JP5828149B2 - Polyamide resin composition for film - Google Patents

Description

The present invention has little thickness unevenness during film formation, prevents breakage during film stretching, has good transparency, and has little unevenness, and is excellent in slipperiness, printability, flexibility, and hot water resistance. The present invention relates to a polyamide resin composition for a film.

The polyamide film is excellent in gas barrier properties, toughness, mechanical properties, and thermal properties. Therefore, polyamide resins are used in various fields as packaging films, especially in the field of food packaging, as a base material for single-layer films or laminate films, and as a constituent material for laminated films by coextrusion with other resins. . The slipperiness in such a polyamide film is one of the important required characteristics in terms of film productivity, quality and commercial value. If slipperiness is poor, workability during post-processing, that is, a film may be caught during bag making, or ink printing misalignment may occur during multicolor printing.

In order to improve the slipperiness of such a polyamide film, a method of blending inorganic filler particles (see Patent Document 1) has been proposed. In a method of improving slipperiness by blending inorganic filler particles, it is possible to obtain a film with satisfactory slipperiness by using a sufficient amount of inorganic filler particles. If the amount is too large, uniform dispersion of the inorganic filler particles in the film is hindered, resulting in a significant decrease in transparency, which is a characteristic of the polyamide film, and the commercial value is impaired. The blending amount was restricted.
In addition, in the method of blending inorganic filler particles, granular defects called fish eyes and streak-like appearance defects called die lines are likely to occur, and polymer degradation products and additive aggregates are formed at the lip mouth of the die. Because of the rapid generation of accumulated grease, it is difficult to stably produce high-quality films with excellent appearance, and it is often forced to stop the extruder and clean the lip of the die. Production efficiency has been reduced.

As various methods for suppressing the generation of die lines and eye grease without impairing slipperiness, a method of blending inorganic filler particles and hydroxy fatty acid magnesium salt (see Patent Document 2), inorganic filler particles and a mixture of zinc oxide and basic fatty acid magnesium (Refer to Patent Document 3), inorganic filler particles and a bisamide compound, a method of compounding a partial ester compound of a 3-6 valent aliphatic alcohol and a fatty acid having 10 to 22 carbon atoms (refer to Patent Document 4) A method of blending inorganic filler particles, a partial ester compound of a 3-6 valent aliphatic alcohol and a fatty acid having 10 to 22 carbon atoms, and a magnesium salt of a hydroxy fatty acid having 12 to 30 carbon atoms (see Patent Document 5). Proposed. In these techniques, although the effect of suppressing the generation of die lines can be obtained, the effect of preventing the occurrence of eye grease due to long-time operation in the film production machine is poor, and there is a problem in practical use. Also, in these documents, there is no description about the effect of preventing breakage during film stretching, there are few breaks during film stretching, continuous stable film formation is possible for a long time, and transparency, slipperiness, printability, flexibility At present, polyamide films having excellent properties have not been obtained industrially. In addition, a polyamide resin composition is proposed in which inorganic filler particles surface-treated with organopolysiloxane and inorganic filler particles having a specific surface area of 200 m ² / g or less are blended (see Patent Document 6). A film made of the same polyamide resin composition is excellent in transparency and slipperiness, and is less likely to cause poor appearance due to die lines, eye grease, and voids. However, with higher discharge and higher speed during film forming, there is room for improvement in the effect of preventing breakage during film stretching, and further improvement in continuous productivity is desired.

A polyamide resin composition containing a polyamide resin and silica containing a terminal amino group and a terminal carboxyl group in a quantitative ratio has been proposed (see Patent Documents 7 and 8). The polyamide resin composition has a heat of fusion during film production. A film having excellent stability and good appearance can be produced stably and continuously.

Japanese Patent Publication No.54-4741 Japanese Patent Laid-Open No. 6-179813 Japanese Patent Laid-Open No. 8-73734 JP-A-5-59274 JP 2005-132929 A JP 2006-241439 A JP-A-6-57021 JP-A-6-65499

However, the effect was not satisfactory. One of the characteristics of polyamide resin film is that it is superior in transparency and surface gloss compared to other resin films such as polypropylene and polyethylene, but the film becomes cloudy and transparent due to the crystallinity of polyamide. Inhomogeneity may be a problem. In particular, in the water-cooled tubular method in the film production method, this phenomenon appears remarkably when the polyamide resin is in direct contact with water in a molten state. Conventionally, this problem has been solved by improving the cooling method and using additives, but the improvement effect is insufficient under the molding conditions of high discharge response and high production speed, and further improvement is required. ing.
Furthermore, as described in the examples below, the inorganic filler particles surface-treated with an organopolysiloxane, a polyalkylene glycol and / or an alkylene oxide adduct of a polyhydric alcohol, and a partial ester compound of a fatty acid can be used in combination. It has been found that the sex may be significantly worsened.

The object of the present invention is to maintain the properties inherent to a film made of polyamide resin, have good transparency, have little unevenness, excellent slipperiness, printability, flexibility, hot water resistance, and film An object of the present invention is to obtain a polyamide resin composition for a film having a good continuous productivity with little occurrence of thickness unevenness during film formation and breakage during film stretching.

As a result of intensive studies aimed at developing a polyamide resin composition for a film that solves the above-mentioned problems, the present inventors have surface-treated with an organopolysiloxane for a polyamide resin having a specific end group concentration, And a polyamide film comprising a polyamide resin composition comprising a partial ester compound of an inorganic filler, a polyalkylene glycol and / or an alkylene oxide adduct of a polyhydric alcohol, and a fatty acid, wherein the ratio of the organopolysiloxane treatment amount and the specific surface area is within a specific range Has found that the above problems can be solved, and has reached the present invention.

That is, the present invention relates to 0.01 to 0.5 parts by mass of (A) an inorganic filler and (B) polyalkylene glycol and / or (C) a partial ester compound to 0.01 to 0.100 parts by mass of polyamide resin. A polyamide resin composition for film containing 5 parts by mass,
When the terminal amino group concentration of the polyamide resin is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A] − [B]> 0.2 × 10000 / ((Ηr− (18−x) / 10) × M)
(A) The inorganic filler is an inorganic filler surface-treated with an organopolysiloxane, the specific surface area of the inorganic filler is S (m ² / g), and the treatment amount of the organopolysiloxane per 1 g of the inorganic filler is N (μ Mol / g), N / S (μmol / m ² ) is 0.002 to 0.1,
(B) The polyalkylene glycol is a polyalkylene glycol having a number average molecular weight of 200 to 4,000,
(C) It is related with the polyamide resin composition for films whose partial ester compound is a partial ester compound of the alkylene oxide adduct of a polyhydric alcohol, and a fatty acid.
In the above formula, x = [CH ₂ ] / [NHCO], [CH ₂ ] and [NHCO] are the number of methylene groups, the number of amide groups, and ηr in the polyamide resin, respectively, were measured according to JIS K-6920. Relative viscosity (96% sulfuric acid, polyamide resin concentration 1%, 25 ° C.), M represents the mass per structural repeating unit of the polyamide resin.

The polyamide resin composition of the present invention has good transparency and little unevenness, is excellent in slipperiness, printability, flexibility and hot water resistance, has little thickness unevenness during film formation, Since it prevents the occurrence of breakage, it has the characteristic of excellent continuous productivity.

Hereinafter, the present invention will be described in detail.
The polyamide resin composition for a film of the present invention is
Film containing 0.01 to 0.5 parts by mass of (A) inorganic filler and (B) polyalkylene glycol and / or (C) partial ester compound with respect to 100 parts by mass of polyamide resin A polyamide resin composition for
When the terminal amino group concentration of the polyamide resin is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A] − [B]> 0.2 × 10000 / ((Ηr− (18−x) / 10) × M)
(A) The inorganic filler is an inorganic filler surface-treated with an organopolysiloxane, the specific surface area of the inorganic filler is S (m ² / g), and the treatment amount of the organopolysiloxane per 1 g of the inorganic filler is N (μ Mol / g), N / S (μmol / m ² ) is 0.002 to 0.1,
(B) The polyalkylene glycol is a polyalkylene glycol having a number average molecular weight of 200 to 4,000,
(C) The polyamide resin composition for a film, wherein the partial ester compound is a partial ester compound of an alkylene oxide adduct of a polyhydric alcohol and a fatty acid.
(In the above formula, x = [CH ₂ ] / [NHCO], where [CH ₂ ] and [NHCO] are the number of methylene groups, the number of amide groups, and ηr in the polyamide resin, respectively, were measured according to JIS K-6920. Relative viscosity (96% sulfuric acid, polyamide resin concentration 1%, 25 ° C.), M represents the mass per structural repeating unit of the polyamide resin))

[Polyamide resin]
The polyamide resin is obtained by polymerization or copolymerization using a lactam, aminocarboxylic acid, or nylon salt composed of diamine and dicarboxylic acid as a raw material by a known method such as melt polymerization, solution polymerization or solid phase polymerization.

Examples of the lactam include caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone and the like, and examples of the aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, and 11-aminoundecane. Examples include acid and 12-aminododecanoic acid. These can use 1 type (s) or 2 or more types.

The diamine constituting the nylon salt includes ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, Dodecamethylenediamine, tridecamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, heptadecamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine, 2- / 3-methyl -1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methyl Aliphatic diamines such as -1,9-nonanediamine, 1,3- / 1,4-cyclohexanediamine, 1,3- / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4- Aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, Cycloaliphatic diamines such as 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornanedimethylamine, tricyclodecanedimethylamine, m -/ Aromatic diamines such as p-xylylenediamine And the like. These can use 1 type (s) or 2 or more types.

On the other hand, the dicarboxylic acid constituting the nylon salt includes adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid. Aliphatic dicarboxylic acids such as octadecanedioic acid, eicosanedioic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid And aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, and 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid. These can use 1 type (s) or 2 or more types.

In the polyamide resin, single polymers or copolymers derived from these lactams, aminocarboxylic acids, or nylon salts composed of diamines and dicarboxylic acids can be used alone or in the form of a mixture.
Specific examples of the polyamide resin used include polycaprolactam (polyamide 6), polyundecane lactam (polyamide 11), polydodecane lactam (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene adipamide ( Polyamide 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), polyhexamethylene Dodecamide (polyamide 612), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T ( H)), polynonamethylene adipamide (polyamide 96), polynonamethylene azelamide (polyamide 99), polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polynonamethylene tele Phthalamide (polyamide 9T), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), polydecamethylene adipa Amide (polyamide 106), polydecamethylene azeamide (polyamide 109), polydecamethylene decanamide (polyamide 1010), polydecamemethylene dodecamide (polyamide 1012), polydecamethylene terephthalamide (polyamide 1) T), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polydodecamethylene adipamide (polyamide 126), polydodecamethylene azelamide (polyamide 129), Polydodecamethylene sebacamide (Polyamide 1210), Polydodecamethylene dodecamide (Polyamide 1212), Polydodecamethylene terephthalamide (Polyamide 12T), Polydodecamethylene hexahydroterephthalamide (Polyamide 12T (H)), Polydodeca Methylene naphthalamide (polyamide 12N), polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), Limetaxylylene sebacamide (polyamide MXD10), polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene naphthalamide (polyamide) MXDN), polybis (4-aminocyclohexyl) methane dodecamide (polyamide PACM12), polybis (4-aminocyclohexyl) methane terephthalamide (polyamide PACMT), polybis (4-aminocyclohexyl) methane isophthalamide (polyamide PACM), Polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (polyamide dimethyl PACM12), polyisophorone adipamide (polyamide IPD6), poly Examples include lysophorone terephthalamide (polyamide IPDT) and polyamide copolymers using these raw material monomers. These can use 1 type (s) or 2 or more types. In consideration of heat resistance, mechanical strength, transparency, economy, availability, etc. of the resulting film, polyamide resin is derived from caprolactam (caprolactam unit), hexamethylenediamine and adipic acid. It is preferably a homopolymer or copolymer composed of at least one selected from the group consisting of units (hexamethylene adipamide units) and units derived from dodecane lactam (dodecalactam units). Specifically, polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer (copolymer of polyamide 6 and polyamide 66, hereinafter the copolymer is also described), polyamide 6/69 copolymer Polymer, polyamide 6/610 copolymer, polyamide 6/611 copolymer, polyamide 6/612 copolymer , Polyamide 6/12 copolymer, polyamide 6/66/12 copolymer, polyamide 6 / 6T copolymer, polyamide 6 / 6I copolymer, polyamide 6 / IPD6 copolymer, polyamide 6 / IPDT copolymer A polymer, polyamide 66 / 6T copolymer, polyamide 66 / 6I copolymer, polyamide 6T / 6I copolymer, polyamide 66 / 6T / 6I copolymer, polyamide MXD6, and at least one selected from the group consisting of polyamide MXD6 Polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6 / IPD6 copolymer, polyamide 6 / IPDT copolymer, polyamide 6/66/12 More preferably, it is at least one selected from the group consisting of copolymers. More preferably, it is at least one selected from the group consisting of polyamide 6, polyamide 6/66 copolymer, polyamide 6/12 copolymer, and polyamide 6/66/12 copolymer.

The relative viscosity of the polyamide resin measured according to JIS K-6920 is preferably 2.0 to 5.0, and more preferably 2.5 to 4.5. When the relative viscosity is less than the above value, the mechanical properties of the resulting polyamide film may be lowered. On the other hand, when the above value is exceeded, the viscosity at the time of melting increases, and it may be difficult to form a film.

The polyamide resin used in the present invention is [A] when the terminal amino group concentration per 1 g of the polyamide resin is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g). − [B]> 0.2 × 10000 / ((ηr− (18−x) / 10) × M) is satisfied. In the above formula, x = [CH ₂ ] / [NHCO], [CH ₂ ] and [NHCO] are the number of methylene groups and amide groups in the polyamide resin, and ηr was measured according to JIS K-6920. Relative viscosity (96% sulfuric acid, polyamide resin concentration 1%, 25 ° C.), M represents the mass per structural repeating unit of the polyamide resin. However, ηr> (18−x) / 10.
When the polyamide resin is polycaprolactam (polyamide 6) and polyhexamethylene adipamide (polyamide 66), [CH ₂ ] / [NHCO] = 5 and the mass M per structural repeating unit of the polyamide resin is 113 . In the case of polydodecane lactam (polyamide 12), [CH ₂ ] / [NHCO] = 11, and the mass M per structural repeating unit of the polyamide resin is 197. In the case of caproamide / hexamethylene adipamide copolymer (polyamide 6/66 copolymer), [CH ₂ ] / [NHCO] = 5 regardless of the polymerization mass ratio and molar ratio of the constitutional repeating units, and the polyamide The mass M per structural repeating unit of the resin is 113. In the case of caproamide / dodecanlacactam copolymer (polyamide 6/12 copolymer), the mass M per structural repeating unit of [CH ₂ ] / [NHCO] or polyamide resin depending on the polymerization mass ratio and molar ratio of the structural repeating units. For example, in the case of a polyamide 6/12 copolymer having a polymerization mass ratio of 80:20, [CH ₂ ] / [NHCO] = 5.75, and the mass M per structural repeating unit of the polyamide resin is 123. 5. Thus, if [CH ₂ ] / [NHCO], the mass M per structural repeating unit of the polyamide resin, and the relative viscosity are known, the conditions for the terminal amino group concentration and terminal carboxyl group concentration can be calculated from the above formula. It becomes.
Furthermore, the polyamide resin is 0.3 × 10000 / ((ηr− (18−x) / 10) × M) <[A] − [B] <1.5 × 10000 / ((ηr− (18−x ) / 10) × M), preferably 0.4 × 10000 / ((ηr− (18−x) / 10) × M) <[A] − [B] <1.4 × 10000 / ( It is more preferable to satisfy (ηr− (18−x) / 10) × M). When [A]-[B] is less than the above value, the effect of improving transparency and the unevenness thereof become large, and the hot water resistance is poor. On the other hand, when the above value is exceeded, it may be difficult to produce the polyamide resin itself.

The terminal amino group concentration [A] (μeq / g) can be measured by dissolving the polyamide in a phenol / methanol mixed solution and titrating with 0.05N hydrochloric acid. The terminal carboxyl group concentration [B] (μeq / g) can be measured by dissolving the polyamide in benzyl alcohol and titrating with 0.05N sodium hydroxide solution.

The polyamide resin is produced by polymerizing or copolymerizing the polyamide resin raw material in the presence of amines by a known method such as melt polymerization, solution polymerization or solid phase polymerization. Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. Thus, amines can be added at any stage during polymerization or at any stage during melt kneading after polymerization, but in the stage during polymerization when considering the melt stability during film formation. It is preferable to add.

Examples of the amines include monoamines, diamines, and polyamines. In addition to amines, carboxylic acids such as monocarboxylic acids and dicarboxylic acids may be added as necessary as long as they do not deviate from the range of the above-mentioned end group concentration conditions. These amines and carboxylic acids may be added simultaneously or separately. Moreover, 1 type (s) or 2 or more types can be used for the amines and carboxylic acids illustrated below.

Specific examples of the monoamine to be added include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine , Aliphatic monoamines such as tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, octadecyleneamine, eicosylamine, docosylamine, alicyclic monoamines such as cyclohexylamine, methylcyclohexylamine, benzylamine, β- Aromatic monoamines such as phenylmethylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, N, N-dihexyl Symmetrical secondary amines such as amine, N, N-dioctylamine, N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine, N -Hybrid secondary amines such as -ethyl-N-hexadecylamine, N-ethyl-N-octadecylamine, N-propyl-N-hexadecylamine, N-propyl-N-benzylamine and the like.

Specific examples of the diamine to be added include ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene. Diamine, Tridecamethylenediamine, Tetradecamethylenediamine, Pentadecamethylenediamine, Hexadecamethylenediamine, Heptadecamethylenediamine, Octadecamethylenediamine, Nonadecamethylenediamine, Eicosamethylenediamine, 2- / 3-methyl-1 , 5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4- / 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1 Aliphatic diamines such as 9-nonanediamine, 1,3- / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) ) Methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, Examples thereof include alicyclic diamines such as bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylamine, and tricyclodecanedimethylamine, and aromatic diamines such as m− / p-xylylenediamine.

The polyamine to be added may be a compound having a plurality of primary amino groups (—NH ₂ ) and / or secondary amino groups (—NH—). For example, polyalkyleneimine, polyalkylenepolyamine, polyvinylamine, polyallylamine, etc. Is mentioned. The amino group with active hydrogen is the reaction point of the polyamine.

The polyalkyleneimine is produced by a method of ionic polymerization of an alkyleneimine such as ethyleneimine or propyleneimine, or a method of polymerizing an alkyloxazoline and then partially hydrolyzing or completely hydrolyzing the polymer. Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, pentaethylenehexamine, or a reaction product of ethylenediamine and a polyfunctional compound. Polyvinylamine can be obtained, for example, by polymerizing N-vinylformamide to poly (N-vinylformamide), and then partially or completely hydrolyzing the polymer with an acid such as hydrochloric acid. Polyallylamine is generally obtained by polymerizing a hydrochloride of an allylamine monomer and then removing hydrochloric acid. These can use 1 type (s) or 2 or more types. Among these, polyalkyleneimine is preferable.

Examples of the polyalkyleneimine include one or more kinds of alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. The homopolymer and copolymer obtained by superposing | polymerizing by a conventional method are mentioned. Among these, polyethyleneimine is more preferable. A polyalkyleneimine is obtained by polymerizing an alkyleneimine as a raw material and using a branched polyalkyleneimine containing a primary amine, a secondary amine or a tertiary amine obtained by ring-opening polymerization of the alkyleneimine or an alkyloxazoline as a raw material. Either a linear polyalkyleneimine containing only a primary amine and a secondary amine obtained in this manner, or a three-dimensionally crosslinked structure may be used. Furthermore, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine, and the like may be included. A polyalkyleneimine is usually derived from the reactivity of an active hydrogen atom on a nitrogen atom contained therein, and in addition to a tertiary amino group, a primary amino group having an active hydrogen atom or a secondary amino group (imino Group).

The number of nitrogen atoms in the polyalkyleneimine is not particularly limited, but is preferably 4 to 3,000, more preferably 8 to 1,500, and still more preferably 11 to 500. The number average molecular weight of the polyalkyleneimine is preferably from 100 to 20,000, more preferably from 200 to 10,000, and further preferably from 500 to 8,000.

On the other hand, as carboxylic acids to be added, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristic acid, Aliphatic monocarboxylic acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, erucic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, methylcyclohexanecarboxylic acid, benzoic acid, toluic acid , Aromatic monocarboxylic acids such as ethylbenzoic acid, phenylacetic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid , Hexadecenedioic acid, octadecadioic acid, octadecenedioic acid, ray Sandioic acid, eicosenedioic acid, docosandioic acid, diglycolic acid, aliphatic dicarboxylic acids such as 2,2,4- / 2,4,4-trimethyladipic acid, 1,4-cyclohexanedicarboxylic acid, norbornane dicarboxylic acid Aromatic dicarboxylic acids such as alicyclic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, m- / p-xylylene dicarboxylic acid, 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid Is mentioned.

The amount of amines to be added is appropriately determined by a known method in consideration of the terminal amino group concentration, terminal carboxyl group concentration and relative viscosity of the polyamide resin to be produced. Usually, the addition amount of amines is preferably 0.5 to 20 meq / mol, and 1.0 to 10 meq / mol with respect to 1 mol of the polyamide raw material (monomer constituting the repeating unit or 1 mol of monomer unit) (Equivalent (eq) of amino group is defined as 1 equivalent of the amount of amino group that reacts 1: 1 with a carboxyl group to form an amide group). When the addition amount is less than the above value, sufficient reactivity may not be obtained, while when it exceeds the above value, it may be difficult to produce a polyamide resin having a desired viscosity.

Further, the terminal amino group concentration [A] (μeq / g) of the polyamide resin preferably satisfies [A]> 1.1 × 10000 / ((ηr− (18−x) / 10) × M), It is more preferable to satisfy [A]> 1.15 × 10000 / ((ηr− (18−x) / 10) × M), and 1.2 × 10000 / ((ηr− (18−x) / 10). It is more preferable to satisfy (M) <[A] <2.0 × 10000 / ((ηr− (18−x) / 10) × M). When the terminal amino group concentration [A] is less than the above value, the effect of improving transparency and the unevenness thereof are increased, and the hot water resistance may be inferior. On the other hand, when the above range is exceeded, problems in the production of the polyamide resin itself tend to occur.

In the polyamide resin, in order to satisfy the condition of the terminal group concentration, it is preferable to add a diamine among the above-exemplified amines, and at the same time reducing the terminal carboxyl group concentration with a relatively small amount of diamine, The base concentration can be increased. When monoamines are added, the terminal carboxyl group concentration can be reduced, and [A]-[B]> 0.2 × 10000 / ((ηr− (18−x) / 10) × M) is satisfied. However, since the terminal amino group concentration does not increase, [A]> 1.1 × 10000 / ((ηr− (18−x) / 10) × M) cannot be satisfied. Furthermore, in order to satisfy [A]-[B]> 0.2 × 10000 / ((ηr− (18−x) / 10) × M), it is necessary to increase the amount of monoamines added, and as a result, This is not preferable because it causes a decrease in polymerization rate.
Therefore, it is preferable to add diamine and / or polyamine at the time of polymerization in order to satisfy the above-mentioned end group concentration without lowering the productivity at the time of polyamide resin production. It is more preferable to add at least one selected from the group consisting of alicyclic diamine and polyamine.

Further, the polyamide resin may be a mixture of two or more types of polyamide resins having different end group concentrations as long as the above end group concentration is satisfied. In this case, the terminal amino group concentration and the terminal group carboxyl concentration of the polyamide resin mixture are determined by the terminal amino group concentration, the terminal carboxyl group concentration and the blending ratio of the polyamide resin constituting the mixture.

For the polyamide resin, the amount of water extraction measured according to the method for measuring the content of low molecular weight substances specified in JIS K-6920 is preferably 1.0% or less, and preferably 0.5% or less. It is more preferable. When the amount of water extraction exceeds the above value, the oligomer component is remarkably attached to the vicinity of the die, and appearance defects are liable to occur due to the generation of die lines and fish eyes caused by these attachments. Furthermore, the polyamide resin has a higher hygroscopicity than the olefin resin, and if a hygroscopic material is used, an oligomer is generated when the raw material is melt-extruded, resulting in difficulty in film production. It is preferable that the moisture content is 0.1% by mass or less after drying.

[(A) inorganic filler]
The inorganic filler (A) used in the present invention is an inorganic filler surface-treated with an organopolysiloxane, and the specific surface area of the inorganic filler is S (m ² / g), per 1 g of the inorganic filler not surface-treated. N / S (μmol / m ² ) is 0.002 to 0.1, where N (μmol / g) is the amount of the organopolysiloxane treated.
The shape of the inorganic filler is not particularly limited as long as a surface projection is formed on the surface and a polyamide film excellent in slipperiness is obtained. The shape of the inorganic filler is powder, particulate, flake, plate, fiber, needle. , Cross, mat, or any other shape, but particles and plates are preferred. The average particle size of the inorganic filler is preferably 0.1 to 20 μm, and more preferably 0.5 to 15 μm. When the average particle size exceeds the above value, a fish eye gel may be generated to impair the film appearance, or even if the effect of improving slipperiness is exhibited, the transparency of the film may be deteriorated. On the other hand, if it is less than the above value, secondary agglomeration is likely to occur, and conversely, even if a fish eye gel occurs, or even if aggregation can be prevented, it is difficult to obtain the uneven effect on the film surface, and slipperiness is reduced. It may not be improved. Therefore, when the particle size of the inorganic filler does not match the above range, it is desirable to perform pulverization or classification in advance.

Specific examples of the inorganic filler include silica such as gel type silica, precipitated type silica, spherical silica, talc, kaolin, montmorillonite, zeolite, mica, glass flake, wollastonite, potassium titanate, magnesium sulfate, sepiolite, zonolite, boron. Examples thereof include aluminum oxide, glass beads, calcium silicate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, and magnesium hydroxide. These can use 1 type (s) or 2 or more types. Among these, talc, kaolin, zeolite, and silica are preferable from the viewpoint of easy dispersibility.

In particular, silica is more preferable from the viewpoints of transparency and slipperiness of the obtained film. Silica is mainly composed of silicon dioxide represented by SiO ₂ · nH ₂ O, and is roughly classified into two types, that is, wet method silica and dry method silica, depending on the production method. it can. Dry silica is generally made by flame hydrolysis. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane and trichlorosilane may be used alone or silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state. On the other hand, wet method silica is further classified into precipitation method silica, gel method silica, and sol method silica according to the production method. Precipitated silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the silica on which particles have grown is agglomerated and settled, and is then commercialized through filtration, water washing, drying, pulverization and classification. The secondary particles of silica produced by this method become loose agglomerated particles, and particles that are relatively easy to grind are obtained. Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. During the ripening, the fine particles dissolve and reprecipitate so as to bind other primary particles, so that the distinct primary particles disappear and form relatively hard aggregated particles having an internal void structure. The sol method silica is also called colloidal silica, and is obtained by heating and aging a silica sol obtained through metathesis of sodium silicate acid or the like through an ion exchange resin layer.

The average particle diameter of silica is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and even more preferably 1 to 10 μm. When the average particle size is less than the above value, it tends to be difficult to express blocking resistance as the polyamide resin composition. On the other hand, when it exceeds the above value, fish eyes tend to occur in a film or the like. .

(A) The organopolysiloxane used as a surface treatment agent for an inorganic filler is represented by the following formula (I).

In formula (I), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an organic group. Although it does not specifically limit as said organic group, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylbutyl group, octyl group etc. Alkyl group, phenyl group, tolyl group, xylyl group, naphthyl group, aryl group of diphenyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, cycloalkyl group such as cyclohexyl group, cyclopentyl group, Hydrocarbon groups in which some or all of the hydrogen atoms in these groups are substituted with halogen atoms, substituted or unsubstituted hydroxyl groups, siloxy groups, alkoxy groups, alkoxycarbonyl groups, carboxyl groups, mercapto groups, epoxy groups, (meta ) acryloxy group, an amino _{group, -O -, - (CH 2} O) n -, - (OCH 2) n —, — (CH ₂ O) _n CH ₂ — and other structural units containing an ether bond site, —CO—, —COCO—, —CO (CH ₂ ) _n CO—, —CO (C ₆ H ₄ ) CO— Examples thereof include a structural unit containing a carbonyl group, a structural unit containing an amide bond site, an ester bond site, a substituent containing a structural unit containing a ketone bond site, and the like.
Among these, R ^{1 to} R ⁴ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group from the viewpoints of stability during production or use, and safety and health. 10 to 10 alkyl groups, aryl groups, and aralkyl groups are more preferable, alkyl groups having 1 to 6 carbon atoms or aryl groups are more preferable, and methyl groups are particularly preferable.

Examples of the organopolysiloxane include dimethylpolysiloxane, methyl hydrogen polysiloxane, methylphenyl polysiloxane, and various modified polysiloxanes. Various modified polysiloxanes include silanol-modified polysiloxanes with silanol groups introduced at both ends of the polysiloxane skeleton, fluorine-modified polysiloxanes with fluoroalkyl groups introduced into the side chains of the polysiloxane skeleton, and side chains of the polysiloxane skeleton. Alkyl-modified polysiloxanes with long-chain alkyl groups introduced into them, aralkyl-modified polysiloxanes with aralkyl groups introduced into the side chains of the polysiloxane skeleton, and fatty acid ester modifications with higher fatty acid ester groups introduced into the side chains of the polysiloxane skeleton Polysiloxane, a fatty acid amide-modified polysiloxane having a higher fatty acid amide group introduced into the side chain of the polysiloxane skeleton, a polyether having a polyether group such as polyethylene oxide or polypropylene oxide introduced at both ends or side chains of the polysiloxane skeleton Strange Both polysiloxane, amino-modified polysiloxane with amino groups introduced at both ends or side chains of the polysiloxane skeleton, epoxy-modified polysiloxane with epoxy groups introduced at both ends or side chains of the polysiloxane skeleton, and both polysiloxane skeletons Epoxy-polyether-modified polysiloxane having an epoxy group and a polyether group introduced at the terminal or side chain, phenol-modified polysiloxane having a phenolic hydroxyl group introduced at both ends of the polysiloxane skeleton, or both ends or sides of the polysiloxane skeleton Carboxyl-modified polysiloxane with a carboxyl group introduced into the chain, (meth) acrylate-modified polysiloxane with a (meth) acryl group introduced at both ends of the polysiloxane skeleton, and an alkoxy group introduced at both ends of the polysiloxane skeleton Alkoxy modified poly Siloxane, carbinol-modified polysiloxane carbinol group introduced into both terminals or side chains of the polysiloxane backbone, mercapto-modified polysiloxane which mercapto group is introduced at both ends or side chains of the polysiloxane skeleton. These can use 1 type (s) or 2 or more types. Among these, dimethylpolysiloxane, methyl hydrogen polysiloxane and / or methylphenyl polysiloxane are preferable, and dimethylpolysiloxane is more preferable.

In the general formula (I), m and n are natural numbers, and the total number of m and n (m + n) is preferably 5 to 500, more preferably 10 to 300, and more preferably 20 to 200. More preferably. The ratio of m to n (n / m) is determined by the type and content of the organic group to be introduced in consideration of the affinity between the polyamide resin to be used and the inorganic filler, and is preferably 1/100 to 10 1/50 to 5 is more preferable.
Furthermore, the organopolysiloxane preferably has a dynamic viscosity at 25 ° C. of 5 to 1,000 cSt, and more preferably 8 to 600 cSt. If the dynamic viscosity is less than the above value, the flash point may be lowered and the material may be easily decomposed, so that it may be difficult to process at a high temperature. On the other hand, when the above value is exceeded, the surface of the inorganic filler cannot be uniformly treated, and coarse aggregated particles are likely to be generated.

The addition amount of the organopolysiloxane is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass with respect to 100 parts by mass of the inorganic filler, and 2 to 10 parts by mass. Is more preferable. When the addition amount of the organopolysiloxane is less than the above value, the stretch breakage preventing effect is small, and the continuous productivity may not be good. On the other hand, when the above value is exceeded, the affinity between the polyamide resin and the inorganic filler is not sufficient, the dispersibility is deteriorated, and the mechanical properties of the finally obtained polyamide film are impaired. Problems such as bleeding out to the film may occur.

Preferably the specific surface area S of the inorganic filler is 50~1000m ² / g, more preferably 100~800m ² / g, more preferably in a 150~500m ² / g, 200~400m ² / Particularly preferred is g. When the specific surface area is less than the above value, the effect of the surface treatment with the surface treatment agent tends to be difficult to be exhibited. On the other hand, when the specific surface area is exceeded, the surface treatment agent is impregnated into the secondary and tertiary particles. It becomes difficult, and a free surface treating agent is present in the polyamide resin composition, which tends to adversely affect the appearance and physical properties of the film. The specific surface area means a value measured by the BET method.

(A) N / S (μmol / m ² ) of the inorganic filler is 0.002 to 0.1, preferably 0.003 to 0.08, and preferably 0.005 to 0.07. It is more preferable. When N / S is less than the above value, the effect of preventing stretch breakage is small and the continuous productivity is not good. On the other hand, when the value exceeds the above value, a free surface treatment agent is present in the polyamide resin composition. Thus, since it is incompatible with the later-described (B) polyalkylene glycol and / or (C) partial ester compound, the transparency of the film is adversely affected.

The method of treating the inorganic filler with the organopolysiloxane is not particularly limited, but the inorganic filler and the organopolysiloxane are added to the solvent and mixed uniformly using a high shear mixer such as a Henschel mixer or a super mixer, and then the solvent. When the inorganic filler is pulverized with a fluid energy pulverizer such as a micronizer, jet mill or Henschel mixer, the organopolysiloxane is added and stirred to be uniform. Then, a dry processing method in which drying is performed at a predetermined temperature and the like can be mentioned. As the fluid, compressed air, heated compressed air, steam or the like is usually used.

In particular, after the surface treatment or during the treatment, by heating and drying the inorganic filler, the hydrophobic surface becomes stronger, so that the water content due to moisture adsorption or the like is greatly reduced. The inorganic filler (A) having a low water content thus obtained has various advantages such as an increase in dispersion force and dispersion time because resin deterioration is suppressed during kneading and dispersion in the resin.

(A) The compounding quantity of an inorganic filler is 0.01-0.5 mass part with respect to 100 mass parts of polyamide resins, It is preferable that it is 0.03-0.3 mass part, 0.05-0 More preferably, it is 2 parts by mass. If the blending amount is less than the above value, the effect of improving the slipperiness of the resulting film is small, whereas if it exceeds the above value, the transparency, appearance, etc. of the polyamide film are impaired.

[(B) polyalkylene glycol]
The (B) polyalkylene glycol used in the present invention is an ether polymer composed of units derived from alkylene glycol. The polyalkylene glycol is preferably a polymer of alkylene glycol having 2 to 6 carbon atoms, such as polyethylene glycol, poly (1,2- or 1,3-propylene) glycol, polytetramethylene glycol, polyhexamethylene glycol, etc. Is mentioned. These units derived from alkylene glycols may be copolymerized in blocks or randomly. Examples thereof include a polyethylene glycol / propylene glycol polymer and a polyethylene glycol / tetramethylene glycol polymer. These can use 1 type (s) or 2 or more types.

(B) The number average molecular weight of the polyalkylene glycol is 200 to 4,000, preferably 300 to 2,000, and more preferably 300 to 1,000. If the number average molecular weight is less than the above value, the effect as a softening agent is great, but the bleed-out property to the surface after film formation is high, and the adhesiveness when a laminated film is formed by coextrusion or lamination is poor. On the other hand, if the above value is exceeded, the effect as a flexibility-imparting agent is not sufficient. Here, the “number average molecular weight” is calculated from a terminal OH quantitative method based on JIS K-1557-1.

[(C) Partial ester compound]
The (C) partial ester compound used in the present invention is a partial ester compound of an alkylene oxide adduct of a polyhydric alcohol and a fatty acid.
(C) As the polyhydric alcohol constituting the ester compound, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3- / 1,4-butanediol, 2-methyl-1, 3-propanediol, 1,2- / 1,3- / 1,4- / 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3- Propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonane Diol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecane All, glycerin, diglycerin, triglycerin, tetraglycerin, polyglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tri- (trimethylolpropane), trimethylolbutane, erythritol, pentaerythritol, dipentaerythritol, tri Pentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitan, isosorbide, sorbitol, adonitol, Arabitol, xylitol, mannitol, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, Somarutosu, trehalose, sucrose, raffinose, gentianose, melezitose, and the like. These can use 1 type (s) or 2 or more types.

(C) As alkylene oxide which comprises a partial ester compound, ethylene oxide, propylene oxide, tetraethylene oxide, etc. are mentioned. These can use 1 type (s) or 2 or more types. These alkylene oxides may be used alone or may be block or randomly copolymerized. Among these, ethylene oxide, propylene oxide, and copolymers thereof are preferable. The number of added moles of alkylene oxide is not particularly limited, but is preferably 0.1 to 60 moles, and more preferably 0.5 to 50 moles.

(C) As a fatty acid which comprises a partial ester compound, a C6-C30 fatty acid is preferable and may be a saturated and unsaturated fatty acid. Further, it may be a structure containing either a straight chain or a branched chain. Specifically, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, erucic acid, Examples include serotic acid, montanic acid, and melissic acid. These can use 1 type (s) or 2 or more types.

In the partial ester compound (C), when the basic structure of the polyhydric alcohol and the alkylene oxide adduct is the same, the partial ester compound of the polyhydric alcohol alkylene oxide adduct, the polyalkylene glycol, and the fatty acid It becomes the same compound as the partial ester compound, and the partial ester compound of polyalkylene glycol and fatty acid is also included in (C) the partial ester compound.

The polyalkylene glycol constituting the partial ester compound of polyalkylene glycol and fatty acid is a polymer composed of units derived from alkylene glycol having 2 to 6 carbon atoms from the viewpoint of availability and safety and health. Preferably, a polymer composed of units derived from an alkylene glycol having 2 to 3 carbon atoms is more preferable. For example, polyethylene glycol, poly (1,2- or 1,3-propylene) glycol, polytetramethylene glycol, Examples include polyhexamethylene glycol. These units derived from alkylene glycols may be copolymerized in a block or random manner, and examples thereof include polyethylene glycol / propylene glycol polymers and polyethylene glycol / tetramethylene glycol polymers. These can use 1 type (s) or 2 or more types. The number average molecular weight of the alkylene glycol is preferably 200 to 4,000, more preferably 300 to 3,000, and further preferably 300 to 2,000. If the number average molecular weight of the alkylene glycol is less than the above value, not only the flexibility is not improved, but also the bleed out may not be suppressed. On the other hand, when the above value is exceeded, not only the transparency of the film is lowered, but also adhesiveness and printability may be deteriorated when a laminated film is formed by coextrusion or lamination.

(C) The partial ester compound needs to be substantially a partial ester, and it is preferable that 30% or more of the total hydroxyl groups in the compound remain without being esterified, and 50% or more do not esterify. More preferably, it remains in That is, the esterification rate of the (C) partial ester is preferably less than 70%, and more preferably less than 50%. As long as the ratio of the hydroxyl groups is satisfied, a mixture of two or more (C) partial ester compounds having different hydroxyl ratios may be used. In this case, the ratio of the hydroxyl group in the (C) partial ester compound mixture is determined by the ratio and the compounding ratio of the hydroxyl group of the compound constituting the mixture.
(C) When the ratio of the hydroxyl group in a partial ester compound exceeds the said value, it may become easy to bleed. On the other hand, when it is less than the above value, the hydrophilicity is lowered and the compatibility with the polyamide resin may be deteriorated.

(C) A partial ester compound can be obtained by performing a conventionally known esterification reaction and alkylene oxide addition reaction. For example, an esterification catalyst is added to a mixture of a fatty acid and a polyhydric alcohol, and an ester compound is obtained by reacting at 150 to 250 ° C. Further, an alkylene oxide is added in the presence of an alkali catalyst or the like. An adduct is obtained. Moreover, you may esterify after adding an alkylene oxide to a fatty acid or a polyhydric alcohol. Further, it may be obtained only by adding an alkylene oxide to a fatty acid.

(C) As the partial ester compound, polyoxyethylene fatty acid partial ester, polyoxypropylene fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester, polyoxypropylene glycerin fatty acid partial ester, polyoxyethylene pentaerythritol fatty acid partial ester, poly Oxyethylene sorbitan fatty acid partial esters and polyoxyethylene sorbitol fatty acid partial esters are preferred because they have a large stretch-improving effect, little inhibition of transparency, and high safety.

Specific examples of the partial ester compound (C) include polyoxyethylene fatty acid partial esters such as polyethylene glycol monolaurate, polyethylene glycol monopalmitate, polyethylene glycol monostearate, polyethylene glycol monooleate, and polyethylene glycol monobehenate. Polyoxypropylene fatty acid partial esters such as polypropylene glycol monolaurate, polypropylene glycol monopalmitate, polypropylene glycol monostearate, polypropylene glycol monooleate, polypropylene glycol monobehenate, polyoxyethylene glycerol monolaurate, polyoxyethylene glycerol Monomyristate, polyoxyethylene glycerin monopalmitate, polyoxy Ethylene glycerol monostearate, polyoxyethylene glycerol monooleate, polyoxyethylene glycerol monobenate, polyoxyethylene glycerol dilaurate, polyoxyethylene glycerol dimyristate, polyoxyethylene glycerol dipalmitate, polyoxyethylene glycerol distearate Polyoxyethylene glycerol fatty acid partial ester such as polyoxyethylene glycerol dioleate, polyoxyethylene glycerol dibehenate, polyoxypropylene glycerol monolaurate, polyoxypropylene glycerol monomyristate, polyoxypropylene glycerol monopalmitate , Polyoxypropylene glycerol monostearate, polyoxypropylene glycerol monooleate , Polyoxypropylene glycerin fatty acid partial ester such as polyoxypropylene glyceryl monobenate, polyoxyethylene pentaerythritol monolaurate, polyoxyethylene pentaerythritol monomyristate, polyoxyethylene pentaerythritol monopalmitate, polyoxyethylene pentaerythritol Monostearate, polyoxyethylene pentaerythritol monooleate, polyoxyethylene pentaerythritol monobehenate, polyoxyethylene pentaerythritol dilaurate, polyoxyethylene pentaerythritol dimyristate, polyoxyethylene pentaerythritol dipalmitate, polyoxyethylene Pentaerythritol distearate, polyoxyethylene pen Taerythritol dioleate, polyoxyethylene pentaerythritol fatty acid partial ester such as polyoxyethylene pentaerythritol dibehenate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monomyristate, polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monobehenate, polyoxyethylene sorbitan dilaurate, polyoxyethylene sorbitan dimyristate, polyoxyethylene sorbitan dipalmitate, polyoxyethylene sorbitan Distearate, polyoxyethylene sorbitan dioleate, polyoxyethylene sorbitan dibenate Polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monomyristate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, poly Oxyethylene sorbitol monobehenate, polyoxyethylene sorbitol dilaurate, polyoxyethylene sorbitol dimyristate, polyoxyethylene sorbitol dipalmitate, polyoxyethylene sorbitol distearate, polyoxyethylene sorbitol dioleate, polyoxyethylene sorbitol dibeate Henate, polyoxyethylene sorbitol trilaurate, polyoxyethylene Sorbitol trimyristate, polyoxyethylene sorbitol tripalmitate, polyoxyethylene sorbitol tristearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tribehenate, polyoxyethylene sorbitol tetralaurate, polyoxyethylene sorbitol tetra Examples include polyoxyethylene sorbitol fatty acid partial esters such as myristate, polyoxyethylene sorbitol tetrapalmitate, polyoxyethylene sorbitol tetrastearate, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene sorbitol tetrabenate. These can use 1 type (s) or 2 or more types.

(B) The compounding quantity of polyalkylene glycol and / or (C) partial ester compound is 0.01-0.5 mass part with respect to 100 mass parts of polyamide resins, and is 0.03-0.3 mass part. It is preferable that it is 0.05 to 0.2 parts by mass. If the blending amount is less than the above value, the effect of the resulting film on flexibility, film thickness unevenness prevention and stretchability improvement is small. On the other hand, if the blending amount exceeds the above value, the amount of bleed out to the surface of the polyamide film Increases, and printability and laminating properties are impaired.
When (B) polyalkylene glycol and (C) partial ester compound are used in combination, considering the balance performance such as flexibility and printability of the resulting film, blending of (B) polyalkylene glycol and (C) partial ester compound The ratio is preferably (B) / (C) = 80/20 to 20/80 (mass ratio), more preferably 70/30 to 30/70 (mass ratio), and 60/40 to More preferably, it is 40/60 (mass ratio).

As a method for adding (A) inorganic filler, (B) polyalkylene glycol, and (C) partial ester compound to the polyamide resin, a polymerization internal addition method in which the polyamide resin is added at any stage of the polymerization step or a high concentration in advance. (A) Inorganic filler, (B) polyalkylene glycol, and (C) partial ester compound are kneaded into a polyamide resin using a single-screw or twin-screw extruder, and this is used after being diluted during molding. Master batch method, kneading method in which (A) inorganic filler, (B) polyalkylene glycol, and (C) partial ester compound are kneaded into polyamide resin in advance at the concentration of additives used for molding, polyamide resin during molding In addition, a predetermined amount of (A) inorganic filler, (B) polyalkylene glycol, (C) a partial ester compound is added. Examples include the iblend method, a method in which (B) polyalkylene glycol and (C) a multipart ester compound dissolved in an organic solvent such as alcohol are attached to a polyamide resin by spraying or dipping, and then the organic solvent is evaporated. It is done. In addition, since (B) polyalkylene glycol and (C) partial ester compound may be solid at room temperature, the polyamide resin is heated in advance to the melting point of (B) polyalkylene glycol or (C) partial ester compound. Alternatively, it is possible to add the (B) polyalkylene glycol and the (C) partial ester compound to the polyamide resin in this state as a solid, melt it with the heat of the raw material, and adhere it as it is.
The blending of (A) inorganic filler, (B) polyalkylene glycol, and (C) partial ester compound into the polyamide resin may be performed simultaneously or separately by different methods.

[(D) Inorganic filler]
In the present invention, (A) an inorganic filler other than the inorganic filler (D), that is, an inorganic filler not surface-treated with an organopolysiloxane, and having a specific surface area S of 200 m ² / g or less. Mixing is preferred from the viewpoint of improving slipperiness. (D) As an inorganic filler, although it can illustrate similarly to the above, it is more preferable that it is at least 1 type chosen from the group which consists of a silica, a kaolin, and a zeolite. The specific surface area S of the (D) inorganic filler is preferably not more than 200 meters ² / g, more preferably 180 m ² / g or less, and more preferably not more than 160 m ² / g. When the specific surface area exceeds the above-mentioned value, the generation of voids during stretching and the breakage of stretching are reduced, but it is not preferable because the occurrence of eye grease due to secondary aggregates may occur frequently. The specific surface area means a value measured by the BET method.

(D) As an inorganic filler, what was surface-treated with surface treating agents other than organopolysiloxane, for example, a silane coupling agent, etc. can also be used. Examples of the silane coupling agent generally include alkoxysilane compounds containing an amino group, an epoxy group, a mercapto group, an isocyanato group, a hydroxyl group, or the like. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminodithiopropyltrihydroxysilane, γ- (polyethyleneamino) propyltrimethoxysilane, N-β- (aminopropyl) -γ-aminopropyl Amino group-containing alkoxysilane compounds such as methyldimethoxysilane, N- (trimethoxysilylpropyl) -ethylenediamine, γ-dibutylaminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoe Ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy group-containing alkoxysilane compounds such as silane, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltriethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxy Silane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane Emissions, .gamma.-isocyanatopropyl isocyanato group-containing alkoxysilane compounds such as trichlorosilane, .gamma.-hydroxypropyl trimethoxysilane, hydroxyl group-containing alkoxysilane compounds such as .gamma.-hydroxypropyl triethoxysilane and the like. These can use 1 type (s) or 2 or more types. Among these, amino group-containing alkoxysilane compounds such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane are more preferable. .

Moreover, it is preferable that the addition amount of a silane coupling agent is 1-10 mass% with respect to 100 mass parts of inorganic fillers (dry matter basis), It is more preferable that it is 2-8 mass%, 3-7 More preferably, it is mass%. When the addition amount of the silane coupling agent is less than the above value, the affinity between the inorganic filler and the polyamide resin is not sufficient, and the dispersibility may deteriorate. On the other hand, if the amount exceeds the above value, the effect of improving the dispersibility is hardly increased even if the addition amount is increased, or the mechanical properties of the finally obtained polyamide film are impaired, or the film of the silane coupling agent is used. Problems such as bleeding out may occur.

The method for treating the inorganic filler with the silane coupling agent is not particularly limited. For example, the silane coupling agent or the silane coupling agent solution is added to the inorganic filler by dropping or spraying, and uniformly with a suitable apparatus such as a Henschel mixer. A dry processing method in which the mixture is stirred and then dried at a predetermined temperature, or a wet process in which an inorganic filler is dispersed in water to form a slurry, and a silane coupling agent is added to the slurry while stirring, followed by dehydration and drying. A processing method etc. are mentioned.

(D) The inorganic filler is an inorganic filler other than (A) an inorganic filler and has a specific surface area S of 200 m ² / g or less, and its blending amount is 0 with respect to 100 parts by mass of the polyamide resin. It is preferably 0.01 to 0.2 parts by mass, more preferably 0.03 to 0.18 parts by mass, and even more preferably 0.05 to 0.15 parts by mass. If the blending amount is less than the above, the effect of improving the slipperiness of the resulting film may be small. On the other hand, if it exceeds the above value, the transparency, appearance, etc. of the polyamide film may be impaired. .

In the polyamide resin composition of the present invention, various additives and modifiers that are usually blended within a range that does not impair the properties of the obtained film, for example, heat stabilizer, ultraviolet absorber, light stabilizer, oxidation Antistatic agents, antistatic agents, lubricants, antiblocking agents, fillers, tackifiers, sealability improvers, antifogging agents, crystal nucleating agents, mold release agents, plasticizers, crosslinking agents, foaming agents, colorants (pigments) , Dyes, etc.), a bending fatigue resistance improving material, and the like can be added.

It is preferable to add a hydroxy fatty acid magnesium salt to the polyamide resin composition in order to prevent occurrence of eyelids. Hydroxy fatty acid magnesium salt is a salt of hydroxy saturated or unsaturated fatty acid carboxylic acid and magnesium, specifically, hydroxy lauric acid magnesium salt, hydroxy myristic acid magnesium salt, hydroxy palmitic acid magnesium salt, hydroxy stearic acid magnesium salt, Examples thereof include magnesium hydroxybehenate. These can use 1 type (s) or 2 or more types.

The compounding amount of the hydroxy fatty acid magnesium salt is preferably 0.003 to 0.3 parts by mass, more preferably 0.004 to 0.2 parts by mass with respect to 100 parts by mass of the polyamide resin. More preferably, it is 005-0.1 mass part. When the blending amount of the hydroxy fatty acid magnesium salt is less than the above value, the anti-grease effect may not be seen. On the other hand, when it exceeds the above value, the transparency and printability of the film may be impaired. is there.

Furthermore, the polyamide resin composition is preferably blended with a bisamide compound from the viewpoint of improving transparency and slipperiness. Examples of the bisamide compound include N, N′-methylenebisstearic acid amide, N, N′-ethylene bisstearic acid amide, N, N′-ethylene bisbehenic acid amide, N, N′-dioctadecyl adipic acid amide, and the like. Can be mentioned. These can use 1 type (s) or 2 or more types.

The blending amount of the bisamide compound is preferably 0.01 to 0.5 parts by mass, more preferably 0.02 to 0.3 parts by mass with respect to 100 parts by mass of the polyamide resin. More preferably, it is 0.2 parts by mass. If the amount of the bisamide compound is less than the above value, the effect of improving the transparency and slipperiness of the resulting film may be small. On the other hand, if the amount exceeds the above value, the printability of the film and the adhesion during the lamination process may be small. May decrease.

In the present invention, when the terminal amino group concentration per 1 g of polyamide resin is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A] − [B]> 0 Polyamide resin satisfying .2 × 10000 / ((ηr− (18−x) / 10) × M), (A) inorganic filler, (B) polyalkylene glycol and / or (C) partial ester compound A polyamide film is obtained by applying a known film production method using a composition (hereinafter, sometimes referred to as a raw material polyamide resin composition) and forming a film. For example, a raw material polyamide resin composition is melt-kneaded with an extruder, extruded into a flat film shape with a T-die or a coat hanger die, cast on a casting roll surface, and cooled to produce a film. There is a tubular method for producing a film by air-cooling or water-cooling a tubular material melt-extruded into a cylindrical shape. The produced film can be used as a substantially non-oriented unstretched film, but is preferably a biaxially stretched film from the viewpoint of the strength and gas barrier properties of the obtained film.

Stretching the obtained unstretched film can be performed by a conventionally known industrial method. For example, a film produced by the casting method can be obtained by a simultaneous biaxial stretching method in which an unstretched sheet is stretched simultaneously in the longitudinal and transverse directions by a tenter-type simultaneous biaxial stretching machine, or an unstretched sheet melt-extruded from a T-die in a longitudinal direction by a roll-type stretching machine. Examples thereof include a sequential biaxial stretching method in which the film is stretched and then stretched in the transverse direction with a tenter-type stretching machine, and a tubular stretching method in which a tubular sheet formed from an annular die is stretched simultaneously in the longitudinal and transverse directions by a gas pressure. The stretching step may be carried out continuously following the production of the polyamide film, or the polyamide film may be wound once and then stretched as a separate step.

Although the draw ratio of the stretched film varies depending on the intended use, in the tenter biaxial stretching method and the tubular method, it is usually preferably 1.5 to 4.5 times in both the longitudinal direction and the transverse direction, and 2.5 to It is more preferable that it is 4.0 times. The stretching temperature is preferably 30 to 210 ° C, and more preferably 50 to 200 ° C.

It is desirable that the film stretched by the above method is subsequently heat treated. Dimensional stability at room temperature can be imparted by heat treatment. The heat treatment temperature in this case is preferably selected within a range of 110 ° C. as the lower limit and 5 ° C. lower than the melting point of the raw material polyamide resin composition as the upper limit. A stretched film having a rate can be obtained. Desirably, the stretched film has poor heat shrinkability or substantially does not have it. Therefore, in the heat treatment conditions performed after stretching, the heat treatment temperature is preferably 150 ° C. or higher, more preferably 180 to 220 ° C., and the relaxation rate is preferably within 20% in the width direction. More preferably, it is 10%.
The stretched film that has been sufficiently heat-set by the heat treatment operation can be cooled and wound up according to a conventional method.

Furthermore, the polyamide film can be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, and acid treatment in order to enhance printability, lamination, and adhesive application. Moreover, after performing such a process as needed, it can be used for each intended use through secondary processing steps such as printing, laminating, adhesive application, and heat sealing.

The polyamide film of the present invention is excellent in transparency, slipperiness and printability, and has high utility value by itself, but it is possible to add more characteristics by laminating other thermoplastic resin on it. It is. Specifically, a thermoplastic resin layer can be laminated on at least one side of the polyamide film of the present invention to be used as a laminated film.

In producing the laminated film, another substrate is laminated on one side or both sides of the layer made of the raw material polyamide resin composition. As the lamination method, a co-extrusion method, extrusion lamination method, dry lamination method, etc. Is mentioned. The co-extrusion method is a method of co-extrusion of the raw material polyamide resin composition and another thermoplastic resin, and examples thereof include co-extrusion sheet molding, co-extrusion casting film molding, and co-extrusion inflation film molding. In the extrusion laminating method, the anchor coating agent is applied to the polyamide film of the present invention and a base material such as a thermoplastic resin, respectively, and after drying, the thermoplastic resin is melt-extruded while being cooled and pressed between rolls. In this method, a laminate film is obtained by pressure bonding. In the dry laminating method, a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound is applied to the polyamide film of the present invention, dried, and then laminated to a base material such as a thermoplastic resin. This is a method for obtaining a film. The film after lamination can be increased in adhesive strength by aging. When laminating, it is preferable to use one or both sides of the polyamide film after corona treatment.

The thermoplastic resin to be laminated includes high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene ( PP), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), saponified ethylene / vinyl acetate copolymer (EVOH), ethylene / acrylic Acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer Polyolefin resin such as coalescence (EEA), acrylic acid, meta Rylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2.2.1] -5 Carboxyl groups such as heptene-2,3-dicarboxylic acid and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] Contains functional groups such as acid anhydride groups such as -5-heptene-2,3-dicarboxylic acid anhydride, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. The above-mentioned polyolefin resin, polybutylene terephthalate (PBT), polyethylene Polyester resins such as tarate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), liquid crystal polyester (LCP) Polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO), polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polyphenylene sulfide (PPS) and polythioethersulfone (PTES) Polyketone resins such as thioether resin, polyether ether ketone (PEEK), polyallyl ether ketone (PAEK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene Polynitrile resins such as len copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), polymethacryl Polymethacrylate resins such as methyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / Polyvinyl resins such as vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, cellulose resins such as cellulose acetate and cellulose butyrate, polycarbonate resins such as polycarbonate (PC), thermoplastic polyimide (PI), polyamideimide (P I), polyimide resins such as polyetherimide, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chloro Trifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV) ), Fluororesin such as tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), thermoplastic polyurethane resin, polyurethane elastomer, polyester elastomer, polyamide elastomer, etc. And the like. It is also possible to laminate the polyamide resin defined in the present invention. From the viewpoint of balance of film strength and gas barrier properties, polymetaxylylene adipamide (polyamide MXD6) or saponified ethylene / vinyl acetate copolymer ( EVOH) is preferably laminated.

The obtained polyamide film is preferably provided with a sealant layer from the viewpoint of imparting heat sealability. The material used for the sealant layer may be any resin that can be heat-sealed, and generally includes polyolefin resins, polyester resins, and the like, and it is preferable to use polyolefin resins. Specifically, polypropylene (PP), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic acid copolymer (EAA), ethylene / Methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA), ionomer resin, amorphous Polyester (A-PET) etc. are mentioned as a preferable thing.

Furthermore, non-stretched, uniaxially or biaxially stretched thermoplastic resin film or sheet, or any base material other than thermoplastic resin, for example, paper, metal-based material, woven fabric, non-woven fabric, metal cotton, wood, etc. may be laminated. Is possible. Examples of the metal-based material include aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, cobalt, and other metals and metal compounds, and two or more of these. Examples include alloy steels such as stainless steel, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys.
In particular, in order to improve the gas barrier and water vapor barrier properties, it is also possible to deposit a metal and / or a metal compound. Examples of the material to be deposited include metals such as Si, Al, Ti, Zn, Zr, Mg, Sn, Cu, and Fe, and oxides, nitrides, fluorides, and sulfides thereof. Specifically, inorganic compounds such as SiOx (x = 1.0 to 2.0), alumina, magnesia, zinc sulfide, titania, zirconia, cerium oxide, organic compounds such as HMDSO (hexamethyldisiloxane), Examples thereof include silicon oxide obtained by reaction after mixing an inorganic gas such as silane gas with a carrier gas and oxygen for oxidizing. As a method for producing a vapor deposition film, a known method, a vacuum deposition method as a physical deposition method (PVD method), an EB deposition method, a sputtering method, an ion plating method, or a plasma CVD method as a chemical deposition method (CVD) method is used. Or a chemical reaction method can be used.

The thickness of the polyamide film may be appropriately determined depending on the use, and is not particularly limited. However, if the thickness of the polyamide film is large, the strength of the polyamide film is improved, but transparency and bending fatigue resistance are lowered. In view of the above, in the case of a polyamide single layer film, the thickness is preferably 5 to 100 μm, more preferably 10 to 80 μm, and further preferably 10 to 60 μm. In the case of a laminated film, the thickness of the raw material polyamide resin composition layer is preferably 2 to 100 μm, more preferably 3 to 80 μm, and further preferably 5 to 60 μm.

The polyamide film of the present invention maintains the properties inherent to the polyamide resin, has good transparency, has little unevenness, is excellent in slipperiness, printability, flexibility, and hot water resistance, and further when the film is formed. There are few thickness irregularities and breakage during stretching, and continuous productivity is good. In particular, an inorganic filler surface-treated with an organopolysiloxane, where the specific surface area of the inorganic filler is S (m ² / g), and the treatment amount of the organopolysiloxane per 1 g of the inorganic filler is N (μmol / g). An N / S (μmol / m ² ) 0.002-0.1 inorganic filler and a polyalkylene glycol having a number average molecular weight of 200 to 4,000 and / or an alkylene oxide adduct of a polyhydric alcohol, By using a partial ester compound with a fatty acid in combination, the film has less thickness unevenness while maintaining the transparency and printability of the film, and is excellent in slipperiness, flexibility, hot water resistance, and breakage prevention property during stretching. Therefore, a film with excellent transparency, less unevenness, excellent slipperiness, printability, flexibility, hot water resistance, and less thickness unevenness can be minimized during film-forming operations such as breaking during stretching. And stable production for a long time.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. The measurement methods for polyamide resin properties, various film evaluation methods, and the raw materials used are shown below.

[Relative viscosity]
According to JIS K-6920, the measurement was performed in 96% sulfuric acid under the conditions of a polyamide concentration of 1% and a temperature of 25 ° C.

[Terminal carboxyl group concentration]
A predetermined amount of polyamide sample is placed in a three-neck pear-shaped flask, 40 mL of benzyl alcohol is added, and then immersed in an oil bath set at 180 ° C. under a nitrogen stream. The mixture was stirred and dissolved by a stirring motor attached to the upper part, and titrated with 0.05N sodium hydroxide solution using phenolphthalein as an indicator to determine the terminal carboxyl group concentration.

[Terminal amino group concentration]
Put a predetermined amount of polyamide sample in a conical flask with a stopcock, add 40 mL of a pre-adjusted solvent phenol / methanol (volume ratio 9/1), stir and dissolve with a magnetic stirrer, and use thymol blue as an indicator Then, titration with 0.05N hydrochloric acid was performed to determine the terminal amino group concentration.

[transparency]
According to ASTM D-1003, the haze was measured using a direct reading haze computer (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP). When the haze value was 3.0% or less, it was judged that the transparency of the film was excellent.

[Uneven transparency]
Using the raw resin composition, in a 40 mmφ extruder equipped with a circular die, it is melted at an extrusion temperature of 260 ° C. and cooled with 35 ° C. water so that a transparent non-uniformity is likely to occur. The film was taken out and unstretched films were continuously produced under a blow-up ratio of 1.0. Sampling the unstretched film 1 hour after the start of film formation, cutting the edge, and measuring haze using a direct reading haze computer (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.) according to ASTM D-1003. did. The measurement was performed at 20 points, and the average value and standard deviation were calculated. When the standard deviation was 2.0% or less, it was judged that there was little unevenness in transparency.

[Sliding]
According to ASTM D-1894, the dynamic friction coefficient between the film surfaces was measured at 23 ° C. and relative humidity (RH) 50%. The measurement was performed 5 times, and the average value was obtained. When the dynamic friction coefficient was 0.4 or less, it was judged that the slipperiness of the film was excellent.

[Printability]
The wetting index was measured according to JIS K-6768. When the wetting index was 36 mN / m or more, it was judged that the printability was excellent.

[Flexibility]
Using an automatic dynamic viscoelasticity measuring device (ARES-2000, manufactured by Rheometric Scientific), the elasticity of the film was evaluated for elastic modulus (E ′) around room temperature (23 ° C.). In addition, it shows that a softness | flexibility is so high that the value of E 'is low.

[Uneven film thickness]
Using the raw material resin composition, in a 40 mmφ extruder equipped with a circular die, it was melted at an extrusion temperature of 260 ° C., and was cooled while being cooled with 20 ° C. water. Under the conditions, an unstretched film was continuously produced. The unstretched film was sampled 1 hour and 8 hours after the start of film formation, the end was cut open, and a film thickness continuous measuring instrument (manufactured by Anritsu Electric Co., Ltd., wide-range electronic micrometer model number: K-306C, film feeding device and The film thickness in the width direction (film length: 314 mm) was measured at a running speed of 25 mm / sec using a recorder model number: K-310C), and thickness unevenness was calculated from the following equation.
Unevenness of thickness (%) = [(maximum value of film thickness−minimum value of film thickness) / average value of thickness] × 100
The rate of change over time of the film thickness unevenness 1 hour after the start of film formation and the film thickness unevenness after 8 hours (the rate of change in uneven thickness over time) is calculated from the following formula, and the rate of change in uneven thickness over time is within 15%. In this case, it was judged that the thickness unevenness was small.
Rate of change in uneven thickness over time (%) = [(film thickness unevenness 8 hours after film formation start-film thickness unevenness 1 hour after film formation start) / film thickness unevenness 1 hour after film formation start] × 100

[Stretchability, continuous productivity]
Using the raw resin composition, in a 40 mmφ extruder equipped with a circular die, it was melted at an extrusion temperature of 260 ° C., and was cooled while being cooled with water at 20 ° C. Manufactured. Subsequently, stretching was performed at a stretching temperature of 180 ° C. and a stretching ratio (both longitudinal and lateral) of 3.0 times by a tubular stretching method in which a longitudinal and lateral stretching was simultaneously performed in an inflation type with a gas pressure. The operation was continued for 24 hours, and the number of breaks in the stretching process was recorded. When the number of breaks within 24 hours was 3 or less, it was judged that continuous productivity (extensibility) was excellent.

[Heat resistant water]
After fixing a polyamide biaxially stretched film (length 300 mm, width 400 mm) to a metal frame, it was placed in a retort food autoclave (Tomy Seiko Co., Ltd., SR-240) and treated at 135 ° C. for 30 minutes. . The tensile strength of the film before and after the retort treatment was measured with a universal material testing machine (Orientec Corp., Tensilon UTM III-200) according to ASTM D-882. The retention of the tensile strength of the film before and after the retort treatment was calculated by the following formula.
Tensile strength retention = [(tensile strength after retorting) / (tensile strength before retorting)] × 100 (%)
It was judged that the higher the retention value of the tensile strength, the smaller the influence of the retort treatment, and the better the hot water resistance.

[Raw materials used]
(A) Inorganic filler (A-1) Silica surface-treated with organopolysiloxane (manufactured by Mizusawa Chemical Industry Co., Ltd., Mizukasil PM-363DS, specific surface area (S) 300 m ² , average particle size 4.0 μm, dimethylpoly Siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Silicone KF-96 100CS, molecular weight: 6000 g / mol) treatment amount: 10% by mass with respect to silica, N / S = 0.056 (μmol / m ² ))
(A-2) Silica surface-treated with organopolysiloxane (manufactured by Mizusawa Chemical Co., Ltd., Mizukasil C-102DS, specific surface area (S) 20 m ² , average particle size 3.0 μm, dimethylpolysiloxane (Shin-Etsu Chemical ( Co., Ltd., Shin-Etsu Silicone KF-96 100CS, molecular weight: 6000 g / mol) Treatment amount: 5% by mass with respect to silica, N / S = 0.417 (μmol / m ² ))

In addition, the said specific surface area and average particle diameter in a silica were measured with the following method, respectively.
[Specific surface area]
Based on JIS K-1150, it measured by the BET method from the adsorption amount of nitrogen.
[Average particle size]
The volume average particle size was measured by a Coulter counter method.

(B) Polyalkylene glycol (B-1) polyethylene glycol (Nippon Yushi Co., Ltd., PEG 400, number average molecular weight: 400)
(B-2) Polyethylene glycol (Nippon Yushi Co., Ltd., PEG 1,000, number average molecular weight: 1,000)
(B-3) Polyethylene glycol (Nippon Yushi Co., Ltd., PEG 20,000, number average molecular weight: 20,000)

(C) Partial ester compound (C-1) polyoxyethylene sorbitan monolaurate (manufactured by NOF Corporation, Nonion LT-221, number of added moles of ethylene oxide: 20 mol, esterification rate 25%)
(C-2) Polyethylene glycol monostearate (manufactured by NOF Corporation, Nonion S-15.4, number average molecular weight of polyethylene glycol: 1,410, esterification rate 50%)
(C-3) Polyoxyethylene sorbitan tristearate (manufactured by Kao Corporation, Rheodor TW-S320V, number of moles of ethylene oxide added: 20 mol, esterification rate 75%)
(C-4) Polyethylene glycol distearate (manufactured by Kao Corporation, Emanon 3299V, number average molecular weight of polyethylene glycol: 6,160, esterification rate 100%)

(D) Inorganic filler (D-1) silica having a specific surface area of 200 m ² / g or less (Mizusawa Chemical Industry Co., Ltd., Mizukasil C-002, average particle size: 2.0 μm, specific surface area (S) 43 m ² / G)
(D-2) Zeolite (manufactured by Mizusawa Chemical Co., Ltd., Shilton AMT-25, average particle size of about 2.5 μm, specific surface area (S) 3 m ² / g) (D-3) silica (Mizusawa Chemical Industry Co., Ltd.) Mizukasil P-707, average particle diameter: 2.2 μm, specific surface area (S) 300 m ² / g)
(D-4) Silica (Mizusawa Chemical Co., Ltd., Mizukasil C-402, average particle size: 2.2 μm, specific surface area (S) 300 m ² / g)

Example 1
(Production of inorganic filler-containing polyamide 6)
Caprolactam 10 kg, water 1 kg, 5-amino-1,3,3-trimethylcyclohexanemethylamine (hereinafter referred to as isophoronediamine) 37.6 g (1/400 eq / mol) Caprolactam) and 15.0 g of silica surface-treated with (A-1) organopolysiloxane were added, heated to 100 ° C., and stirred at this temperature so that the reaction system was in a uniform state. Subsequently, the temperature was further raised to 260 ° C., and the mixture was stirred for 1 hour under a pressure of 2.5 MPa. Thereafter, the polymerization reaction was performed at 260 ° C. for 2 hours under atmospheric pressure while releasing the pressure to evaporate water from the reaction vessel, and further for 4 hours under reduced pressure at 260 ° C. and 53 kPa. After completion of the reaction, the reaction product taken out in a strand form from the lower nozzle of the reaction vessel was introduced into a water bath, cooled, and cut to obtain polyamide resin pellets in which silica was uniformly dispersed. Then, after immersing this pellet in hot water and extracting and removing an unreacted monomer, it dried under reduced pressure and obtained polyamide resin (PA-1). The polyamide resin (PA-1) had a relative viscosity of 3.36, a terminal amino group concentration of 55 μeq / g, and a terminal carboxyl group concentration of 35 μeq / g. When the terminal amino group concentration of the polyamide resin is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A] − [B] = 20> 0.2 × 10000 / ((Ηr− (18−x) / 10) × M) = 0.2 × 10000 / ((3.36− (18−5) / 10) × 113) = 8.6 μeq / g is satisfied. [A] = 55> 1.1 × 10000 / ((ηr− (18−x) / 10) × M) = 1.1 × 10000 / ((3.36− (18-5) / 10) × 113) = 47 μeq / g.

(Manufacture of evaluation film)
Next, using a cylindrical mixer, the amount of (B-1) polyalkylene glycol and N, N′-ethylenebisstearic acid amide 0.08 parts by mass shown in Table 1 with respect to the polyamide resin composition In the extruder of 40 mmφ uniaxial full flight screw equipped with a circular die, the same composition was used, melted at an extrusion temperature of 260 ° C., and cooled while being cooled with water at 20 ° C. A tubular polyamide unstretched film which was substantially amorphous and not oriented was obtained. Subsequently, stretching was performed at a stretching temperature of 180 ° C. and a stretching ratio (both longitudinal and lateral) of 3.0 times by a tubular stretching method in which a longitudinal and lateral stretching was simultaneously performed in an inflation type with a gas pressure. Then, the end of the tubular film was cut open, the flat film was introduced into the tenter, and subjected to heat setting treatment at 210 ° C. while performing relaxation treatment in the width direction. Both ends of the film were released from the clip, and the ears were trimmed and wound to obtain a biaxially stretched polyamide film having a thickness of 15 μm. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Example 2
A polyamide was prepared in the same manner as in Example 1 except that 37.6 g of isophoronediamine (1/400 eq / mol caprolactam) was changed to 51.3 g of hexamethylenediamine (1/200 eq / mol caprolactam) in Example 1. Resin (PA-2) was obtained. The relative viscosity of the polyamide resin (PA-2) was 3.19, the terminal amino group concentration was 68 μeq / g, and the terminal carboxyl group concentration was 27 μeq / g. When the terminal amino group concentration of the polyamide resin is [A] (μeq / g) and the terminal carboxyl group is [B] (μeq / g), [A] − [B] = 41> 0.2 × 10000 / ( (Ηr− (18−x) / 10) × M) = 0.2 × 10000 / ((3.19− (18−5) / 10) × 113) = 9.4 μeq / g is satisfied. [A] = 68> 1.1 × 10000 / ((ηr− (18−x) / 10) × M) = 1.1 × 10000 / ((3.19− (18-5) / 10) × 113) = 52 μeq / g.
Subsequently, a biaxially stretched polyamide film was obtained in the same manner as in Example 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Example 3
In Example 1, 37.6 g (1/400 eq / mol caprolactam) of isophoronediamine was mixed with 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl-1,6-hexanediamine. A polyamide resin (PA-3) was obtained in the same manner as in Example 1 except that the mixture was changed to 46.6 g (1/300 eq / mol caprolactam). The polyamide resin (PA-3) had a relative viscosity of 3.60, a terminal amino group concentration of 52 μeq / g, and a terminal carboxyl group concentration of 25 μeq / g. When the terminal amino group concentration of the polyamide resin is [A] (μeq / g) and the terminal carboxyl group is [B] (μeq / 1 g), [A] − [B] = 27> 0.2 × 10000 / ( (Ηr− (18−x) / 10) × M) = 0.2 × 10000 / ((3.60− (18−5) / 10) × 113) = 7.7 μeq / g. [A] = 52> 1.1 × 10000 / ((ηr− (18−x) / 10) × M) = 1.1 × 10000 / ((3.60− (18−5) / 10) × 113) = 42 μeq / g.
Subsequently, a biaxially stretched polyamide film was obtained in the same manner as in Example 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Examples 4-5
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the blending amount of (B-1) polyalkylene glycol was changed to the amount shown in Table 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Example 6
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (B-1) polyalkylene glycol was changed to (B-2) polyalkylene glycol in Example 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Example 7
A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that (B-1) polyalkylene glycol was changed to (C-1) polyoxyethylene sorbitan monolaurate in Example 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Example 8
In Example 7, a biaxially stretched polyamide film was obtained in the same manner as in Example 7 except that (C-1) polyoxyethylene sorbitan monolaurate was changed to (C-2) polyethylene glycol monostearate. It was. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Example 9
In Example 1, (A-1) A method similar to Example 1 except that (D) (D-1) silica was blended in the proportion shown in Table 1 together with silica surface-treated with organopolysiloxane. A biaxially stretched polyamide film was obtained. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Example 10
In Example 9, except that (D-1) silica was changed to (D-2) zeolite and (B-1) polyalkylene glycol was changed to (C-1) polyoxyethylene sorbitan monolaurate A biaxially stretched polyamide film was obtained in the same manner as in Example 9. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Example 11
In Example 1, the same procedure as in Example 1 was repeated except that (C-1) polyoxyethylene sorbitan monolaurate was blended together with (B-1) polyalkylene glycol at the ratio shown in Table 1. An axially stretched polyamide film was obtained. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Example 12
In Example 9, (B-1) Polyalkylene glycol and (C-1) polyoxyethylene sorbitan monolaurate were blended in the proportions shown in Table 1 in the same manner as in Example 9, except that An axially stretched polyamide film was obtained. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 1
Example 1 (Production of inorganic filler-containing polyamide 6) is the same as Example 1 except that 37.6 g (1/400 eq / mol caprolactam) of isophoronediamine is not used and the reduced pressure is changed from 53 kPa to 93 kPa. Thus, a polyamide resin (PA-4) was obtained. The polyamide resin (PA-4) had a relative viscosity of 3.30, a terminal amino group concentration of 42 μeq / g, and a terminal carboxyl group concentration of 43 μeq / g. When the terminal amino group concentration of the polyamide resin is [A] (μeq / g) and the terminal carboxyl group is [B] (μeq / g), [A] − [B] = − 1 <0.2 × 10000 / It was (((eta) r- (18-x) / 10) * M) = 0.2 * 10000 / ((3.30- (18-5) / 10) * 113) = 8.6microeq / g. [A] = 41 <1.1 × 10000 / ((ηr− (18−x) / 10) × M) = 1.1 × 10000 / ((3.30− (18−5) / 10) × 113) = 49 μeq / g.
Subsequently, a biaxially stretched polyamide film was obtained in the same manner as in Example 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 2
The procedure was the same as that in Example 1 (Production of inorganic filler-containing polyamide 6), except that 37.6 g (1/400 eq / mol caprolactam) of isophoronediamine was changed to 15.2 g of acetic acid (1/700 eq / mol caprolactam). A polyamide resin (PA-5) was obtained in the same manner as in Example 1. The polyamide resin (PA-5) had a relative viscosity of 3.45, a terminal amino group concentration of 31 μeq / g, and a terminal carboxyl group concentration of 41 μeq / g. When the terminal amino group concentration of the polyamide is [A] (μeq / g) and the terminal carboxyl group is [B] (μeq / g), [A] − [B] = − 10 <0.2 × 10000 / ( (Ηr− (18−x) / 10) × M) = 0.2 × 10000 / ((3.45− (18−5) / 10) × 113) = 8.2 μeq / g. [A] = 31 <1.1 × 10000 / ((ηr− (18−x) / 10) × M) = 1.1 × 10000 / ((3.45− (18−5) / 10) × 113) = 45 μeq / g.
Subsequently, a biaxially stretched polyamide film was obtained in the same manner as in Example 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 3
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (A-1) silica surface-treated with organopolysiloxane was not used. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 4
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (B-1) polyalkylene glycol was not used. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Examples 5-6
In Example 11, except that the blending amount of (B-1) polyalkylene glycol and (C-1) polyoxyethylene sorbitan monolaurate was changed to the amount shown in Table 1, the same method as in Example 11 was used. A biaxially stretched polyamide film was obtained. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 7
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (B-1) polyalkylene glycol was changed to (B-3) polyalkylene glycol in Example 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 8
A biaxially stretched polyamide film was prepared in the same manner as in Example 7 except that (C-1) polyoxyethylene sorbitan monolaurate was changed to (C-3) polyoxyethylene sorbitan tristearate in Example 7. Got. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 9
In Example 7, a biaxially stretched polyamide film was obtained in the same manner as in Example 7 except that (C-1) polyoxyethylene sorbitan monolaurate was changed to (C-4) polyethylene glycol distearate. It was. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 10
In Example 1, (A-1) Silica surface-treated with organopolysiloxane was changed to (A-2) Silica surface-treated with organopolysiloxane, and the same procedure as in Example 1 was repeated. An axially stretched polyamide film was obtained. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 11
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (A-1) silica surface-treated with organopolysiloxane was changed to (D-3) silica. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Comparative Example 12
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (A-1) silica surface-treated with organopolysiloxane was changed to (D-4) silica. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film. In addition, Table 2 shows the results of investigation on continuous productivity by the above method.

Claims (9)

Film containing 0.01 to 0.5 parts by mass of (A) inorganic filler and (B) polyalkylene glycol and / or (C) partial ester compound with respect to 100 parts by mass of polyamide resin A polyamide resin composition for
When the terminal amino group concentration is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), the polyamide resin satisfies [A] − [B] ≧ 20 ,
(A) the inorganic filler is an inorganic filler which has been surface-treated with the organopolysiloxane, a specific surface area S (m2 / g) of inorganic filler, processing amount of the organopolysiloxane per inorganic filler 1g of N (mu Mol / g), N / S (μmol / m2) is 0.002 to 0.1,
The (B) polyalkylene glycol is a polyalkylene glycol having a number average molecular weight of 200 to 4,000,
A polyamide resin composition for a film, wherein the (C) partial ester compound is a partial ester compound of an alkylene oxide adduct of a polyhydric alcohol and a fatty acid having an esterification rate of less than 70% . The polyamide for a film according to claim 1, wherein the inorganic filler (A) is silica, and is surface-treated with 0.5 to 15 parts by mass of organopolysiloxane with respect to 100 parts by mass of silica. Resin composition. The composition further comprises 0.01 to 0.2 parts by mass of (D) inorganic filler other than (A) inorganic filler, wherein S is 200 m ² / g or less with respect to 100 parts by mass of the polyamide resin. Item 3. The polyamide resin composition for film according to Item 1 or 2. The polyamide resin composition for a film according to any one of claims 1 to 3, wherein the (D) inorganic filler is at least one selected from the group consisting of silica, kaolin, and zeolite. The polyamide resin is a homopolymer or copolymer composed of at least one selected from the group consisting of units derived from caprolactam, units derived from hexamethylene adipamide, and units derived from dodecane lactam. The polyamide resin composition for a film according to any one of claims 1 to 4, which is a coalescence. The polyamide resin is any one selected from the group consisting of a polyamide 6 polymer, a polyamide 6/66 copolymer, a polyamide 6/12 copolymer, and a polyamide 6/66/12 copolymer. The polyamide resin composition for a film according to claim 5. The polyamide resin is, during the polymerization, aliphatic diamines, one cycloaliphatic diamine, and claims 1, characterized in that the polyamides prepared by adding at least one selected from the group consisting of polyamine 6 A polyamide resin composition for a film according to claim 1. Polyamide film consisting of a film for the polyamide resin composition according to any of claims 1 to 7. The polyamide film according to claim 8 , which is a biaxially stretched polyamide film.