described.

The dicarboxylic acid component constituting the semi-aromatic polyamide (A) needs to contain terephthalic acid as a main component. The ratio of terephthalic acid in the dicarboxylic acid component is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 85 to 100 mol%. Since the ratio of terephthalic acid in the dicarboxylic acid component is 60 to 100 mol%, it is possible to obtain a polyamide having high heat resistance and low water absorption.

Examples of the dicarboxylic acid component other than terephthalic acid contained in the dicarboxylic acid component constituting the semi-aromatic polyamide (A) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, and dodecanedioic acid. , Tetradecanedioic acid, octadecanedioic acid and other aliphatic dicarboxylic acids, 1,4-silhohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, and 1 , 4-Naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, isophthalic acid and other aromatic dicarboxylic acids can be mentioned.

The diamine component of the semi-aromatic polyamide (A) needs to contain an aliphatic diamine having 9 carbon atoms as a main component. The proportion of the aliphatic diamine having 9 carbon atoms in the diamine component is preferably 60 to 100 mol%, more preferably 75 to 100 mol%, and further preferably 90 to 100 mol%. preferable. When the proportion of the aliphatic diamine having 9 carbon atoms is 60 to 100 mol%, the heat resistance and chemical resistance of the obtained film are improved, and the water absorption is lowered.

Examples of the aliphatic diamine having 9 carbon atoms include linear aliphatic diamines such as 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 4-methyl-1,8-octanediamine. Etc. can be mentioned as a branched chain aliphatic diamine. These may be used alone or in combination of two or more. Above all, from the viewpoint of film moldability, it is preferable to use 1,9-nonanediamine and 2-methyl-1,8-octanediamine in combination.

Examples of the diamine component other than the above-mentioned aliphatic diamine having 9 carbon atoms contained in the diamine component constituting the semi-aromatic polyamide (A) include 1,4-butanediamine, 1,5-pentanediamine, and the like. Linear aliphatic diamines such as 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. , 4-Methyl-1,8-octaneamine, 5-methyl-1,9-nonandiamine and other branched chain aliphatic diamines, and isophoronediamine, norbornandimethylamine, tricyclodecanedimethylamine and other alicyclic diamines. , Aromatic diamines such as phenylenediamine.

The semi-aromatic polyamide (A) includes lactams such as ε-caprolactam, ζ-enantractam, η-caprilactam, and ω-laurolactam, aminocaproic acid, and 11-amino, as long as the effects of the present invention are not impaired. It may contain ω-aminocarboxylic acid such as undecanoic acid.

Among the semi-aromatic polyamides (A) obtained by the combination of the monomers, a dicarboxylic acid component consisting only of terephthalic acid (100 mol% of terephthalic acid) and 1 from the viewpoint of heat resistance and film forming processability. , 9-Nonanediamine and 2-methyl-1,8-octanediamine are preferably contained in a total of 60 to 100 mol% in the diamine component, and a semi-aromatic polyamide (A) composed of a diamine component is preferable.

In the above semi-aromatic polyamide (A), the copolymerization ratio (molar ratio) of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is (1,9-nonanediamine) / (2-methyl). -1,8-octanediamine) = 50/50 to 100/0, more preferably 70/30 to 100/0, and even more preferably 75/25 to 95/5. When the copolymerization ratio (molar ratio) of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 50/50 to 100/0, the heat resistance of the obtained film is improved and water absorption is achieved. The sex is reduced.

The type and copolymerization ratio of the monomers constituting the semi-aromatic polyamide (A) are preferably selected so that the Tm (melting point) of the obtained semi-aromatic polyamide (A) is in the range of 280 to 350 ° C. .. By setting the Tm of the semi-aromatic polyamide (A) in the above range, thermal decomposition of the semi-aromatic polyamide (A) during processing into a film can be efficiently suppressed. If Tm is less than 280 ° C., the heat resistance of the obtained film may be insufficient. On the other hand, if Tm exceeds 350 ° C., thermal decomposition may occur during film production.

The ultimate viscosity of the semi-aromatic polyamide (A) is preferably 0.8 to 2.0 dL / g, more preferably 0.9 to 1.8 dL / g. When the ultimate viscosity of the semi-aromatic polyamide (A) is 0.8 to 2.0 dL / g, a film having excellent mechanical properties can be obtained. If the ultimate viscosity of the semi-aromatic polyamide (A) is less than 0.8 dL / g, it may be difficult to form a film and maintain the film shape. On the other hand, if it exceeds 2.0 dL / g, it may be difficult to adhere to the cooling roll during film production, and the appearance of the film may be deteriorated.

As the semi-aromatic polyamide (A), a commercially available product can be preferably used. Examples of such commercially available products include "Genesta (registered trademark)" manufactured by Kuraray.

The semi-aromatic polyamide (A) can be produced by using any method known as a method for producing a crystalline polyamide. For example, a solution polymerization method or an interfacial polymerization method using an acid chloride and a diamine component as raw materials can be mentioned. Alternatively, a method of producing a prepolymer using a dicarboxylic acid component and a diamine component as raw materials and increasing the molecular weight of the prepolymer by melt polymerization or solid phase polymerization can be mentioned.

The prepolymer can be obtained, for example, by heating and polymerizing a salt prepared by collectively mixing a diamine component, a dicarboxylic acid component and a polymerization catalyst at a temperature of 200 to 250 ° C.

The ultimate viscosity of the above prepolymer is preferably 0.1 to 0.6 dL / g. By setting the ultimate viscosity of the prepolymer in the above range, the molar balance between the carboxyl group in the dicarboxylic acid component and the amino group in the diamine component is not disturbed in the subsequent solid phase polymerization or melt polymerization, and the polymerization rate is increased. It has the advantage of being able to. If the ultimate viscosity of the above prepolymer is less than 0.1 dL / g, the polymerization time becomes long and the productivity may be inferior. On the other hand, if it exceeds 0.6 dL / g, the obtained semi-aromatic polyamide may be colored.

The solid phase polymerization of the above prepolymer is preferably carried out under reduced pressure or under an inert gas flow. The temperature of the solid phase polymerization is preferably 200 to 280 ° C. By setting the temperature of the solid phase polymerization in the above range and setting the upper limit of the range to 280 ° C., coloring and gelation of the obtained semi-aromatic polyamide can be suppressed. On the other hand, if the temperature of the solid phase polymerization is less than 200 ° C., the polymerization time becomes long and the productivity may be inferior.

The melt polymerization of the above prepolymer is preferably carried out at a temperature of 350 ° C. or lower. By carrying out the polymerization at a temperature of 350 ° C. or lower, it is possible to carry out the polymerization efficiently while suppressing decomposition and thermal deterioration. The above-mentioned melt polymerization also includes melt polymerization using a melt extruder.

A polymerization catalyst may be used in the polymerization of the above-mentioned semi-aromatic polyamide (A). As the polymerization catalyst, it is preferable to use a phosphorus-based catalyst from the viewpoint of reaction rate and economy. Phosphorus-based catalysts include, for example, hypophosphoric acid, phosphoric acid, phosphoric acid, salts thereof (eg, sodium hypophosphite), or esters thereof (eg, 2,2-methylenebis (di-t-). Butylphenyl) octylphosphite, etc.) can be mentioned. These may be used alone or in combination of two or more.

Above all, the semi-aromatic polyamide (A) obtained by polymerization using phosphorous acid as a polymerization catalyst is more preferable. By using phosphorous acid as the polymerization catalyst, a filter is used in film formation as compared with the case of using a semi-aromatic polyamide polymerized using another polymerization catalyst (for example, a hypophosphorous acid catalyst). As a result, it is possible to suppress an increase in the filtration pressure during filtration of the film-forming raw material.

Further, by using the semi-aromatic polyamide (A) obtained by polymerization using phosphorous acid as a catalyst, gelation of the obtained resin itself can be suppressed. As a result, the generation of fish eyes is suppressed.

The content of the polymerization catalyst in the obtained semi-aromatic polyamide (A) is preferably 0.01 to 5% by mass, preferably 0.05 to 2% by mass, based on 100% by mass of the total amount of all the monomer components. %, More preferably 0.07 to 1% by mass. When the content of the polymerization catalyst is 0.01 to 5% by mass, the semi-aromatic polyamide can be efficiently polymerized while suppressing the deterioration of the semi-aromatic polyamide. If the content of the polymerization catalyst is less than 0.01% by mass, the catalytic action may not be exhibited. On the other hand, if it exceeds 5% by mass, it may be disadvantageous from the viewpoint of economic efficiency.

Further, a terminal encapsulant may be used together with a diamine component, a dicarboxylic acid component and a polymerization catalyst. The terminal encapsulant is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the terminal of the semi-aromatic polyamide (A). Examples of such terminal sealants include monocarboxylic acids, monoamines, acid anhydrides, monoisocyanates, monohalides, monoesters, and monoalcohols.

Among them, monocarboxylic acid or monoamine is preferable from the viewpoint of reactivity and stability of the sealed terminal group, and monocarboxylic acid is more preferable from the viewpoint of ease of handling. Examples of the monocarboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid and benzoic acid.

The amount of the terminal encapsulant to be used can be appropriately selected depending on the reactivity of the end encapsulant used, the boiling point, the reaction apparatus, the reaction conditions and the like. The detailed amount of the terminal encapsulant used is preferably 0.1 to 15 mol% with respect to the dicarboxylic acid component in the case of monocarboxylic acid from the viewpoint of adjusting the molecular weight and suppressing the decomposition of the resin, and monoamine. In the case of, it is preferably 0.1 to 15 mol% with respect to the diamine component.

In the semi-aromatic polyamide (A) used in the present invention, it is preferable that the terminal group of the molecular chain is sealed with the terminal encapsulant as described above. The ratio of the amount of end-sealed end groups to the total amount of end groups is preferably 10 mol% or more, more preferably 40 mol% or more, still more preferably 70 mol% or more. When the ratio of the amount of the sealed terminal groups is 10 mol% or more, it is possible to suppress the decomposition of the resin during the molding process of the film and the increase in the molecular weight due to the progress of condensation. Further, since the generation of bubbles due to the decomposition of the resin is suppressed along with this, the appearance of the film obtained by using the semi-aromatic polyamide (A) can be improved.

Next, the thermoplastic elastomer (B) having a functional group used in the present invention will be described.

The thermoplastic elastomer (B) used in the present invention has a configuration including a hard segment and a soft segment.

Examples of the type of the thermoplastic elastomer (B) include a polyolefin-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, and a styrene-based thermoplastic elastomer. These thermoplastic elastomers (B) may be used alone or in combination of two or more.

Examples of the polyolefin-based thermoplastic elastomer include those in which the hard segment is a thermoplastic high-crystalline polyolefin and the soft segment is an ethylene-α-olefin-based copolymer rubber. Specifically, examples of the hard segment include homopolymers of α-olefins having 1 to 4 carbon atoms or copolymers of two or more thereof. Of these, polyethylene or polypropylene is preferable. Examples of soft segments include butyl rubber, halobutyl rubber, EPDM (ethylene / propylene / diene rubber), EPR (ethylene / propylene rubber), acrylonitrile / butadiene rubber, NBR (nitrile rubber), EBR (ethylene 1-butene rubber), and natural products. Rubber is mentioned.

As the polyester-based thermoplastic elastomer, for example, a high melting point and highly crystalline aromatic polyester such as polybutylene terephthalate (PBT) is used for the hard segment, and an amorphous material such as polytetramethylene ether glycol (PTMG) is used for the soft segment. Examples thereof include multi-block polymers in which sex polyether is used.

Examples of the polyamide-based thermoplastic elastomer include block polymers in which the hard segment is polyamide and the soft segment is polyester or polyol.

Examples of the styrene-based thermoplastic elastomer include a polymer in which the hard segment is polystyrene and the soft segment is a copolymer of a conjugated diene compound and a polymer in which the hydrogenated compound thereof is used. Examples of the soft segment include isoprene rubber, butadiene rubber, hexadiene rubber, and 2,3-dimethyl-1,3-butadiene.

The thermoplastic elastomer (B) used in the present invention needs to have a functional group capable of reacting with an amino group or a carboxyl group which is a terminal group of the semi-aromatic polyamide (A) and an amide group of the main chain. The functional group is preferably at least one functional group selected from a carboxyl group or an anhydride thereof, an amino group, a hydroxyl group, an epoxy group, an amide group and an isocyanate group, and a dicarboxylic acid and / or a derivative thereof is more preferable. When a thermoplastic elastomer having no functional group capable of reacting with the terminal group of the semi-aromatic polyamide (A) is used, the stretchability during biaxial stretching is lowered and a uniform stretched film cannot be obtained, or the relative temperature is reached. It is not preferable because the index may be less than 100 ° C.

In the present invention, among the thermoplastic elastomers modified with dicarboxylic acid and / or a derivative thereof, it is preferable that the thermoplastic elastomer is a polyolefin-based thermoplastic resin. Examples of such a resin include toughmers manufactured by Mitsui Chemicals, Inc. and the like.

The semi-aromatic polyamide film of the present invention has a compounding ratio (A) / (B) of the semi-aromatic polyamide (A) and the thermoplastic elastomer (B) of 97/3 to 90/10 (mass ratio). It is necessary, preferably 96/4 to 92/8 (mass ratio). If the compounding ratio of the thermoplastic elastomer (B) is less than 3% by mass, the addition effect is small and the relative temperature index does not reach 100 ° C., which is not preferable. On the other hand, when the compounding ratio of the thermoplastic elastomer (B) exceeds 10% by mass, the melt viscosity at the time of extrusion film formation is too high and the film forming property is lowered, or the stretchability at the time of biaxial stretching is lowered and uniform. It is not preferable because a stretched film cannot be obtained and the tensile strength retention rate is low.

The kneader used for kneading the semi-aromatic polyamide (A) and the thermoplastic elastomer (B) is not particularly limited, but for example, a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, a mixing roll, or the like is usually used. Examples thereof include known melt kneaders. Above all, a twin-screw extruder is preferable from the viewpoint of improving the dispersibility of the thermoplastic elastomer (B). The melt-kneading temperature is usually equal to or higher than the melting point of the semi-aromatic polyamide (A). As for the thermoplastic elastomer (B), it is preferable to prepare a masterbatch in which the thermoplastic elastomer (B) is blended in a high concentration, and then knead the masterbatch with the semi-aromatic polyamide (A). In the master batch, the semi-aromatic polyamide (A) is melt-kneaded first, and the thermoplastic elastomer (B) is added from the middle. Specifically, the semi-aromatic polyamide (A) is added to the top feeder of the kneader. It is preferable to prepare by a method of adding the thermoplastic elastomer (B) from the side feeder of the kneader. According to this method, the mixing uniformity of the semi-aromatic polyamide (A) and the thermoplastic elastomer (B) is further enhanced, and as a result, the relative temperature index can be improved.

The semi-aromatic polyamide film of the present invention enhances thermal stability during film formation, prevents deterioration of film strength and elongation, and is suitable for oxidation and decomposition during use, as long as the effects of the present invention are not impaired. A heat stabilizer may be contained in order to prevent deterioration of the film due to the deterioration. Examples of the heat stabilizer include copper compounds, halogen compounds, hindered phenol-based heat stabilizers, hindered amine-based heat stabilizers, phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and bifunctional heat stabilizers.

Examples of the copper compound include copper halide compounds such as copper chloride, copper iodide and copper bromide, inorganic copper acid compounds such as copper oxide, copper sulfate, copper nitrate and copper phosphate, copper acetate and copper stearate. Organic copper acid compounds of.

Examples of the halogen compound include alkali halide compounds such as sodium chloride, potassium chloride, sodium iodide, potassium iodide, sodium bromide, and potassium bromide.

Examples of the hindered phenolic heat stabilizer include Irganox 1010 (registered trademark) (Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] manufactured by BASF Japan), Irganox 1076. (Registered Trademark) (BASF Japan, Inc., Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), Cyanox1790 (Registered Trademark) (Sianamide, Inc., 1,3,5-Tris) (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid), Irganox1098 (registered trademark) (BASF Japan, Inc., N, N'-(hexane-1,6-diyl) bis [3] -(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]), etc., as well as hindered phenolic compounds having the structure of the general formula (1) (hereinafter referred to as "specific hindered phenolic compounds"). It may be abbreviated.). Specific hindered phenol compounds include Sumilyzer GA-80 (registered trademark) (Sumitomo Chemical Co., Ltd., 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyl). Oxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane), Irganox245® (BASF Japan, Inc., bis (3-tert-butyl-4) -Hydroxy-5-methylbenzenepropanoic acid) ethylene bis (oxyethylene)) and the like.

（式中、Ｒ１およびＲ２は、独立して、メチル基、エチル基または水素を示す。）

(In the formula, R1 and R2 independently represent a methyl group, an ethyl group or hydrogen.)

Examples of the hindered amine-based heat stabilizer include Nylostab S-EED (registered trademark) (2-ethyl-2'-ethoxy-oxalanilide manufactured by Clariant Japan, Inc.).

Examples of the phosphorus-based heat stabilizer include Irgafos 168 (registered trademark) (BASF Japan, Tris (2,4-di-tert-butylphenyl) phosphite) and Irgafos 12 (registered trademark) (BASF Japan, 6). , 6', 6 "-[Nitrilotris (ethyleneoxy)] Tris (2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepine)) , Irgafos38 (registered trademark) (BASF Japan, bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphite), ADKSTAB329K (registered trademark) (Asahi Denka) , Tris (mono-dinonylphenyl) phosphite), ADKSTAB PEP36 (registered trademark) (Asahi Denka Co., Ltd., bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite) , Hostanox P-EPQ® (Clariant, Tetrakiss (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite), GSY-P101® (Sakai Chemical Industry) Tetrakiss (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite), Sumilyzer GP (registered trademark) (Sumitomo Chemical Co., Ltd., 6- [3- (3) 3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] -dioxaphosphepine ).

Examples of the sulfur-based heat stabilizer include DSTP (registered trademark) (manufactured by Yoshitomi Co., Ltd., chemical formula name: distearylthiodipropionate) and Seenox 412S (registered trademark) (manufactured by Cipro Chemical Co., Ltd., pentaerythritol tetrakis- (3-). Dodecylthiopropionate)), Cyanox 1212® (Cyanamide, laurylstearylthiodipropionate).

Examples of the bifunctional heat stabilizer include Sumilyzer GM (registered trademark), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4 manufactured by Sumitomo Chemical Co., Ltd. -Methylphenyl acrylate), Sumilyzer GS (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd., 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert- (Pentylphenyl acrylate).

Above all, when a hindered phenolic heat stabilizer and a copper compound are used in combination, the relative temperature index can be synergistically improved, and the tensile strength retention rate at high temperatures can be further improved. Further, if a hindered phenol-based heat stabilizer and a phosphorus-based heat stabilizer are used in combination, it is possible to prevent the pressure rise of the raw material filtration filter during film formation and to prevent deterioration of the film strength. .. In addition, if a hindered phenol-based heat stabilizer, a phosphorus-based heat stabilizer, and a bifunctional heat stabilizer are used in combination, it is possible to prevent the pressurization of the filter for raw material filtration during film formation and to improve the film strength. Deterioration can be further reduced.

As a combination of the hindered phenol-based heat stabilizer and the copper compound, a combination of the specific hindered phenol compound and copper iodide is preferable. As a combination of the hindered phenol-based heat stabilizer and the phosphorus-based heat stabilizer, a combination of Hostanox P-EPQ or GSY-P101 and a specific hindered phenol compound is preferable. As a combination of a hindered phenol-based heat stabilizer, a phosphorus-based heat stabilizer, and a bifunctional heat stabilizer, a combination of HostanoxP-EPQ or GSY-P101, a specific hindered phenol compound, and a simulator GS is preferable, and GSY- A combination of P101, a specific hindered phenol compound, and a simulator GS is more preferable.

The semi-aromatic polyamide film of the present invention contains a copper compound, a halogen compound, a hindered phenol-based heat stabilizer, a hindered amine-based heat stabilizer, a phosphorus-based heat stabilizer, a sulfur-based heat stabilizer, and a bifunctional heat stabilizer. The content thereof is preferably 0.006 to 2 parts by mass with respect to a total of 100 parts by mass of the semi-aromatic polyamide (A) and the thermoplastic elastomer (B) having a functional group, and is 0. More preferably, it is 0.05 to 1 part by mass. When the content of the heat stabilizer is 0.01 to 2 parts by mass, thermal decomposition can be suppressed more efficiently. When two or more kinds of the above heat stabilizers are used in combination, it is preferable that both the individual content of each heat stabilizer and the total content of the heat stabilizers are in the above range.

The semi-aromatic polyamide film of the present invention may contain lubricant particles as long as the effects of the present invention are not impaired. Examples of the lubricant particles include inorganic particles such as silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate, and organic fine particles such as acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles. Be done.

The semi-aromatic polyamide film of the present invention may contain various additives as long as the effects of the present invention are not impaired. Examples of the additive include colorants such as pigments and dyes, color inhibitors, antioxidants different from the above heat stabilizers, weather resistance improvers, flame retardants, plasticizers, mold release agents, strengthening agents, and modifications. Examples include agents, antistatic agents, UV absorbers, antifogging agents, and various polymers. Examples of the pigment include titanium oxide and carbon black. Examples of the weather resistance improving agent include benzotriazole-based compounds. Examples of the flame retardant include brominated flame retardants and phosphorus flame retardants. Examples of the fortifier include talc and the like. The above additives may be added at any stage during the production of the film.

The semi-aromatic polyamide film of the present invention may be an unstretched film or a stretched film, but is preferably a stretched film stretched in the uniaxial or biaxial direction, and is biaxial. It is more preferable that the stretched film is stretched. It is preferable that the polyamide resin is oriented and crystallized by stretching. The stretching conditions and the magnification are not particularly limited, but when stretched in the biaxial direction, it may be abbreviated in the longitudinal direction (hereinafter, may be abbreviated as "MD") and the width direction (hereinafter, abbreviated as "TD"). It is preferable that both of them are stretched by 2 times or more, and more preferably 2.5 times or more. When the draw ratio is 2 times or less, the degree of orientation crystallization by stretching is low, and therefore the strength and heat resistance of the film may be inferior.

The semi-aromatic polyamide film of the present invention needs to have a relative temperature index of 100 ° C. or higher, preferably 105 ° C. or higher. As will be described later, the relative temperature index calculates the time when the tensile strength becomes 50% before the treatment at the treatment temperatures of 180 ° C, 160 ° C, 140 ° C, and 120 ° C, and the inverse of each absolute temperature and each. The logarithmic strength half-time at temperature is plotted to set the temperature at which the tensile strength becomes 50% in 100,000 hours.

The semi-aromatic polyamide film of the present invention preferably has a tensile strength retention rate of 80% or more, more preferably 90% or more. In order to increase the tensile strength retention rate to 80% or more, it is preferable to use a copper compound and a hindered phenolic heat stabilizer as the heat stabilizer.

The stretched semi-aromatic polyamide film of the present invention preferably has a small heat shrinkage rate. For example, the heat shrinkage rate by heating with hot air at 200 ° C. for 15 minutes is preferably 3.0% or less, more preferably 1.0% or less, still more preferably 0.5% or less. ..

The tensile strength of the stretched semi-aromatic polyamide film of the present invention is preferably 130 MPa or more for both MD and TD, and the tensile elongation is preferably 50% or more for both TD and MD.

The thickness unevenness of the stretched semi-aromatic polyamide film of the present invention is preferably 10% or less, more preferably 8% or less, still more preferably 6% or less. When the thickness unevenness is 10% or less, it is possible to reduce the sagging and wrinkles of the film when processing the film. The definition of thickness unevenness and its measuring method will be described in detail in the "Examples" section below.

The stretched semi-aromatic polyamide film of the present invention can be subjected to a treatment for improving the adhesiveness of its surface, if necessary. Examples of the method for improving the adhesiveness include corona treatment, plasma treatment, acid treatment, and flame treatment.

Various coating agents may be applied to the surface of the stretched semi-aromatic polyamide film of the present invention in order to impart functions such as easy adhesion, antistatic property, mold release property, and gas barrier property.

The stretched semi-aromatic polyamide film of the present invention may be laminated with an inorganic substance such as a metal or an oxide thereof, a polymer of another kind, paper, a woven fabric, a non-woven fabric, wood or the like.

Next, the method for producing the stretched semi-aromatic polyamide film of the present invention will be described by taking the case of biaxial stretching as an example.

As an example of the method for producing the biaxially stretched semi-aromatic polyamide film of the present invention, the semi-aromatic polyamide (A) and the thermoplastic elastomer (B) are blended in an appropriate ratio, and the blend is placed in an extruder. After melting and mixing at a temperature of 280 to 340 ° C. for 3 to 15 minutes, the sheet is extruded into a sheet through a T-die, and the sheet is brought into close contact with a drum whose temperature has been adjusted to 30 to 80 ° C. and cooled. An unstretched film is produced, and the obtained unstretched film is subsequently guided to a simultaneous biaxial stretching machine. A method of stretching and further heat-treating at 150 to 300 ° C. for several seconds with TD relaxation as a few percent can be mentioned. The film may be preliminarily stretched about 1 to 1.2 times before being guided to the simultaneous biaxial stretching machine.

The biaxially stretched semi-aromatic polyamide film of the present invention can also be produced by a sequential stretching method. As an example, there is a method of obtaining an unstretched film by performing the same operation as described above, subjecting it to heat treatment such as roll heating and infrared heating, and then stretching it in the vertical direction to obtain a vertically stretched film. .. This longitudinal stretching utilizes the difference in peripheral speed between two or more rolls, with the glass transition point of the semi-aromatic polyamide as Tg, and is 2.0 to 3.6 times in the temperature range of Tg to (Tg + 40 ° C.). It is preferable to stretch it. The longitudinally stretched film is subsequently continuously subjected to lateral stretching, heat fixing, and relaxing treatment to obtain a biaxially stretched film. At this time, the transverse stretching starts in the same temperature range of Tg to (Tg + 40 ° C.) as in the case of the longitudinal stretching, and the maximum temperature may be 100 to 150 ° C. lower than the melting point (Tm) of the semi-aromatic polyamide. preferable. The ratio of lateral stretching is adjusted by the required physical properties of the final film, but is preferably 2.5 times or more, and more preferably 3.0 times or more. During the heat fixing treatment following the transverse stretching, 2 to 20% stretching may be applied in the transverse direction, that is, the width direction of the film. However, the stretch ratio is included in the total stretch ratio. After the heat fixing treatment, a relaxing treatment is performed, and then the film is cooled to Tg or less thereof to obtain a biaxially stretched film.

In film manufacturing equipment, the surface of cylinders, barrel melts, measuring parts, single tubes, filters, T-dies, etc. is treated to reduce the surface roughness in order to prevent resin from staying. Is preferable. As a method of reducing the surface roughness, for example, a method of modifying with a substance having low polarity can be mentioned. Alternatively, a method of depositing silicon nitride or diamond-like carbon on the surface thereof can be mentioned.

Examples of the method for stretching the film include a flat type sequential biaxial stretching method, a flat simultaneous biaxial stretching method, and a tubular method. Above all, it is preferable to adopt the flat type simultaneous biaxial stretching method from the viewpoint of improving the thickness accuracy of the film and making the physical properties of the MD of the film uniform.

Examples of the stretching device for adopting the flat type simultaneous biaxial stretching method include a screw type tenter, a pantograph type tenter, and a linear motor drive clip type tenter.

The heat treatment after stretching is preferably provided in order to impart dimensional stability of the film. Examples of the heat treatment method include known methods such as a method of blowing hot air, a method of irradiating infrared rays, and a method of irradiating microwaves. Above all, the method of blowing hot air is preferable because it can be heated uniformly and accurately.

The obtained semi-aromatic polyamide film may be made into a single leaf, or may be taken into a film roll by being wound on a take-up roll. From the viewpoint of productivity when used for various purposes, it is preferable to use a film roll. When it is made into a film roll, it may be slit to a desired width.

The semi-aromatic polyamide film of the present invention obtained as described above is used for packaging materials for pharmaceuticals; packaging materials for foods such as retort foods; packaging materials for electronic parts such as semiconductor packages; motors, transformers, cables, etc. Electrical insulation materials; dielectric materials for capacitor applications, etc .; materials for magnetic tapes such as cassette tapes, magnetic tapes for data storage for digital data storage, video tapes; solar cell substrates, liquid crystal plates, conductive films, display equipment Protective plate for etc .; LED mounting board, flexible printed wiring board, electronic board material such as flexible flat cable; Coverlay film for flexible printed wiring, heat-resistant masking tape, heat-resistant tape such as industrial process tape; Heat-resistant bar code label; Heat-resistant reflector; Insulation tape; Various release films; Heat-resistant base film; Photo film; Push switch, Tactile switch, Rocker switch, Toggle switch, Rotary switch and other molding materials; Agricultural materials; Medical materials It can be used as a film for household and industrial materials such as civil engineering and construction materials; filter membranes and the like. Above all, since the semi-aromatic polyamide film of the present invention has excellent long-term heat resistance, it can be suitably used as a substrate for flexible flat cable wiring, a coverlay film, a heat resistant tape, and an insulating tape.

1. 1. Analytical physical properties were measured by the following method.

(1) Melt Viscosity of Thermoplastic Elastomer Measured at 230 ° C. under a load of 2.16 kg according to ISO1133.

(2) Extreme Viscosity of Semi-Aromatic Polyamide In concentrated sulfuric acid having a concentration of 96% by mass, semi-aromatic polyamide was added at 30 ° C. at 0.05 g / dL, 0.1 g / dL and 0.2 g, respectively. The reduced viscosity of the semi-aromatic polyamide was determined by dissolving the mixture so as to have a concentration of / dL and 0.4 g / dL. Then, the value of each reduction viscosity was used, and the value extrapolated to the concentration of 0 g / dL was taken as the ultimate viscosity.

(3) Melting point (Tm) and glass transition temperature (Tg) of semi-aromatic polyamide or thermoplastic elastomer
Using a differential scanning calorimeter (“DSC-7”, manufactured by PerkinElmer), heat the temperature of semi-aromatic polyamide or thermoplastic elastomer 10 mg from 20 ° C to 350 ° C at 10 ° C / min under a nitrogen atmosphere. (1st Scan), held at 350 ° C. for 5 minutes. Then, the temperature was lowered to 20 ° C. at 100 ° C./min, held at 20 ° C. for 5 minutes, and then further heated to 350 ° C. at 20 ° C./min (2nd Scan). Then, the peak top temperature of the crystal melting peak observed in the 2nd Scan was defined as the melting point, and the midpoint between the temperatures of the two bending points derived from the glass transition was defined as the glass transition temperature.

(4) Using an unstretched film and an average thickness thickness meter (“MT12B” manufactured by HEIDENHAIN), the thickness of the film was adjusted to the center of the TD of the roll-shaped film in an environment of a temperature of 20 ° C. and a humidity of 65%. At the position of, the measurement was performed 10 times for every 1 m of MD. Then, the average thickness was obtained from the obtained 10 measured values.

(5) Uneven thickness of stretched film With respect to the range of 20 cm × 20 cm in the center of the stretched film in the width direction, the thicknesses of 30 points were randomly measured at a temperature of 20 ° C. and a humidity of 65%. The maximum value of the measured value was Lmax, the minimum value was Lmin, and the average value was La. Then, the value represented by the following formula was defined as "thickness unevenness R" and evaluated according to the following criteria.
R = [(Lmax-Lmin) / La] x 100 (%)
⊚: R ≦ 10
◯: 10 <R ≦ 15
□: 15 <R≤20
×: 20 <R

(6) Retention rate of tensile strength of the stretched film The tensile strength was measured before and after the stretched film was heat-treated at 260 ° C. for 5 minutes, and the retention rate was calculated.
The tensile strength was measured according to JIS K7127 in an environment of a temperature of 20 ° C. and a humidity of 65%.
The size of the sample was 10 mm × 150 mm, the initial distance between the chucks was 100 mm, and the tensile speed was 500 mm / min.

(7) Relative temperature index of stretched film A stretched film cut to A4 size is heat-treated with a precision thermostat (Yamato FINE OVEN DF-61) manufactured by Yamato Scientific Co., Ltd. set at 180 ° C, 160 ° C, 140 ° C, and 120 ° C. Then, in the same manner as in (6), the tensile strength was measured until it was less than 50% of the tensile strength before the heat treatment. At 180 ° C, every 1 to 1 day after heat treatment, at 160 ° C, every 4 to 4 days after heat treatment, at 140 ° C, every 16 to 16 days after heat treatment, and at 120 ° C, 64 days after heat treatment. It was measured every 64 days from the above, and the time for the tensile strength to be 50% before the treatment was calculated according to UL746B.
The reciprocal of each absolute temperature and the logarithm of the strength half time at each temperature were plotted, and the temperature at which the tensile strength became 50% in 100,000 hours was calculated.

2. 2. Raw material <raw material monomer>
(1) Linear aliphatic diamine 1,9-nonandiamine (hereinafter, may be abbreviated as "NMDA")

(2) Branched chain aliphatic diamine 2-methyl-1,8-octanediamine (hereinafter, may be abbreviated as "MODA")

(3) Dicarboxylic acid Terephthalic acid (hereinafter, may be abbreviated as "TPA")

(4) End sealant Benzoic acid (hereinafter, may be abbreviated as "BA")

<Catalyst>
Phosphorous acid (hereinafter sometimes abbreviated as "PA")

<Copper compound>
Copper iodide (hereinafter sometimes abbreviated as "CuI")

<Hindered phenolic heat stabilizer>
Sumilyzer GA-80: Made by Sumitomo Chemical Co., Ltd. (hereinafter, may be abbreviated as "GA")
Irganox 1098: Made by BASF (hereinafter, may be abbreviated as "IR")

<Phosphorus heat stabilizer>
GSY-P101: Manufactured by Sakai Chemical Industry Co., Ltd. (hereinafter, may be abbreviated as "GSY")

<Bifunctional heat stabilizer>
Sumilyzer GS: manufactured by Sumitomo Chemical Co., Ltd. (hereinafter, may be abbreviated as "GS")

<Additives>
Carbon Black # 980: Made by Mitsubishi Chemical Corporation

[Semi-aromatic polyamide (A)]
(1) Semi-aromatic polyamide A1
1343 g of NMDA, 237 g of MODA, 1627 g of TPA (average particle size: 80 μm) (NMDA: MODEA: TPA = 85: 15: 99, molar ratio), 48.2 g of BA (total number of moles of dicarboxylic acid component and diamine component) 4.0 mol%), 3.2 g PA (0.1% by weight based on the total amount of the dicarboxylic acid component and the diamine component), and 1100 g of water were placed in the reactor and substituted with nitrogen. Further, the mixture was stirred at 80 ° C. for 0.5 hours at 28 rpm, and then the temperature was raised to 230 ° C. Then, it heated at 230 degreeC for 3 hours. After that, it was cooled and the reaction product was taken out. After pulverizing the reaction product, the semi-aromatic polyamide A1 was produced by solid-phase polymerization by heating at 220 ° C. for 5 hours under a nitrogen stream in a dryer.

(2)-(3) Semi-aromatic polyamides A2-A3
As shown in Table 1, the same operations as in the case of producing the semi-aromatic polyamide A1 were performed except that the molar ratios of the diamine component, the dicarboxylic acid component and the monocarboxylic acid component were changed, and the semi-aromatic polyamides A2 to A3 were performed. Manufactured.

Table 1 shows the composition ratios of the semi-aromatic polyamides A1 to A3 and their characteristic values.

[Thermoplastic elastomer (B)]
(1) Toughmer MH7020: Mitsui Chemicals, Inc., maleic anhydride-modified polyolefin, melt viscosity 1.5 g / 10 minutes, Tg-65 ° C.
(2) Tough Tech M1913: Maleic anhydride-modified polystyrene-hydrogenated polybutadiene copolymer, melt viscosity 5.0 g / 10 min, Tg -20 ° C and 105 ° C, manufactured by Asahi Kasei Corporation.
(3) Toughmer A1050S: Mitsui Chemicals, Inc., acid-modified polyolefin, melt viscosity 2.2 g / 10 minutes, Tg-65 ° C.

[Semi-aromatic polyamide masterbatch]
(1) Semi-aromatic polyamide masterbatch AM1
100 parts by mass of semi-aromatic polyamide A1 and 0.4 parts by mass of GA were dry-blended and melt-kneaded using a twin-screw extruder having a screw diameter of 26 mm. The cylinder temperature of the twin-screw extruder was 310 ° C. Then, it was extruded into a strand shape, cooled, and cut to produce a pellet-shaped semi-aromatic polyamide masterbatch AM1.

(2)-(11) Semi-aromatic polyamide masterbatch AM2-AM11
As shown in Table 2, the semi-aromatic polyamide masterbatch AM1 is operated in the same manner as in the case of producing the semi-aromatic polyamide masterbatch AM1, except that the types and blending ratios of the semi-aromatic polyamide, heat stabilizer and additives used are changed. Polyamide master batches AM2 to AM11 were produced.

Table 2 shows the compounding composition of the semi-aromatic polyamide masterbatch AM1 to AM11.

[Masterbatch containing thermoplastic elastomer]
(1) Masterbatch BM1 containing thermoplastic elastomer
Semi-aromatic polyamide A1 75 parts by mass and GA 0.4 parts by mass were dry blended.
This is charged into the top feeder of a twin-screw extruder whose cylinder temperature is heated to 310 ° C. and has a screw diameter of 26 mm. , To produce a pellet-shaped thermoplastic elastomer-containing masterbatch BM1.

(2)-(6) Thermoplastic Elastomer-Containing Masterbatch BM2-BM6
Except for changing the type and blending ratio of the semi-aromatic polyamide and thermoplastic elastomer used as shown in Table 3, the same operation as when manufacturing the thermoplastic elastomer-containing master batch BM1 was performed, and the thermoplastic elastomer master batch BM2 was performed. -BM6 was manufactured.

(7) Masterbatch BM7 containing thermoplastic elastomer
Semi-aromatic polyamide A1 75 parts by mass, Toughmer MH7020 25 parts by mass, and GA 0.4 parts by mass were dry-blended. This is put into the top feeder of a twin-screw extruder whose cylinder temperature is heated to 310 ° C. and has a screw diameter of 26 mm, melt-kneaded, extruded into strands, cooled and cut, and contains pellet-shaped thermoplastic elastomer. A masterbatch BM7 was manufactured.

Table 3 shows the compounding composition of the thermoplastic elastomer-containing master batches BM1 to BM7.

Example 1
67.5 parts by mass of semi-aromatic polyamide masterbatch AM1, 12.5 parts by mass of semi-aromatic polyamide masterbatch AM4, and 20 parts by mass of thermoplastic elastomer-containing masterbatch BM1 were heated to a cylinder temperature of 320 ° C. However, it was put into a uniaxial extruder having a screw diameter of 40 mm and melted to obtain a molten polymer. The molten polymer was filtered using a metal fiber sintered filter (Nippon Seisen Co., Ltd., "NF-13", absolute particle size: 60 μm). Then, the molten polymer was extruded into a film from a T-die heated to 320 ° C. to obtain a film-like melt. The melt was brought into close contact with a cooling roll set at 50 ° C. by an electrostatic application method and cooled to obtain a substantially unoriented unstretched film (average thickness: 230 μm).
While gripping both ends of the obtained unstretched film with clips, biaxial stretching was performed with a flat type simultaneous biaxial stretching machine. The stretching conditions were that the temperature of the preheated part was 125 ° C, the temperature of the stretched part was 130 ° C, the stretching strain rate of MD was 2400% / min, the stretching strain rate of TD was 2760% / min, and the stretching ratio of MD was 3.0. The draw ratio of TD was 3.3 times. After stretching, the film was continuously heat-fixed at 270 ° C. in the same tenter of the biaxial stretching machine and subjected to a 5% relaxation treatment in the width direction of the film to obtain a biaxially stretched film having an average thickness of 25 μm.

Examples 2 to 16, Comparative Examples 1 to 7
An unstretched film was produced and a biaxially stretched film was produced by performing the same operations as in Example 1 except that the types and blending ratios of the semi-aromatic polyamide masterbatch and the thermoplastic elastomer-containing masterbatch to be used were changed. ..

Table 4 shows the types and blending ratios of the raw materials used, the characteristic values of the unstretched film, and the characteristic values of the stretched film for Examples 1 to 16 and Comparative Examples 1 to 7.

Since the semi-aromatic polyamide films of Examples 1 to 16 satisfied the requirements of the present invention, the relative temperature index was 100 ° C. or higher.

The semi-aromatic polyamide films of Examples 1 and 8 to 10 had a high relative temperature index and a high tensile strength retention rate because a copper compound was further used in comparison with the semi-aromatic polyamide film of Example 11.
Since the semi-aromatic polyamide film of Example 1 was used in combination with a copper compound, the relative temperature was compared with that of the semi-aromatic polyamide films of Examples 12 and 13 in which a phosphorus-based heat stabilizer and a bifunctional heat stabilizer were used in combination. The index was high and the tensile strength retention rate was high.
Since GA was used as the hindered phenolic heat stabilizer in the semi-aromatic polyamide film of Example 1, the relative temperature index was higher and the tensile strength was higher than that of Example 15 in which IR was used as the hindered phenolic heat stabilizer. The retention rate was high.

In the semi-aromatic polyamide film of Comparative Example 1, the thermoplastic elastomer used did not have a functional group. Therefore, the stretchability was poor, the thickness unevenness of the film was large, the tensile strength was low, and the relative temperature index was less than 100 ° C.
In the semi-aromatic polyamide film of Comparative Example 2, the content of the thermoplastic elastomer used was less than the range specified in the present invention. Therefore, the relative temperature index was less than 100 ° C.
In the semi-aromatic polyamide film of Comparative Example 3, the content of the thermoplastic elastomer used was larger than the range specified in the present invention. Therefore, the stretchability was poor, the thickness unevenness of the film was large, the tensile strength was low, and the tensile strength retention rate was low.
The semi-aromatic polyamide film of Comparative Examples 4 and 5 did not use a thermoplastic elastomer. Therefore, the relative temperature index was less than 100 ° C.
As the semi-aromatic polyamide film of Comparative Examples 6 and 7, a master batch prepared by simultaneously adding the semi-aromatic polyamide (A) and the thermoplastic elastomer (B) was used. Therefore, the uniformity of the thermoplastic elastomer in the semi-aromatic polyamide was low, and the relative temperature index was less than 100 ° C.

Claims (1)

Semi-aromatic polyamide (A) 97-90% by mass consisting of a dicarboxylic acid containing terephthalic acid as a main component and a diamine containing an aliphatic diamine having 9 carbon atoms as a main component.
A thermoplastic elastomer (B) having at least one functional group selected from a carboxyl group or an anhydride thereof, an amino group, a hydroxyl group, an epoxy group, an amide group and an isocyanate group, and 3 to 10% by mass of the thermoplastic elastomer (B).
Consists of heat stabilizers ,
The total of (A) and (B) is 100% by mass,
The heat stabilizer consists of only one or more heat stabilizers selected from hindered phenolic heat stabilizers, phosphorus heat stabilizers and bifunctional heat stabilizers.
A semi-aromatic polyamide stretched film having a relative temperature index of 100 ° C. or higher at which the tensile strength of MD becomes 50% in 100,000 hours.