JP2012011776A - Film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film superior in a gas barrier property and delamination resistance under high temperature and high humidity, especially in the gas barrier property and durability of delamination strength after processing under high temperature high humidity environment.SOLUTION: The film contains a resin layer (S) which is laminated with a resin layer (a) and resin layer (b) each of which has specific polyamide polymer (A), polyglycolic acid polymer (B1) and aromatic polyester system polymer (B2) as principal components respectively, and a resin layer (e) containing modified polyester elastomer polymer (C), wherein (e) includes a laminating layer formed by contacting the resin layer (c) which has (C) as a principal component or (c), with the resin layer (d) which includes (A), (B1), (B2), and (C) as principal components; (B1) and (B2) have specific mass ratios; (e) contacts (a) and (b) and is laminated between (a) and (b); and (c) composing (e) contacts (a) and/or (b).

Description

  The present invention relates to a film excellent in gas barrier properties.

  Polyamide resin film is excellent in strength, flexibility, heat resistance, chemical resistance, and also has excellent gas barrier properties. Widely used in packaging materials, agricultural chemicals and reagents containers.

  However, depending on the application, the gas barrier properties are not always sufficient, and various methods for improving the gas barrier properties of packaging materials, containers and the like have been proposed.

  In particular, in a field where gas barrier properties are highly required, a film in which polymetaxylylene adipamide (polyamide MXD6) or saponified ethylene / vinyl acetate copolymer (EVOH) is laminated on polyamide 6 is used. However, these laminated films have a problem that the gas barrier property is lowered under high humidity, and their use is limited such that they cannot be used for packaging foods with high water activity.

  Polyglycolic acid has excellent gas barrier properties such as heat resistance, mechanical strength, oxygen gas barrier property, carbon dioxide gas barrier property, and water vapor barrier property, and has been actively researched and developed in recent years as a suitable material for packaging materials such as foods and pharmaceuticals. It has become. In particular, a laminated film of polyglycolic acid and polyamide has been proposed as a material whose gas barrier property does not deteriorate under high humidity (see Patent Documents 1 and 2). The laminated film according to the present technology is very excellent in gas barrier properties. In the laminated film, a carboxyl-modified polyolefin polymer, a glycidyl group-containing polyolefin copolymer, or the like has been proposed as an adhesive resin interposed between the polyamide and polyglycolic acid layers.

JP 2006-182018 A JP 2007-111979 A

  However, these documents do not describe the delamination strength in the laminated film, nor provide any technical suggestion, and the delamination strength is not always sufficient when a stretched film is used. In addition, food packaging containers are often subjected to heat sterilization treatment such as boil treatment or retort treatment after packaging the food, so that there is no delamination phenomenon or delamination after the heat sterilization treatment. Development of a laminated film of a polyglycolic acid polymer and a polyamide polymer, which is excellent in durability of delamination strength after the treatment in is required.

  An object of the present invention is to provide a film having excellent gas barrier properties and delamination resistance under high temperature and high humidity, in particular, excellent durability of gas barrier properties and delamination strength after treatment in a high temperature and high humidity atmosphere.

The present invention
A resin layer (a) mainly composed of a polyamide polymer (A);
A resin layer (b) mainly composed of a polyglycolic acid polymer (B1) and an aromatic polyester polymer (B2);
Resin layer (e) containing polymer (C)
Is a film including a resin layer (S) laminated,
The polymer (A) is represented by the following formula (1):
[X] − [Y] ≧ 0.2 × 10000 / ((ηr− (18−x) / 10) × M) (1)
([X] is the terminal amino group concentration per 1 g of the polymer (A) (μeq / g) (eq is equivalent),
[Y] is a terminal carboxyl group concentration (μeq / g) per 1 g of the polymer (A) (eq is equivalent),
x = [CH ₂ ] / [NHCO] ([CH ₂ ] is the number of methylene groups in the polymer (A), [NHCO] is the number of amide groups in the polymer (A),
ηr is a relative viscosity measured in JIS K-6920 in 96% by weight sulfuric acid in the polymer (A) concentration of 1% by weight at 25 ° C., and ηr> (18−x) / 10.
M represents the mass per mole of the structural repeating unit of the polymer (A). )
The filling,
The polymer (C) is a modified polyester elastomer polymer graft-modified with an α, β-ethylenically unsaturated carboxylic acid (excluding the polymer (B2)).
The resin layer (e) is a resin layer (c) containing the polymer (C) as a main component, or
The resin layer (c) and the polymer layer (d) (provided that the polymer (A), the polymer (B1), the polymer (B2), and the polymer (C) are the main components) (A), (b) and (c) are excluded.)
Mass ratio of the polymer (B1) and the polymer (B2) to the total amount of 100% by mass of the polymer (B1) and the polymer (B2) (polymer (B1) / polymer (B2)) Is 60/40 to 90/10, in units of mass%,
The resin layer (e) is laminated between the resin layer (a) and the resin layer (b) in contact with the resin layer (a) and the resin layer (b),
The resin layer (c) constituting the laminated resin layer (e) is in contact with the resin layer (a) and / or the resin layer (b).

  According to the film of the present invention, it is possible to provide a film having excellent gas barrier properties and delamination resistance under high temperature and high humidity, in particular, excellent durability of gas barrier properties and delamination strength after treatment in a high temperature and high humidity atmosphere. it can.

[Polymer (A)]
The polyamide polymer (A) used in the present invention (hereinafter also referred to as polymer (A)) is:
Following formula (1)
[X] − [Y] ≧ 0.2 × 10000 / ((ηr− (18−x) / 10) × M) (1)
([X] is the terminal amino group concentration per 1 g of the polymer (A) (μeq / g) (eq is equivalent),
[Y] is a terminal carboxyl group concentration (μeq / g) per 1 g of the polymer (A) (eq is equivalent),
x = [CH ₂ ] / [NHCO] ([CH ₂ ] is the number of methylene groups in the polymer (A), [NHCO] is the number of amide groups in the polymer (A),
ηr is a relative viscosity measured in 96 mass% sulfuric acid in JIS K-6920 in a polyamide polymer (A) concentration of 1 mass% at 25 ° C., and ηr> (18−x) / 10.
M represents the mass per mole of the structural repeating unit of the polymer (A). )
(Hereinafter, the polymer (A) is also referred to as a terminal-adjusted polyamide polymer).

  The terminal-adjusted polyamide polymer is polymerized or copolymerized by a known method such as melt polymerization, solution polymerization or solid phase polymerization using a lactam, an aminocarboxylic acid, or a nylon salt composed of a diamine and a dicarboxylic acid as a raw material. can get.

  Examples of lactams include caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, and aminocarboxylic acids 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.

  Examples of the diamine constituting the nylon salt include 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8- Octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecane Diamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2- / 3-methyl-1,5 -Pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4- / 2,4,4-to Aliphatic diamines such as methyl-1,6-hexanediamine, 5-methyl-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, 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5- / 2,6-norbornane dimethylamine, tricyclodecane dimethylamine, etc. Cyclic diamines, aromatic diamines such as m-/ p-xylylenediamine. 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 terminal-adjusted polyamide polymer, these homopolymers or copolymers derived from lactam, aminocarboxylic acid, or nylon salt composed of diamine and dicarboxylic acid can be used alone or in the form of a mixture.
Specific examples of the terminal-adjusted polyamide polymer used include polycaprolactam (polyamide 6), polyundecane lactam (polyamide 11), polydodecane lactam (polyamide 12), polyethylene adipamide (polyamide 26), polytetra Methylene 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 sebamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), poly Nonamethylene terephthalamide (Polyamide 9T), Polytrimethylhexamethylene terephthalamide (Polyamide TMHT), Polynonamethylene hexahydroterephthalamide (Polyamide 9T (H)), Polynonamethylene naphthalamide (Polyamide 9N), Polydeca Methylene adipamide (polyamide 106), polydecamethylene azelamide (polyamide 109), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydecamethylene terephthalami (Polyamide 10T), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamemethylene 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)), Polydodecamethylene naphthalamide (polyamide 12N), polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide) MXD9), polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene dodecamide (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 PACMI), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (polyamide dimethyl PACM12), polyisophorone adipamide (polyamide) DopD6), polyisophorone 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 the heat resistance, mechanical strength, transparency, economy, availability, etc. of the film of the present invention obtained, polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer (polyamide 6 and A copolymer of polyamide 66, hereinafter the copolymer is described in the same manner), polyamide 6/69 copolymer, 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, Polyamide 66 / 6T copolymer, polyamide 66 / 6I copolymer, polyamide 6T / 6I copolymer, polyamide 66 / 6T / 6I copolymer, and poly At least one selected from the group consisting of amide MXD6 is preferable, and polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6 / IPD6 copolymer, polyamide 6 / More preferred is at least one selected from the group consisting of an IPDT copolymer and polyamide 6/66/12. More preferred 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.

  From the viewpoints of securing preferable mechanical properties of the obtained film of the present invention and ensuring preferable moldability of the film by setting the viscosity at the time of melting to an appropriate range, terminal-adjusted polyamide measured according to JIS K-6920 The relative viscosity ηr of the polymer is preferably 2.0 to 5.0, and more preferably 2.5 to 4.5.

When the terminal-adjusted polyamide polymer is polycaprolactam (polyamide 6) and polyhexamethylene adipamide (polyamide 66), [CH ₂ ] / [NHCO] = 5, and the mass M per mole of the structural repeating unit is 113. It is.

When the terminal-adjusted polyamide polymer is polydodecane lactam (polyamide 12), [CH ₂ ] / [NHCO] = 11 and the mass M per mole of the structural repeating unit is 197.

When the terminally adjusted polyamide polymer is a caprolactam / hexamethylene adipamide copolymer (polyamide 6/66 copolymer), [CH ₂ ] / [NHCO] = The mass M per mole of the structural repeating unit is 113.

When the terminal-adjusted polyamide polymer is a caprolactam / dodecanlactam copolymer (polyamide 6/12 copolymer), [CH ₂ ] / [NHCO] or 1 mol of the constitutional repeating unit depends on the polymerization mass and molar ratio of the constitutional repeating unit. 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 mole of the structural repeating unit. Is 123.5. Thus, if the [CH ₂ ] / [NHCO], the mass M per mole of the structural repeating unit, and the relative viscosity are known, the conditions for the terminal amino group concentration and the terminal carboxyl group concentration can be calculated from the above formula. Become.

Further, the obtained film of the present invention preferably has hot water resistance and delamination resistance, particularly durability of delamination strength after treatment in a high-temperature and high-humidity atmosphere, and suitably produces a terminal-adjusted polyamide polymer. From the viewpoint, [X]-[Y]
0.3 × 10000 / ((ηr− (18−x) / 10) × M)
≦ [X]-[Y]
≦ 1.5 × 10000 / ((ηr− (18−x) / 10) × M)
It is preferable that
0.4 × 10000 / ((ηr− (18−x) / 10) × M)
≦ [X]-[Y]
≦ 1.4 × 10000 / ((ηr− (18−x) / 10) × M)
It is more preferable that

  The terminal amino group concentration [X] (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 [Y] (μeq / g) can be measured by dissolving the polyamide in benzyl alcohol and titrating with 0.05N sodium hydroxide solution.

  The terminal-adjusted polyamide polymer is produced by polymerizing or copolymerizing the polyamide 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. In addition, the following exemplified amines and carboxylic acids can be used alone or in combination of two or more.

  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 and docosylamine, alicyclic monoamines such as cyclohexylamine and 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 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 1,7-heptanediamine. 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2- / 3- Methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4- / , 4,4-trimethyl-1,6-hexanediamine, aliphatic diamine such as 5-methyl-1,9-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 (isophoronediamine), bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5- / 2,6-norbornanedimethylamine Alicyclic diamines such as tricyclodecane dimethylamine, m- / p-key Aromatic diamines such Rirenjiamin like.

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.

  As polyalkyleneimine, one or more kinds of alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine, etc. Homopolymers and copolymers obtained by polymerizing the above by a conventional method. 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, 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 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 terminal-adjusted polyamide polymer to be produced. From the viewpoint of obtaining sufficient reactivity and facilitating the production of a terminal-adjusted polyamide polymer having a desired viscosity, the amine is usually used with respect to the polyamide raw material (monomer or monomer unit 1 mol constituting the repeating unit). It is preferable that the addition amount of each is 0.5 to 20 meq / mol, more preferably 1.0 to 10 meq / mol (the equivalent of the amino group reacts 1: 1 with the carboxyl group). The amount of the amino group forming the amide group is 1 equivalent).

Furthermore, the terminal amino group concentration [X] (μeq / g) of the terminal-adjusted polyamide polymer is determined according to the hot water resistance and delamination resistance of the obtained film of the present invention, in particular, delamination after treatment in a high temperature and high humidity atmosphere. From the viewpoint of suitably ensuring the durability of the strength and suitably producing the terminal-adjusted polyamide polymer,
[X] ≧ 1.1 × 10000 / ((ηr− (18−x) / 10) × M) (2)
Preferably satisfying
[X] ≧ 1.15 × 10000 / ((ηr− (18−x) / 10) × M)
More preferably,
1.2 × 10000 / ((ηr− (18−x) / 10) × M) ≦ [X] ≦ 2.0 × 10000 / ((ηr− (18−x) / 10) × M)
It is further preferable to satisfy

  In the terminal-adjusted polyamide polymer, the terminal carboxyl group concentration is decreased with a relatively small amount of diamines and the terminal amino group concentration is increased in order to satisfy all the conditions of the terminal group concentrations of the formulas (1) and (2) Therefore, it is preferable to add diamines among the above-exemplified amines.

  Therefore, in order to satisfy the condition of the terminal group concentration without reducing the productivity at the time of production of the terminal-adjusted polyamide polymer, it is preferable to add a diamine at the time of polymerization. , Aliphatic diamine, alicyclic diamine, and at least one selected from the group consisting of polyamines, 1,6-hexamethylenediamine, 2,2,4- / 2,4,4-trimethyl -1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 5-amino-1,3,3-trimethylcyclohexanemethanamine (isophoronediamine), 5-amino-2,2,4-trimethyl-1- Black pentane methylamine, and more preferably at least one selected from the group consisting of 2,5- / 2,6-norbornane dimethylamine.

  The terminal-adjusted polyamide polymer may be a mixture of two or more types of terminal-adjusted polyamide polymers having different terminal group concentrations as long as the terminal group concentration is satisfied. In this case, the terminal amino group concentration and terminal group carboxyl concentration of the terminal-adjusted polyamide polymer mixture are determined by the terminal amino group concentration, terminal carboxyl group concentration and blending ratio of the terminal-adjusted polyamide polymer constituting the mixture.

  Regarding the terminal-adjusted polyamide polymer, when producing the terminal-adjusted polyamide polymer, the viewpoint of reducing the adhesion of the oligomer component near the die and suppressing the appearance defect by the generation of die lines and fish eyes due to these adhering substances. From the above, the amount of water extraction measured based on the method for measuring the content of low molecular weight substances specified in JIS K-6920 is preferably 1.0% by mass or less, more preferably 0.5% by mass or less. preferable. Furthermore, since the terminal-adjusted polyamide polymer has a higher hygroscopicity than the olefin resin, the use of the hygroscopic resin suppresses the occurrence of hydrolysis when the raw material is melt-extruded, thereby preventing the generation of oligomers. From the viewpoint of suppressing and securing suitable film manufacturability, it is preferable to dry in advance and make the moisture content 0.1% by mass or less.

[Resin layer (a)]
In the film of the present invention, the resin layer (a) is responsible for the excellent strength, flexibility, heat resistance, chemical resistance, and particularly gas barrier properties that are characteristic of a polyamide-based resin film. Therefore, the resin layer (a) contains the polymer (A) as a main component. The main component of the polymer (A) is that the resin layer (a) contains the polymer (A) to the extent that the above-mentioned characteristics derived from the polymer (A) are included. The content of the polymer (A) in a) is usually 60 to 100% by mass, preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and 85 to 100%. More preferably, it is 95 mass%, More preferably, it is 95-100 mass%, It is more preferable that it is 97-100 mass%, It is more preferable that it is 99-100 mass%.

  In addition, from the viewpoint of ensuring gas barrier properties and delamination resistance under high temperature and high humidity of the film of the present invention, the resin layer (a) contains a polymer other than the polymer (A). The content of the polymer (A) is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, based on the total amount of the polymer (A) and the other polymer, 97 More preferably, it is -100 mass%, More preferably, it is 99-100 mass.

  When producing a polymer (A), when producing a polymer composition containing a polymer (A) such as a resin containing the polymer (A), and / or when producing a resin layer (a) ( Hereinafter, it is also referred to when the resin layer (a) or the like is produced.), Usually blended within a range not impairing the effect of the film of the present invention, for example, a heat stabilizer, an ultraviolet absorber, a light stabilizer. , Antioxidants, antistatic agents, lubricants, antiblocking agents, fillers, tackifiers, sealability improvers, antifogging agents, crystal nucleating agents, mold release agents, plasticizers, crosslinking agents, foaming agents, colorants Various additives such as (pigment, dye, etc.) and a bending fatigue resistance improving material can be added. Components of these additives remaining in the resin layer (a) are constituent components of the resin layer (a).

  When various 3rd components, such as the above-mentioned additive, are contained in the resin layer (a), the quantity of the 3rd component in a resin layer (a) is computed as follows. For example, after the polymer (A) is kneaded with the third component (p) to obtain a resin, the resin is further mixed with the third component (q) (p may be q). In the case of the layer (a), the total amount of the third component in the resin layer (a) is the sum of the amount of the third component (p) in the resin and the amount of the third component (q) added separately. The same calculation is performed for the resin layers (b), (c), and (d) described later.

  When producing the resin layer (a) and the like, from the viewpoint of ensuring the heat resistance of the film of the present invention obtained, improvement of hot water resistance and melt stability during film formation, processing stability, It is preferable to add a phenolic compound or a phosphorus compound. As the phenol compound, a hindered phenol compound is more preferably used. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, 2,6- Di-t-butyl-4-ethylphenol, 2,5-di-t-amylhydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (6-t -Butyl-3-methylphenol), 2,2'-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-butylidenebis (3-methyl) -6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [ -(2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di (t-pentyl) phenyl acrylate, 2,2'-methylenebis [4-methyl-6- (α-methyl) -Cyclohexyl) phenol], 4,4'-methylenebis (2,6-di-t-butylphenol), 4,6-bis (octylthiomethyl) -o-cresol, 2,2'-ethylenebis (4,6 -Di-t-butylphenol), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], hydrazobis (3,5-di- -T-butyl-4-hydroxy-hydrocinnamoyl), N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,6-hexanediol- Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] Methane, pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris- (3 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine-2,4,6- ( H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) ), N-octadecyl-3- (3,5-di-t-butyl-4-hydroxy-phenyl) propionate, 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tris- (3,5-di-t-butyl-4-hydroxy Benzyl) isocyanurate, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) calcium, 3,5-di-tert-butyl-4-hydroxy-benzylphosphone To-diethyl ester, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d · f] [1 · 3.2] dioxaphosphepine and the like. These can use 1 type (s) or 2 or more types.

  Examples of phosphorus compounds include triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, diphenyl monooctyl phosphite, tri (p-cresyl) phosphite, tris (nonylphenyl) phosphite, diphenyl monodecyl. Phosphite, diphenyl mono (tridecyl) phosphite, tris (2-ethylhexyl) phosphite, phenyl didecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tridecyl phosphite, trilauryl phosphite Phyto, trioctadecyl phosphite, trioleyl phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t -Butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetraphenyldipropylene glycol diphosphite Bis (2,4-di-t-6-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t -Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite Bis (nonylphenyl) pentaerythritol diphosphite, tris (tridec Phosphite, bis [2,4-di (1-phenylisopropyl) phenyl] pentaerythritol diphosphite, tristearyl sorbitol triphosphite, trilauryl trithiophosphite, tris (monononylphenyl) phosphite, tris (di Nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyloxy) -4,4'-biphenylene-diphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyloxy) -4 , 4'-biphenylene-diphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-di-t-butylphenyl) Octyl phosphite, t-hexa (tridecyl) -1,1,3-to Lis (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane-triphosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, 2,2 ′ -Ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t- Butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, t4,4′-butylidenebis (3-methyl-6-tert-butylphenylditri) Decyl) phosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidenediphenyl diphosphite, tri [2-[[2,4,8,10-Tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (2,2 ', 2' '-nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl)] phosphite), 2- ( 2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetra Ilbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite and the like can be mentioned. These can use 1 type (s) or 2 or more types.

  It is preferable that content of a phenol type and / or phosphorus type compound is 0.005-0.3 mass part with respect to 100 mass parts of polymers (A), and is 0.01-0.2 mass part. More preferably, it is 0.02-0.1 mass part.

  Moreover, when manufacturing resin layer (a) etc., it is preferable to add an inorganic filler as an additive for the purpose of improving slipperiness. 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. Furthermore, the inorganic filler is more preferably an inorganic filler surface-treated with a silane coupling agent or organopolysiloxane.

  Furthermore, in order to ensure the transparency of the film and not impair the film appearance while ensuring the effect of improving slipperiness, it suppresses secondary agglomeration and the like to suppress the generation of fish eye gel, From the viewpoint of obtaining an effect, the average particle size of the inorganic filler is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm. It is desirable that substantially no particles having a particle diameter of 20 μm or more are contained. It is desirable to perform pulverization and classification in advance so that the average particle size of the inorganic filler falls within the above-mentioned preferable range. Moreover, as long as an average particle diameter satisfy | fills the said value, it is also possible to use together the inorganic filler from which a particle size differs.

  The average particle size of the inorganic filler is determined by adding a slurry in which 0.5 g of inorganic filler is dispersed in 150 g of ion-exchanged water while stirring 150 g of ion-exchanged water at 5000 rpm. The volume average particle diameter measured by the Coulter counter method after being dispersed with a sonic disperser.

  As a method of adding an inorganic filler when producing the resin layer (a) and the like, an internal polymerization method in which an inorganic filler is added at any stage of the polymerization step of the polymer (A), or a high concentration inorganic filler in advance is used as the polymer. In (A), kneading using a single or twin screw extruder, the so-called masterbatch method in which this is diluted during molding, the inorganic filler is kneaded in advance with the additive concentration used for molding. Examples thereof include a kneading and mixing method, a dry blending method in which a predetermined amount of an inorganic filler is added to a polyamide polymer at the time of molding, and the like. Among these, from the viewpoints of dispersibility of the inorganic filler, stability of film formation, and economic efficiency, an internal polymerization method and a master batch method are preferable.

  The content of the inorganic filler is 0.01 to 0.00 with respect to 100 parts by mass of the polymer (A) from the viewpoint of ensuring the effect of improving the slipperiness of the film without impairing the transparency and appearance of the film. It is preferably 5 parts by mass, more preferably 0.03 to 0.3 parts by mass, and even more preferably 0.05 to 0.2 parts by mass.

  Moreover, when manufacturing resin layer (a) etc., it is preferable to add a hydroxy fatty acid magnesium salt as an additive for prevention of the generation of eye grease. 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 content of the hydroxy fatty acid magnesium salt is 0.003 to 0.3 with respect to 100 parts by mass of the polymer (A) from the viewpoint of securing the anti-grease effect without impairing the transparency and printability of the film. It is preferable that it is a mass part, It is more preferable that it is 0.004-0.2 mass part, It is further more preferable that it is 0.005-0.1 mass part.

  Furthermore, when manufacturing a resin layer (a) etc., it is preferable from a viewpoint of improving transparency and slipperiness to add a bisamide compound as an additive. Examples of bisamide compounds 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 content of the bisamide compound is the polymer (A) 100 from the viewpoint of ensuring the effect of improving the transparency and slipperiness of the film of the present invention obtained without lowering the printability of the film and the adhesion during lamination. It is preferable that it is 0.01-0.5 mass part with respect to a mass part, It is more preferable that it is 0.02-0.3 mass part, It is further that it is 0.03-0.2 mass part preferable.

  Moreover, when manufacturing resin layer (a) etc., amorphous polyamide (however, a polymer (A) is excluded) may be added as an additive for the improvement of the drawability at the time of film manufacture. preferable. Amorphous polyamide refers to a polyamide whose endothermic curve measured using a differential scanning calorimeter is indistinguishable from a change in base and does not exhibit a clear melting point.

  As the amorphous polyamide, for example, a polyamide containing units derived from an aromatic aminocarboxylic acid such as m- / p-aminomethylbenzoic acid and p-aminoethylbenzoic acid, or an aromatic such as terephthalic acid and isophthalic acid There are semi-aromatic polyamides containing units derived from dicarboxylic acids and aliphatic diamines, and semi-aromatic polyamides containing units derived from aliphatic diamines and terephthalic acid and / or isophthalic acid are preferred. As a unit derived from an aliphatic diamine, a unit derived from 1,6-hexanediamine is preferably selected. The polyamide containing units derived from an aliphatic diamine and terephthalic acid and / or isophthalic acid may be a polymer in which the above units are composed of 100% by mass, but other units such as lactam, aminocarboxylic acid, etc. It may be a copolymer containing units derived from dicarboxylic acids other than acid, terephthalic acid and isophthalic acid and other diamines other than aliphatic diamines. As other units, a unit derived from hexamethylene adipamide, a unit derived from caprolactam, and a unit derived from dodecane lactam are preferable.

  Specific examples of the amorphous polyamide include polyamide 6T / 6I copolymer, polyamide 6T / 6I / 66 copolymer, polyamide 6T / 6I / 6 copolymer, polyamide 6T / 6 copolymer, polyamide 6I / 6. Examples include a copolymer, a polyamide 6T / 66 copolymer, a polyamide 6I / 66 copolymer, a polyamide 6T / 12 copolymer, a polyamide 6I / 12 copolymer, and a polyamide 6T / 6I / 12 copolymer.

  The content of the amorphous polyamide is 1 to 100 parts by mass of the polymer (A) from the viewpoint of improving the stretchability and securing the preferable moldability of the film by setting the viscosity at the time of melting to an appropriate range. It is preferably 30 parts by mass, more preferably 3 to 25 parts by mass, and even more preferably 5 to 20 parts by mass.

  Furthermore, when the resin layer (a) or the like is produced, an olefin copolymer as an additive for the purpose of improving the bending fatigue resistance within a range that does not impair the transparency of a molded product such as a film, In addition, a bending fatigue resistance improving material such as a modified product or an elastomer thereof can be contained. As the olefin copolymer, ethylene / α-olefin copolymer having 3 to 10 carbon atoms, ethylene / α, β-unsaturated carboxylic acid ester copolymer, ethylene / vinyl acetate copolymer, ethylene / acetic acid Examples thereof include a partially saponified vinyl copolymer, an ethylene / α, β-unsaturated carboxylic acid copolymer, and an ionomer polymer. Acrylic acid, methacrylic 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] Carboxyl groups such as -5-heptene-2,3-dicarboxylic acid and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2 .1] Acid anhydride groups such as-5-heptene-2,3-dicarboxylic acid anhydride, functional groups such as epoxy groups such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. The above-mentioned polyolefin-based copolymer in which is contained. These can use 1 type (s) or 2 or more types.

  As described below, the elastomer includes a polyester elastomer other than the polymer (C) in the present invention, a polyether ester amide elastomer other than the polymer (A), a polyamide elastomer such as a polyether amide elastomer, and a polystyrene phase at both ends. Examples thereof include styrene-based elastomers, which are block copolymers having a hydrogenated polyolefin as a rubber intermediate phase and a polystyrene phase serving as a crosslinking point. These can use 1 type (s) or 2 or more types.

  The content of the olefin-based copolymer, its modified product and elastomer is 100 parts by mass of the polymer (A) from the viewpoint of improving the bending fatigue resistance of the obtained film of the present invention and ensuring good transparency. On the other hand, it is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 2 to 7 parts by mass.

[Polymer (B1)]
The polyglycolic acid polymer (B1) (hereinafter also referred to as polymer (B1)) used in the present invention is represented by the following general formula (3).

It is a homopolymer or a copolymer containing the repeating unit represented by these. The content ratio of the repeating unit represented by the formula (3) in the polyglycolic acid polymer (B1) does not impair the crystallinity inherent in the polyglycolic acid polymer (B1), and the gas barrier property and heat resistance of the film. From the viewpoint of suitably maintaining the properties and the like, it is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and further preferably 100% by mass. More preferred.

  In addition to the repeating unit represented by the general formula (3), the polyglycolic acid polymer (B1) does not impair the crystallinity inherent to the polyglycolic acid homopolymer and adversely affects the gas barrier properties. For example, at least one type of repeating unit selected from the group consisting of the following formulas (4) to (8) can be contained within a range that does not exist.

In the said General formula (4), n represents the integer of 1-10 and m represents the integer of 0-10. Moreover, in the said General formula (5), j represents the integer of 1-10. Further, in the above general formula (6), _{R 1} and _{R 2} may be the same or different, represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, k is an integer of 2 to 10. By introducing these other repeating units at a ratio of 1% by mass or more, the melting point of the polyglycolic acid homopolymer can be lowered. And if melting | fusing point of a polyglycolic acid polymer (B1) is lowered | hung, processing temperature can be lowered | hung and the thermal decomposition at the time of melt processing can be reduced. Also, the processability can be improved by controlling the crystallization rate of the polyglycolic acid polymer (B1) by copolymerization.

  Examples of a method for synthesizing the polyglycolic acid polymer (B1) include a method of dehydrating polycondensation of glycolic acid, a method of dealcoholating polycondensation of glycolic acid alkyl ester, a method of ring-opening polymerization of glycolide, and the like. Among these, glycolide is subjected to ring-opening polymerization by heating to a temperature of about 120 to 250 ° C. in the presence of a small amount of a catalyst (for example, a cation catalyst such as organic carboxylate tin, tin halide, antimony halide, etc.). A method of synthesizing polyglycolic acid (ie, polyglycolide) by a method is preferred. Such ring-opening polymerization is preferably performed by a bulk polymerization method or a solution polymerization method.

  On the other hand, the polyglycolic acid polymer (B1) can copolymerize at least one repeating unit selected from the group consisting of glycolic acid, glycolic acid alkyl ester, and glycolide with other repeating units. Other repeating units include, for example, ethylene oxalate, lactide, β-propiolactone, β-butyrolactone, pivalolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, etc. Units derived from lactones, units derived from cyclic compounds such as trimethylene carbonate and 1,3-dioxane, lactic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 6-hydroxy Units derived from hydroxycarboxylic acids such as caproic acid or their alkyl esters, units derived from aliphatic diols such as 1,2-ethane glycol and 1,4-butanediol, fats such as succinic acid and adipic acid Derived from aliphatic dicarboxylic acids or their alkyl esters Unit, and the like. These can use 1 type (s) or 2 or more types.

  Among these, it is derived from lactones such as lactide and ε-caprolactone, cyclic compounds such as trimethylene carbonate, and hydroxycarboxylic acids such as lactic acid, because it is easy to copolymerize and excellent in physical properties. Are preferred. The content ratio of the other repeating units in the polyglycolic acid polymer (B1) does not impair the crystallinity of the polymer to be produced, and preferably provides the heat resistance, gas barrier properties, mechanical strength, etc. of the resulting film of the present invention. From the standpoint of maintaining, it is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, with respect to 100 parts by mass of all polymerization units.

From the viewpoint of ensuring the oxygen gas barrier property of the film of the present invention obtained by selecting the polyglycolic acid polymer (B1) having the preferred range of configuration described above, the temperature is 23 ° C. in JIS K-7126. In addition, the oxygen gas permeability coefficient (PO ₂ ) of the polyglycolic acid polymer (B1) measured under the condition of 80% relative humidity (RH) is 0.6 ml · mm / (m ² · day · MPa) or less. Is preferably 0.35 ml · mm / (m ² · day · MPa) or less, more preferably 0.07 to 0.35 ml · mm / (m ² · day · MPa). Further preferred. In addition, the oxygen gas permeability of the polyglycolic acid polymer (B1) is hardly affected by humidity. EVOH (saponified ethylene / vinyl acetate copolymer) or polyamide MXD6 (polymetaxylylene adipamide) It is superior compared to.

From the viewpoint of suppressing the water vapor permeability of the resulting film of the present invention by selecting the polyglycolic acid polymer (B1) having the constitution in the preferred range described above, the temperature is 40 ° C. in JIS K-7129. The moisture permeability of the polyglycolic acid polymer (B1) measured under the condition of 90% relative humidity (RH) is preferably ^{2 to} 20 g / m ² · day. The polyglycolic acid polymer (B1) is superior to EVOH (saponified ethylene / vinyl acetate copolymer) from the viewpoint of measurement with an odor sensor, measurement of the amount of L-menthol permeation, and the like. In addition, the polyglycolic acid polymer (B1) is superior to EVOH (saponified ethylene / vinyl acetate copolymer) from the viewpoint of alcohol permeation prevention.

When producing a polymer composition containing a polymer (B1) such as a resin containing a polyglycolic acid polymer (B1) or a resin layer (b) described later, the viscosity at the time of melting is set to an appropriate range. From the viewpoint of ensuring preferable moldability of the film of the present invention, the melt viscosity measured under the conditions of a temperature 20 ° C. higher than the melting point (Tm) (Tm + 20 ° C.) and a shear rate of 120 sec ⁻¹ is 300 to 10,000 Pa · s is preferable, 400 to 8,000 Pa · s is more preferable, and 500 to 5,000 Pa · s is further preferable. From the viewpoint of suppressing the degradation of the polyglycolic acid polymer (B1) and the accompanying molecular weight reduction and foaming, the polymer composition containing the polyglycolic acid polymer (B1) or the melt processing of the resin layer (b) described later The temperature is desirably set to a temperature around 260 ° C. (for example, within a range of 250 to 270 ° C.).

The melting point (Tm) of the polyglycolic acid polymer (B1) is preferably 200 ° C. or higher, preferably 210 ° C. or higher, from the viewpoint of suitably maintaining the gas barrier properties, heat resistance, etc. of the film of the present invention. More preferred. The polyglycolic acid homopolymer has a melting point of about 220 ° C., a glass transition temperature of about 38 ° C., and a crystallization temperature of about 91 ° C. However, these thermal properties vary depending on the molecular weight of the polyglycolic acid polymer (B1), the copolymerization component, and the like. The crystal density (ρ) of the polyglycolic acid homopolymer is about 1.7 g / cm ³ .

  The melting point (Tm) of the polyglycolic acid polymer (B1) is determined by heating the sample to Tm + 20 ° C., which is higher than the expected melting point, using a differential scanning calorimeter, The temperature is defined as the peak value of the melting curve measured by lowering the temperature at a rate of 10 ° C., cooling to 30 ° C., leaving it for about 1 minute, and then increasing the temperature at a rate of 10 ° C. per minute.

[Polymer (B2)]
The aromatic polyester polymer (B2) (hereinafter also referred to as polymer (B2)) used in the present invention is a polymer having an aromatic ring structural unit and an ester bond in the main chain, A polymer or copolymer composed of units derived from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.

  Units derived from aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 1,4- / 1,5- / 2,6- / 2,7-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 4, 4′-diphenyldicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylethane-4,4′-dicarboxylic acid, diphenylpropane-4,4′-dicarboxylic acid, 4,4′-diphenylethercarboxylic acid, 4, 4'-diphenyl sulfide dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, sodium 3-sulfoisophthalate, potassium 3-sulfoisophthalate, etc., or ester-forming derivatives thereof Units derived from. These can use 1 type (s) or 2 or more types. Among these, units derived from terephthalic acid, 2,6-naphthalenedicarboxylic acid, dimethyl terephthalate, and dimethyl 2,6-naphthalene are preferred.

  It is also possible to copolymerize units derived from other dicarboxylic acids. Units derived from other dicarboxylic acids include aliphatics such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc. Examples thereof include units derived from alicyclic dicarboxylic acids such as dicarboxylic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, and ester-forming derivatives thereof. These can use 1 type (s) or 2 or more types.

  The unit derived from diol is preferably an aliphatic diol unit having 2 to 12 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1, Examples thereof include units derived from 10-decanediol, 1,12-dodecanediol and the like. These can use 1 type (s) or 2 or more types. Among these, units derived from 1,2-ethanediol and 1,4-butanediol are more preferable.

  It is also possible to copolymerize units derived from other diols. Examples of units derived from other diols include alicyclic diols such as 1,3- / 1,4-cyclohexanediol, xylylene glycol, 1,2- / 1,3- / 1,4-dihydroxybenzene, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 1,1-bis (4-hydroxyphenyl) methane, 4,4′-dihydroxydiphenylethane, 2,2-bis (4-hydroxyphenyl) propane , Units derived from aromatic diols such as 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl sulfide, and 4,4′-dihydroxydiphenyl sulfone. These can use 1 type (s) or 2 or more types.

  In addition, the aromatic polyester polymer (B2) is a copolymer of trifunctional or higher functional compounds such as glycerin, trimethylpropane, pentaerythritol, trimellitic acid, pyromellitic acid, etc., as long as the molding performance is not substantially lost. It is also possible.

  Specific examples of the aromatic polyester polymer (B2) include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, ethylene terephthalate / isophthalate. Examples thereof include a copolymer, a butylene terephthalate / isophthalate copolymer, a butylene terephthalate / sebacate copolymer, and an ethylene terephthalate / cyclohexylene dimethylene terephthalate copolymer. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate are preferable, and polyethylene terephthalate and polybutylene terephthalate are more preferable because of excellent economy, hot water resistance, dimensional stability, and fragrance retention .

  The aromatic polyester polymer (B2) is obtained by polycondensing the raw material components using a conventionally known polyester production method. The monomer component is charged into the reaction vessel at a predetermined ratio, and the reaction is started in the presence of a catalyst while blowing an inert gas such as nitrogen. By-product low molecular weight compounds are continuously removed from the reaction system. The reaction can be carried out under normal pressure, reduced pressure, or increased pressure, but the reaction is preferably performed under reduced pressure. Then, if desired, the polymer is used in the form of chips or pellets or in the form of blocks. If necessary, solid phase polymerization may be performed according to a conventional method.

  Examples of the catalyst used include tin, antimony, cobalt, manganese, calcium, germanium, nickel, zinc, lead, iron, magnesium and / or titanium compounds. The addition amount of the catalyst is preferably 5 to 100 mmol%, more preferably 10 to 50 mmol%, based on the raw material components. Furthermore, an alkali metal may be added to control the quality such as the number of carboxyl terminal groups. As an alkali metal, lithium, sodium, and potassium are preferable, and potassium is preferable among these. It is preferable that the addition amount of an alkali metal is 0.1-20 mmol% based on a raw material component.

  For the purpose of adjusting the molecular weight and controlling the reaction, monocarboxylic acid, monoalcohol and the like may be used as necessary. Examples of the monocarboxylic acid include benzoic acid, p-oxybenzoic acid, toluene carboxylic acid, salicylic acid, acetic acid, propionic acid, stearic acid and the like. Examples of the monoalcohol include benzyl alcohol, toluene-4-methanol, and cyclohexanemethanol.

  The intrinsic viscosity of the aromatic polyester polymer (B2) measured at 25 ° C. using a 1: 1 mixed solvent of phenol / tetrachloroethane is the productivity during polymerization and the mechanical strength of the resulting film of the present invention. From the standpoint of ensuring, it is preferably 0.25 to 3.0, more preferably 0.40 to 2.5.

[Resin layer (b)]
In the film of the present invention, when the resin layer (b) is laminated with the resin layer (a) and a resin layer (e) to be described later interposed therebetween, particularly good gas barrier properties and interlayer resistance under high temperature and high humidity. It plays a role of ensuring releasability. A resin layer (b) has a polymer (B1) and a polymer (B2) as a main component. When the polymer (B1) and the polymer (B2) are the main components, the resin layer (b) is heavy enough to achieve the role derived from the polymer (B1) and the polymer (B2). The total content of the polymer (B1) and the polymer (B2) in the resin layer (b) is usually 60 to 100% by mass, including the combination (B1) and the polymer (B2). It is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, further preferably 95 to 100% by mass, 97 More preferably, it is -100 mass%, More preferably, it is 99-100 mass%.

  In addition, from the viewpoint of ensuring gas barrier properties under high humidity and delamination resistance under high temperature and high humidity of the film of the present invention, in the resin layer (b), other than the polymers (B1) and (B2) When other polymers are included, the total content of the polymer (B1) and the polymer (B2) is 90 to It is preferably 100% by mass, more preferably 95-100% by mass, and even more preferably 97-100% by mass.

  In addition, the relative content ratio of the polymer (B1) and the polymer (B2) is from the viewpoint of ensuring good gas barrier properties and delamination resistance under high temperature and high humidity of the obtained film of the present invention. The mass ratio of the polymer (B1) and the polymer (B2) to the total amount of the polymer (B1) and the polymer (B2) of 100% by mass (polymer (B1) / polymer (B2)) is mass%. The unit is 60/40 to 90/10, preferably 65/35 to 87/13, and more preferably 68/32 to 85/15.

  In the present invention, when producing the polymer (B1), when producing a polymer composition containing the polymer (B1) such as a resin containing the polymer (B1), and / or producing the resin layer (b). (Hereinafter also referred to as the production of the polymer (B1) or the resin layer (b), etc.), usually added within a range not impairing the effect of the film of the present invention, for example, inorganic Fillers, other thermoplastic resins, plasticizers, catalyst deactivators, heat stabilizers, UV absorbers, light stabilizers, moisture-proofing agents, waterproofing agents, water repellents, lubricants, mold release agents, coupling agents, pigments Various additives such as dyes can be added. The components of these additives remaining in the resin layer (b) are constituent components of the resin layer (b).

  The end of the polymer (B1) becomes a hydroxyl group and / or a carboxyl group at the time of synthesis. The polymer (B1) can be modified with a non-acid-forming OH group blocking agent and / or a carboxyl group blocking agent. The polymer (B1) exhibits hydrolyzability and is easily colored during melt processing. When the polymer (B1) or the resin layer (b) is produced, the non-acid-forming OH group is sealed. By adding an agent and / or a carboxyl group-capping agent, water resistance and hydrolyzability can be improved and coloring can be suppressed.

  “Non-acid-forming” in a non-acid-forming OH group-capping agent means that a carboxyl group is not generated when the OH group remaining in the polymer (B1) is bonded and sealed. is doing. Examples of the non-acid-forming OH group blocking agent include diketene compounds and isocyanates. These can use 1 type (s) or 2 or more types. Among these OH group blocking agents, diketene compounds are preferable from the viewpoint of reactivity. It is preferable that it is 0.01-20 mass parts with respect to 100 mass parts of polymers (B1), and, as for content of OH group terminal blocker, it is more preferable that it is 0.1-10 mass parts.

  As the carboxyl group blocking agent, a compound having a carboxyl group end blocking action and known as a water resistance improver for aliphatic polyesters can be used. Specific examples of the carboxyl group-capping agent include, for example, carbodiimide compounds such as N, N-2,6-diisopropylphenylcarbodiimide, 2,2′-m-phenylenebis (2-oxazoline), 2,2′-p. -Oxazoline compounds such as phenylenebis (2-oxazoline), 2-phenyl-2-oxazoline, styrene isopropenyl-2-oxazoline, and oxazines such as 2-methoxy-5,6-dihydro-4H-1,3-oxazine Examples thereof include epoxy compounds such as compounds, N-glycidylphthalimide, cyclohexene oxide, and tris (2,3-epoxypropyl) isocyanurate. These can use 1 type (s) or 2 or more types.

  Among these carboxyl group-capping agents, carbodiimide compounds are more preferable, and aromatic, alicyclic, and aliphatic carbodiimide compounds are also used, but aromatic carbodiimide compounds are more preferable, and those with particularly high purity are used. Gives water resistance stabilization effect. The content of the carboxyl group sealing agent is preferably 0.01 to 10 parts by mass and more preferably 0.05 to 2.5 parts by mass with respect to 100 parts by mass of the polymer (B1). .

  When producing the polymer (B1) or the resin layer (b), a heat stabilizer can be contained in order to increase the melt stability of the polymer (B1). As the heat stabilizer, a heavy metal deactivator, a phosphate ester having a pentaerythritol skeleton structure, a phosphorus compound having at least one hydroxyl group and at least one long-chain alkyl ester group, a metal carbonate, and the like are preferable. These can use 1 type (s) or 2 or more types.

  Many phosphorous compounds such as phosphite antioxidants are rather unfavorable for use as heat stabilizers because they rather exhibit the effect of inhibiting the melt stability of the polymer (B1). On the other hand, the phosphate ester having a pentaerythritol skeleton structure exhibits an action of specifically improving the melt stability of the polymer (B1). Specific examples of the phosphate ester having a pentaerythritol skeleton structure include cyclic neopentanetetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, cyclic neopentanetetrayl bis (2 , 4-di-t-butylphenyl) phosphite, bis (monononylphenyl) pentaerythritol diphosphite, bis (4-octadecylphenyl) pentaerythritol diphosphite, and the like. These can use 1 type (s) or 2 or more types. Among the phosphorus compounds, phosphorus compounds having at least one hydroxyl group and at least one long-chain alkyl ester group are preferable. The long chain alkyl preferably has 8 to 24 carbon atoms. Specific examples of such phosphorus compounds include mono- or di-stearyl acid phosphate.

  Examples of heavy metal deactivators include 2-hydroxy-N-1H-1,2,4-triazol-3-yl-benzamide, bis [2- (2-hydroxybenzoyl) hydrazine] dodecanedicarboxylic acid, and the like. . Examples of the metal carbonate include calcium carbonate and strontium carbonate.

  Content of a heat stabilizer is 0.001-5 mass parts with respect to 100 mass parts of polymers (B1) from a viewpoint of ensuring the melt stability at the time of film forming of this invention, and process stability. It is preferably 0.003 to 3 parts by mass, and more preferably 0.005 to 1 part by mass.

  When producing the polymer (B2), when producing a resin containing the polymer (B2), and / or when producing the resin layer (b) (hereinafter referred to as the polymer (B2) or the resin layer (b). And so on.), If necessary, within a range that does not impair the effects of the film of the present invention, it is usually blended, for example, each shape such as fibrous, plate-like, and granular. Strengthening agent, antioxidant, heat stabilizer, colorant, UV absorber, mold release agent, antistatic agent, antibacterial agent, fluorescent whitening agent, crystallization accelerator, crystal nucleating agent, filler, lubricant, antibacterial agent Various additives such as a clouding agent, an anti-blocking agent, a slip agent, a plasticizer, a bending fatigue resistance improving material, a flame retardant, and a flame retardant aid can be added. The components of these additives remaining in the resin layer (b) are constituent components of the resin layer (b).

  In the resin layer (b), the resin containing the polymer (B1) and the resin containing the polymer (B2) may be added and mixed separately, or the resin containing the polymer (B1) and the polymer (B2). And a resin containing a mixed composition (hereinafter, also referred to as a polyester polymer composition (B)) obtained by blending and mixing with a resin containing a resin. From the viewpoint of ensuring good delamination resistance with a resin layer (e) described later, the resin layer (b) is preferably molded using a resin containing the polyester polymer composition (B).

  In the resin containing the polyester polymer composition (B), various additives such as a fiber, a plate, and a powder as long as the effects of the film of the present invention are not impaired as necessary. Strengthening agent having shape, antioxidant, heat stabilizer, colorant, ultraviolet absorber, mold release agent, antistatic agent, antibacterial agent, fluorescent whitening agent, crystallization accelerator, crystal nucleating agent, filler, Various additives such as lubricants, anti-fogging agents, anti-blocking agents, slip agents, plasticizers, flexural fatigue resistance improving materials, flame retardants, flame retardant aids, etc. can be added. The component remaining in the layer (b) becomes a constituent component of the resin layer (b).

  In the resin containing the polyester polymer composition (B), the method of blending and mixing the resin containing the polymer (B1) and the resin containing the polymer (B2) is not particularly limited and has been conventionally known. Various methods can be employed. Along with other additives blended as necessary, it can be produced by, for example, a dry blending method of both, a melt kneading method of both, or the like. The melt kneading can be performed using a kneader such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer.

[Polymer (C)]
The polymer (C) used in the present invention is a polyester-based elastomer polymer (α, β-ethylenically unsaturated carboxylic acid (including anhydrides thereof) graft-modified with α, β-ethylenically unsaturated carboxylic acid. ) Is obtained by graft-modifying a polyester-based elastomer, excluding the polymer (B2).), And a resin layer (c) (between the resin layer (a) and the resin layer (b) described later) It is an adhesive polymer that imparts delamination resistance under high temperature and high humidity to the film of the present invention as the main component.

  The polyester elastomer that is a constituent of the polymer (C) is preferably a saturated polyester elastomer, and more preferably a saturated polyester elastomer containing a soft segment made of polyalkylene ether glycol. For example, an aromatic polyester as the hard segment, a polyalkylene ether glycol or an aliphatic polyester as the soft segment is more preferable, and a polyester polyether block copolymer using polyalkylene ether glycol as the soft segment is more preferable. The content of the polyalkylene ether glycol component from the viewpoint of the resin layer (c) described later exhibiting sufficient adhesiveness to the resin layers (a) and (b) and providing sufficient strength to the film of the present invention. Is preferably from 5 to 90 mass%, more preferably from 30 to 80 mass%, still more preferably from 55 to 80 mass%, based on the block copolymer to be produced.

The content of the polyalkylene ether glycol component can be calculated based on the chemical shift of the hydrogen atom and its content using H ¹ -NMR.

  Polyester polyether block copolymers include aliphatic and / or alicyclic diols having 2 to 12 carbon atoms, aromatic dicarboxylic acids and / or alicyclic dicarboxylic acids or ester-forming derivatives thereof, and poly A material obtained by polycondensing an oligomer obtained by an esterification reaction or a transesterification reaction using alkylene ether glycol as a raw material is preferable.

  As the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, those usually used as raw materials for polyesters, particularly polyester thermoplastic elastomers, can be used, for example, 1,2-ethanediol, , 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octane Examples include diol, 1,10-decanediol, 1,12-dodecanediol, 1,3- / 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like. be able to. Among these, 1,2-ethanediol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable.

  As the aromatic dicarboxylic acid and / or alicyclic dicarboxylic acid, those generally used as raw materials for polyesters, particularly polyester thermoplastic elastomers can be used. For example, terephthalic acid, isophthalic acid, phthalic acid 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid, and the like. These can use 1 type (s) or 2 or more types. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid is more preferable. Examples of the ester-forming derivative of aromatic dicarboxylic acid and / or alicyclic dicarboxylic acid include alkyl esters such as dimethyl ester and diethyl ester of the dicarboxylic acid. These can use 1 type (s) or 2 or more types. Among these, dimethyl terephthalate and dimethyl 2,6-naphthalene are preferable.

  In addition to the above components, trifunctional triols, tricarboxylic acids, or esters thereof may be copolymerized in small amounts, and aliphatic dicarboxylic acids such as adipic acid or dialkyl esters thereof may also be copolymerized.

  As the polyalkylene ether glycol, the number average molecular weight is 400 to 6,000 from the viewpoint of securing the block property of the copolymer, suppressing phase separation in the system, and sufficiently securing the physical properties of the polymer. It is preferable that it is 500-4,000, It is more preferable that it is 600-3,000. The number average molecular weight means that measured by gel permeation chromatography (GPC).

  Specific examples of the polyalkylene ether glycol include polyethylene glycol, poly (propylene ether) glycol, poly (tetramethylene ether) glycol, poly (hexamethylene ether) glycol and the like. These can use 1 type (s) or 2 or more types. Among these, poly (tetramethylene ether) glycol is preferable.

  Examples of the α, β-ethylenically unsaturated carboxylic acid that is a constituent of the polymer (C) include acrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. Unsaturated carboxylic acid, succinic acid 2-octen-1-yl anhydride, succinic acid 2-dodecen-1-yl anhydride, succinic acid 2-octadecen-1-yl anhydride, maleic anhydride, 2,3 -Dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, 1-butene-3,4-dicarboxylic anhydride, 1-cyclopentene-1,2- Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3,6-epoxy -1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, endo-bicyclo [2.2 .2] Unsaturated carboxylic acids such as oct-5-ene-2,3-dicarboxylic acid anhydride and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid anhydride An acid anhydride is mentioned. The above α, β-ethylenically unsaturated carboxylic acid can be appropriately selected depending on the copolymer containing the polyalkylene ether glycol segment to be modified and the modification conditions, and one or two or more types are used. Can do. The α, β-ethylenically unsaturated carboxylic acid can be used by dissolving in an organic solvent or the like.

  The modification reaction of the polyester elastomer polymer is preferably performed by reacting the polyester elastomer polymer with an α, β-ethylenically unsaturated carboxylic acid. And this modification | denaturation reaction can also be performed simultaneously with high molecular weight reaction by performing in presence of an active hydrogen compound. In the modification, a radical generator is preferably used. In this modification reaction, a graft reaction in which an α, β-ethylenically unsaturated carboxylic acid or a derivative thereof is added to a polyester elastomer polymer mainly occurs, but a decomposition reaction also occurs. As a result, the polymer (C) has a lower molecular weight and a lower melt viscosity. Further, in the above modification reaction, it is generally considered that a transesterification reaction or the like occurs as another reaction, and the obtained reaction product is generally a composition containing unreacted raw materials, The polymer (C) alone may be used. When the reactant is a composition, the content of the polymer (C) is preferably 10% by mass or more, and more preferably 30% by mass or more.

  As radical generators, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis (tertiary butyl) Oxy) hexane, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, dibutyl peroxy Organic and inorganic peroxides such as oxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (isobutylamide) dihalide, 2,2 '-Azobis [2-methyl-N- (2-hydroxyethyl Propionamide], azo compounds such as azodi -t- butane, carbon radical generating agents such as dicumyl like. The above radical generator can be appropriately selected according to the type of polyester elastomer polymer used for the modification reaction, the type of α, β-ethylenically unsaturated carboxylic acid and the modification conditions, and can be one or two types. The above can be used. The radical generator can be used by dissolving in an organic solvent or the like.

  As the modification reaction for obtaining the polymer (C), known reaction methods such as a melt-kneading reaction method, a solution reaction method, a suspension-dispersion reaction can be used, but a melt-kneading reaction method is usually preferable.

  In the case of the melt-kneading reaction method, the resin containing the polyester-based elastomer polymer and the above-mentioned components may be melt-kneaded after uniformly mixing other additives at a predetermined content as required. For mixing, a Henschel mixer, ribbon blender, V-type blender, etc. are used for uniform mixing, and for melt kneading, a Banbury mixer, kneader, roll, uniaxial or biaxial multi-screw kneading extruder, etc. are used. The Further, an active hydrogen compound described later and other optional components may be supplied from the middle and melt kneaded. The melt kneading temperature is preferably 100 to 300 ° C., more preferably 120 to 280 ° C., and further preferably 150 to 250 ° C. so that the resin is not thermally deteriorated.

  The content of the α, β-ethylenically unsaturated carboxylic acid is sufficiently modified to ensure the adhesiveness of the polymer (C), and excessively lower the viscosity at the time of melting of the produced polymer (C). From the viewpoint of securing the moldability of the polymer (C), it is preferably 0.01 to 30 parts by mass, and 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyester elastomer polymer. More preferably, it is 0.1-1 mass part.

  The content of the radical generator is obtained by sufficiently modifying, ensuring the adhesion of the polymer (C), and suppressing the lower molecular weight (decrease in viscosity) during the modification of the polymer (C). From the viewpoint of securing the strength of the film of the invention, it is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the polyester elastomer polymer. It is more preferable that it is 0.01-0.2 mass part, and it is especially preferable that it is 0.01-0.1 mass part.

  For the polymer (C) obtained as described above, the durometer type was measured in accordance with JIS K-6253 from the viewpoint of ensuring the mechanical strength of the obtained film of the present invention and ensuring rubber elasticity and interlayer adhesion. The hardness according to D (JIS-D hardness) is preferably 10 to 80, more preferably 15 to 70, and still more preferably 20 to 60. Furthermore, the MFR (230 ° C., 2.16 kg load) of the polymer (C) does not excessively lower the melt tension of the polymer (C), does not cause problems such as drawdown during molding, and is fluid. From the viewpoint of securing moldability without excessively shorting out, it is preferably 1 to 300 g / 10 minutes, more preferably 3 to 150 g / 10 minutes, and 5 to 100 g / 10 minutes. Is more preferable.

The modification rate (graft amount) of the polymer (C) can be determined according to the following formula from the spectrum obtained by H ¹ -NMR measurement.
Graft amount (mass%) = 100 × (C ÷ 3 × 98) / {(A × 148 ÷ 4) + (B × 72 ÷ 4) + (C ÷ 3 × 98)}
(However, A is an integral value of 7.8 to 8.4 ppm, B is an integral value of 1.2 to 2.2 ppm, and C is an integral value of 2.4 to 2.9 ppm.)

  The modification rate (graft amount) of the polymer (C) determined as described above is such that the functional group in the polymer (C) is not too small, ensuring adequate adhesion, and molecular degradation during the modification process. From the viewpoint of securing the strength of the film of the present invention, it is preferably 0.01 to 10% by mass, more preferably 0.03 to 7% by mass, and 0.05 to 5% by mass. More preferably.

  Further, in order to improve the adhesion, vinyl aroma such as styrene, methyl styrene, ethyl styrene, isopropyl styrene, phenyl styrene, o-methyl styrene, 2,4-dimethyl styrene, o-chloro styrene, o-chloromethyl styrene, etc. A group monomer or the like can also be contained as a modification aid.

[Resin layer (c)]
In the film of the present invention, the resin layer (c) is laminated between the resin layer (a) and the resin layer (b) in contact with the resin layer (a) and / or the resin layer (b). The film of the present invention is imparted with delamination resistance under high temperature and high humidity without hindering gas barrier properties under high humidity under high temperature and high humidity.

  The resin layer (c) contains the polymer (C) as a main component. The main component of the polymer (C) is that the resin layer (c) contains the polymer (C) to such an extent that the above-described role derived from the polymer (C) can be achieved. The content of the polymer (C) in (c) is usually 70 to 100% by mass, preferably 80 to 100% by mass, more preferably 90 to 100% by mass, More preferably, it is -100 mass%, It is more preferable that it is 97-100 mass%, It is more preferable that it is 99-100 mass%.

  In addition, from the viewpoint of securing the gas barrier property under high humidity and the delamination resistance under high temperature and high humidity of the film of the present invention, a polymer other than the polymer (C) is contained in the resin layer (c). Is included, the content of the polymer (C) is preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the polymer (C) and the other polymer. Is more preferable, and it is still more preferable that it is 97-100 mass%.

  When producing a polymer (C), when producing a polymer composition containing a polymer (C) such as a resin containing the polymer (C), and / or when producing a resin layer (c) ( Hereinafter, it is also referred to when producing the resin layer (c), etc.), within a range not impairing the effect of the film of the present invention, depending on the purpose, resin component, rubber component, talc, calcium carbonate, mica, Fillers such as glass fibers, plasticizers such as paraffin oil, antioxidants, heat stabilizers, light stabilizers, UV absorbers, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, crosslinking agents, crosslinking Various additives such as auxiliaries, colorants, flame retardants, dispersants, antistatic agents, antibacterial agents, and fluorescent brighteners can be added. The component remaining in the resin layer (c) of these additives becomes a constituent component of the resin layer (c).

[Resin layer (d)]
In the film of the present invention, the resin layer (d) is formed from the viewpoint of recycling and using the raw material of the film, and the film barrier property of the film of the present invention under the high humidity and the interlayer adhesion resistance under the high temperature and high humidity. This is useful when substituting a part of the resin layer (c) without hindering.

  The resin layer (d) is composed mainly of the polymer (A), the polymer (B1), the polymer (B2), and the polymer (C) (hereinafter also referred to as polymer (A) or the like). And resin layers (a), (b) and (c) are excluded). To have the polymer (A) or the like as a main component means that the resin layer (d) contains the polymer (A) or the like to such an extent that the role derived from the polymer (A) or the like can be achieved. The total content of the polymer (A), the polymer (B1), the polymer (B2) and the polymer (C) in the resin layer (d) is usually 70 to 100% by mass, and 80 to 100 It is preferably mass%, more preferably 90 to 100 mass%, further preferably 95 to 100 mass%, further preferably 97 to 100 mass%, and 99 to 100 mass%. More preferably it is.

  In addition, from the viewpoint of securing the gas barrier property under high humidity and the delamination resistance under high temperature and high humidity of the film of the present invention, the resin layer (d) contains other heavy materials other than the polymer (A) and the like. From the viewpoint of ensuring releasability with respect to the total amount of the polymer (A), the polymer (B1), the polymer (B2), the polymer (C) and the other polymer, the resin layer When (d) contains a polymer other than the polymer (A) or the like, the polymer (A), polymer (B1), polymer (B2), and polymer (in the resin layer (d) ( The total content of C) is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and still more preferably 97 to 100% by mass.

  The resin layer (d) may be a mixture of virgin raw materials, or a film of the present invention or a laminated film constituting the film of the present invention (hereinafter also referred to as the film of the present invention). ) May be prepared by adding a virgin raw material to the scrap mixture generated as a non-standard film generated at the time of manufacturing, a cut end material (ear trim) of the film side end portion, or the scrap mixture. . Industrially, it is advantageous from the viewpoint of material cost reduction and waste reduction to recycle trimming film or the like obtained by cutting the edge of the film discharged during the production process of the present invention as a mixed resin.

  In the resin layer (d), the polymer (B1), the polymer (B2), and the polymer from the viewpoint of securing the gas barrier property under high humidity and the delamination resistance under high temperature and high humidity of the film of the present invention. The total amount of the polymer (B1) and the polymer (B2) and the mass ratio of the polymer (C) (the sum of the polymer (B1) and the polymer (B2) with respect to 100% by mass of the total amount of (C). / Polymer (C)) is preferably 15 to 85/85 to 15 in terms of mass%.

  In the resin layer (d), from the viewpoint of ensuring gas barrier properties and delamination resistance under high temperature and high humidity of the film of the present invention, the content of the polymer (A) in the resin layer (d) is 30 to 30%. It is preferably 90% by mass, more preferably 35 to 85% by mass, and further preferably 40 to 80% by mass.

[Resin layer (e)]
The resin layer (e) formed in the film of the present invention is composed of a resin layer (c) or a laminate in which the resin layer (c) and the resin layer (d) are in contact with each other. The resin layer (e) is laminated between the resin layer (a) and the resin layer (b) in contact with both layers, and the film of the present invention is highly humid by the resin layer (a) and the resin layer (b). It plays the role of ensuring interlayer adhesion resistance under high temperature and high humidity without impairing the gas barrier property. From the viewpoint of recycling and using the raw material of the film of the present invention, the resin layer (e) is preferably constituted by the resin layer (d).

  The resin layer (e) is a resin layer (a) and a resin layer (from the viewpoint of ensuring interlayer adhesion resistance under high temperature and high humidity without impairing gas barrier properties under high humidity of the film of the present invention. At least one surface side in contact with b) is the resin layer (c). Therefore, the lamination mode of the resin layer (c) and the resin layer (d) of the resin layer (e) is preferably a single layer of the fat layer (c), and further, the raw material of the film of the present invention is recycled. From the viewpoint of use, it is a lamination of a resin layer (c) and a resin layer (d).

The resin layer (c) is represented by “(c)”, the resin layer (d) is represented by “(d)”, and the contact surface between the resin layer (c) and the resin layer (d) is represented by “/”. ) And the resin layer (d) as a preferred lamination mode,
(C) / (d) / (c)
(C) / (d) / (c) / (d) / (c)
(C) / (d),
(C) / (d) / (c) / (d),
(C) / (d) / (c) / (d) / (c) / (d),
Etc.

In addition, when there are a plurality of resin layers (c) in the resin layer (e), the resin layer (c) belongs to the resin layer (c) as long as the condition of the resin layer (c) is satisfied. A plurality may be selected. The same applies when there are a plurality of resin layers (d) in the resin layer (e). For example, a polymer belonging to the resin layer (c) and a resin layer (c ₁ ) and a resin layer (c ₂ ) having different compositions are selected, and (c ₁ ) / (c ₂ ), (c ₁ ) / (d ) / (C ₂ ) may be used to form the resin layer (e).

〔the film〕
The film of the present invention is a film including a resin layer (S) in which a resin layer (a), a resin layer (b), and a resin layer (e) are laminated, and the resin layer (S) The resin layer (e) is laminated between the resin layer (a) and the resin layer (b) in contact with the resin layer (a) and the resin layer (b), and the resin layer of the oil layer (e) At least one of the surfaces in contact with (a) and the resin layer (b) is the resin layer (c). When the resin layer (S) is manufactured, for example, a laminated film (u) of the resin layer (a) and the resin layer (c), and a laminated film (v) of the resin layer (d) and the resin layer (b) (v) ), The resin layer (c) and the resin layer (d) are brought into contact with each other to form a resin layer (S). In the obtained resin layer (S), the resin layer (a) and the resin layer It is considered that the resin layer (e) in which the layer (c) and the resin layer (d) are laminated and the resin layer (b) are laminated. That is, in the resin layer (S), the resin layer (c) or the laminated portion composed of the resin layers (c) and (d) is regarded as the resin layer (e).

  The film of the present invention is excellent in delamination resistance due to the resin layer (S) being formed, and particularly excellent in durability of delamination strength after treatment in a high temperature and high humidity atmosphere.

  Further, the number of the resin layers (S) is not particularly limited, but is preferably 8 or less, more preferably 4 to 8 layers, more preferably 4 layers as judged from the mechanism of the film or laminate production apparatus. More preferably, it is ˜7 layers.

  The resin layer (a) is “(a)”, the resin layer (b) is “(b)”, and the resin layer (e) is “[e: Lamination of resin layer (c) and resin layer (d)]” When the contact surface between the respective layers is represented by “/”, the following preferable examples of the lamination of the resin layer (S) are as follows.

Three-layer structure:
(A) / [e: (c)] / (b)
4-layer structure:
(A) / [e: (c) / (d)] / (b),
(A) / [e: (d) / (c)] / (b),
5-layer structure:
(A) / [e: (c)] / (b) / [e: (c)] / (a),
6-layer structure:
(A) / [e: (c)] / (b) / [e: (c) / (d)] / (a)
(A) / [e: (c)] / (b) / [e: (d) / (c)] / (a)
7-layer structure:
(A) / [e: (d) / (c)] / (b) / [e: (c) / (d)] / (a),
(A) / [e: (c) / (d)] / (b) / [e: (d) / (c)] / (a)

In addition, when there are a plurality of resin layers (a) in the resin layer (S), the resin layer (a) belongs to the resin layer (a) as long as the condition of the resin layer (a) is satisfied. A plurality may be selected. The same applies when there are a plurality of resin layers (b) and resin layers (e) in the resin layer (S). For example, a polymer belonging to the resin layer (a) and a resin layer (a ₁ ) and a resin layer (a ₂ ) having different compositions are selected,
(A ₁ ) / (a ₂ ) / [e: (c)] / (b),
(A ₁ ) / [e: (c)] / (b) / [e: (c)] / (a ₂ ),
(A ₁ ) / [e: (c)] / (b) / [e: (c)] / (a ₁ ) / (a ₂ ),
(A ₁ ) / (a ₂ ) / [e: (c)] / (b) / [e: (c)] / (a ₂ ) (a ₁ ),
(A ₁ ) / (a ₂ ) / [e: (c)] / (b) / [e: (c)] / (a ₁ ),
(A ₁ ) / (a ₂ ) / [e: (c)] / (b) / [e: (c)] / (a ₁ ) / (a ₂ ),
The resin layer (S) may be configured in such a laminated manner.

In the resin layer (S), the resin layer (e) is laminated between the resin layer (a) and the resin layer (b) in contact with the resin layer (a) and the resin layer (b). If a laminate in an embodiment in which at least one surface side of the surface in contact with the resin layer (a) and the resin layer (b) of the layer (e) is the resin layer (c) is included, other laminate embodiments and polymers Other resin layers having different compositions may be further laminated. For example, the following lamination | stacking aspects are mentioned.
(A) / [e: (c)] / (b) / (c),
(D) / (a) / [e: (c)] / (b),
(A) / [e: (c)] / (b) / (d)
(A) / [e: (c)] / (b) / [e: (c) / (d)]
(A) / [e: (c)] / (b) / (d) / (a)
(A) / [e: (c)] / (b) / [e: (c)] / (a) / (d)
[E: (d) / (c)] / (b) / [e: (c)] / (a) / (d)
(D) / (a) / [e: (c)] / (b) / [e: (c)] / (a) / (d)

From the viewpoint of ensuring gas barrier properties under high humidity and interlayer adhesion resistance under high temperature and high humidity of the film of the present invention, preferably, as a lamination mode of the resin layer (S),
(A) / [e: (c)] / (b) / [e: (c)] / (a),
(A ₁ ) / (a ₂ ) / [e: (c)] / (b) / [e: (c)] / (a ₁ ),
(A ₁ ) / (a ₂ ) / [e: (c)] / (b) / [e: (c)] / (a ₁ ) / (a ₂ ),
(A) / [e: (d) / (c)] / (b) / [e: (c) / (d)] / (a),
(A) / [e: (c) / (d)] / (b) / [e: (d) / (c)] / (a)
It is.

  In addition, as a packaging material for boil sterilization, when the film of this invention is comprised only by the resin layer (S), from a viewpoint of ensuring water resistance and hot water resistance, resin layers other than the resin layer (b) are films. It is preferable to arrange in the outermost layer.

  The resin layer (S) contained in the film of the present invention preferably has a polymer (A), a polymer (B1), a polymer (B2) (or a polyester polymer composition (B)), and a weight Using the union (C), an unstretched laminated film that is substantially amorphous and not oriented can be produced by a method such as a coextrusion method, and then the unstretched laminated film can be obtained by stretching. . For example, a resin raw material melted in a separate extruder is continuously extruded from a T-die, and co-extruded T-die method in which it is formed into a film while cooling with a casting roll, continuously extruded from an annular die, A co-extrusion water-cooled inflation method in which water is brought into contact and cooling, a co-extrusion air-cooled inflation method in which extrusion is performed from an annular die, and cooling is performed by air can be used. The produced film can be used as a substantially non-oriented unstretched laminated film, but is preferably a biaxially stretched film from the viewpoint of the strength and gas barrier of the resulting film of the present invention. As a method for forming a raw film for stretched laminated film, a coextrusion T-die method and a coextrusion water-cooled inflation method are particularly excellent in terms of continuous stretching.

  In order to stretch the obtained unstretched laminated film, conventionally known industrial methods can be applied. For example, a film produced by the casting method can be obtained by a simultaneous biaxial stretching method in which an unstretched laminated sheet is stretched simultaneously in the vertical and horizontal directions with a tenter-type simultaneous biaxial stretching machine, or an unstretched laminated sheet melt-extruded from a T-die in a roll-type stretching machine. An example is a sequential biaxial stretching method in which the film is stretched in the direction and then stretched in the transverse direction with a tenter type stretching machine. There is a tubular stretching method in which a tubular sheet formed from an annular die is stretched simultaneously in the longitudinal and lateral directions by gas pressure. The stretching step may be carried out continuously following the production of the unstretched laminated sheet, or the unstretched laminated sheet may be wound once and stretched as a separate step.

  Although the draw ratio of the laminated film varies depending on the intended use, from the viewpoint of securing the strength and gas barrier properties of the obtained film of the present invention and preventing the film from tearing and breaking during stretching, a tenter type biaxial stretching method, tube In the Luller method, it is usually preferably 1.5 to 5.0 times in both the vertical and horizontal directions, and more preferably 2.5 to 4.5 times.

The stretching temperature is preferably 30 to 210 ° C., more preferably 50 to 200 ° C., from the viewpoint of suppressing deterioration of formability due to increased stress during stretching and suppressing whitening due to accelerated crystallization.
For example, in the tenter-type sequential biaxial stretching method, the laminated unstretched film is heated to a temperature range of 40 to 120 ° C., stretched in the machine direction by a roll-type longitudinal stretching machine, and subsequently 60-180 by a tenter-type lateral stretching machine. A laminated biaxially stretched film can be produced by stretching in the transverse direction within a temperature range of ° C. More preferably, the stretching temperature in the longitudinal direction is 70 to 100 ° C, and the stretching temperature in the transverse direction is 80 to 160 ° C.

  The laminated film produced by the above method is subsequently heat treated. Dimensional stability at room temperature can be imparted by heat treatment. In this case, it is preferable to select a heat treatment temperature in a range in which the lower limit is 80 ° C. and the upper limit is a temperature 5 ° C. lower than the melting point of the resin. A stretched film can be obtained.

  It is desirable that the laminated film has poor or substantially no heat shrinkability. Therefore, the temperature of the heat treatment performed after stretching is preferably 80 ° C. or higher, and more preferably 80 to 180 ° C. The relaxation rate is preferably within 20% in the width direction, and more preferably 3 to 10%. The laminated biaxially stretched film sufficiently heat-set by the heat treatment operation can be cooled and wound up according to a conventional method.

  Furthermore, the obtained laminated 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. In addition, after such processing is performed as necessary, it is used for the intended purpose through secondary processing steps such as printing, laminating, adhesive coating, heat sealing, vapor deposition, bag making, deep drawing, etc. can do.

  The film of the present invention is preferably composed of only the resin layer (S) from the viewpoint of securing gas barrier properties under high humidity and delamination resistance under high temperature and high humidity, but is based on the resin layer (S). The resin layer (having gas barrier properties and delamination resistance under high temperature and high humidity, and within a range not deteriorating the gas barrier properties under high humidity and delamination resistance under high temperature and high humidity of the film of the present invention) S) may be processed other than the lamination of the resin layers.

  The resin layer (S) contained in the film of the present invention is excellent in gas barrier properties under high humidity and delamination resistance under high temperature and high humidity. The resin layer (a), resin layer (b) and resin layer Even if it consists only of e), the utility value is high, but in addition to the resin layer (a), the resin layer (b), and the resin layer (e), a further function is provided or an economically advantageous film is obtained. Therefore, a base resin layer made of another thermoplastic resin can be laminated on the inner side or the outer side of the resin layer (S) and included in the resin layer (S).

  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, polyacetal (POM), polyphenylene oxide (PP) ), Etc., polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polyphenylene ether resins such as polyphenylene sulfide (PPS) and polythioethersulfone (PTES), polyetheretherketone (PEEK) ), Polyketone resins such as polyallyl ether ketone (PAEK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene Polymethacrylate resins such as copolymers (ABS), methacrylonitrile / styrene / butadiene copolymers (MBS), polymethacrylates such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA) Rate resins, polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymers, vinylidene chloride / methyl acrylate copolymers, etc. Polyvinyl resins, cellulose resins such as cellulose acetate and cellulose butyrate, polycarbonate resins such as polycarbonate (PC), polyimide resins such as thermoplastic polyimide (PI), polyamideimide (PAI), and polyetherimide, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene Rene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / perfluoro (alkyl vinyl ether) Examples thereof include fluorine resins such as copolymers (PFA), thermoplastic polyurethane resins, polyurethane elastomers, polyester elastomers other than those specified in the present invention, polyamide elastomers, and the like.

  Moreover, the obtained laminated film can be 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 method for laminating the sealant layer, a general method such as extrusion laminating and dry laminating, or a combination thereof is adopted, but the method is not limited thereto. For example, in the case of extrusion lamination, an anchor coat agent is applied to the laminated film of the present invention and a substrate such as a thermoplastic resin, respectively, and after drying, a roll is melted and extruded while a thermoplastic resin such as a polyethylene resin is melted. A laminate film can be obtained by cooling between the layers and press-bonding them under pressure. In the case of dry lamination, a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound is applied to the laminated film of the present invention, and after drying, it is bonded to a base material such as a thermoplastic resin. Thus, a laminate film is obtained. When laminating, it is preferable to use one side or both sides of the laminated film of the present invention after corona treatment. The film after lamination can be increased in adhesive strength by aging.

  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 inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, chromium oxide, zinc oxide, cobalt oxide, and tin oxide, organic compounds such as HMDSO (hexamethyldisiloxane), and silane gas. Examples thereof include silicon oxide obtained by a reaction after mixing such an inorganic gas with a carrier gas and oxygen for oxidizing. As a method for producing a vapor deposition film, a vacuum deposition method, an EB deposition method, a sputtering method, an ion plating method, a chemical deposition method (CVD) method as a physical deposition method (PVD method), a plasma CVD method or a chemical reaction method. Etc. can be used.

  The thickness of the film of the resin layer (S) is not particularly limited as long as it is appropriately determined depending on the use, but the gas barrier property, pinhole resistance balance is secured, and the obtained film of the present invention is suppressed from becoming hard, Furthermore, it is preferable that it is 5-200 micrometers from a viewpoint of ensuring the suitability for soft packaging, and the whole film at the time of being laminated is not too thick, It is more preferable that it is 10-150 micrometers, It is 12-100 micrometers. Is more preferable.

  The thickness of each layer in the resin layer (S) is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the resin layer (S), the use of the film of the present invention, and the like. However, the thickness of each layer is such that the resin layers (a), (b) and (c) have the thicknesses of the resin layer (S) such as gas barrier properties, mechanical properties, flexibility, and transparency. The thickness is preferably 3 to 90% with respect to the total thickness of the resin layer (S). In consideration of gas barrier properties, the thickness of the resin layer (b) is preferably 5 to 70%, more preferably 10 to 50% with respect to the total thickness of the resin layer (S).

  By selecting the resin layers (a), (b), (c) and (d) having the configuration in the above preferred range, the resin layer (S) has a delamination strength as a packaging bag. From the viewpoint of suppressing the delamination phenomenon, so-called delamination, it is preferably 1.8 N / cm or more, and more preferably 2.0 N / cm or more. In the present invention, the delamination strength means that after peeling a film edge having a width of 15 mm between layers, in a 20% C. relative humidity (RH) 65% atmosphere, using a universal material testing machine, a tensile rate of 200 mm / This is a value obtained by conducting a T-peeling test under the condition of minutes, obtaining a maximum point in the elongation-strength graph, and averaging each data.

The resin layer (S) preferably has an oxygen gas permeability of 250 ml / (m ² · day · MPa) or less measured under an atmosphere of 20 ° C. and relative humidity (RH) 100% in JIS K-7126. More preferably, it is 200 ml / (m ² · day · MPa) or less.

  The film of the present invention is useful as a film for food packaging, medical treatment, and medicine packaging that dislikes alteration of the contents due to oxygen, and is particularly suitable for food, medical treatment, and medicine packaging applications with high water activity. In the heat sterilization treatment such as retort treatment and post-processing such as printing and laminating, the delamination phenomenon (delamination) does not occur, and its utility value is extremely large.

  The film of the present invention is used for general foods, seasonings such as mayonnaise and dressing, fermented foods such as miso, fat and oil foods such as salad oil, processed meat packaging, powdered food packaging, electric / electronic Used for parts packaging, beverages, cosmetics, pharmaceuticals, detergents, cosmetics, industrial chemicals, agricultural chemicals, fuel packaging, wallpaper, mats, flooring, flexible containers, containers, antifouling films, dustproof films, balloons, etc. Can do. In particular, it is useful as a packaging material for foods, pharmaceuticals, medicines, fragrances and the like having a high water activity because the contents do not change due to oxygen. More specific uses of the film packaging material include lid materials, pouches, vacuum packaging, skin packs, deep drawing packaging, and rocket packaging. The pouches are used in the form of a three-side seal, a four-side seal, a pillow, a gusset, a standing pouch, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.

  Various evaluation methods for raw materials and films used in Examples and Comparative Examples are shown.

[Raw materials used in Examples and Comparative Examples]
(1) Polymer (A)
As the polymer (A), polymers (A-1), (A-2), (A-3) and (A-4) were produced under the conditions of the production examples described later.

Production Example (1-1) Polymer (A-1)
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) in a pressure-resistant reaction vessel equipped with a stirrer with an internal volume of 70 liters The mixture was 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 pellets. Then, after immersing this pellet in hot water and extracting and removing an unreacted monomer, it dried under reduced pressure and obtained the polymer (A-1).

  The polymer (A-1) had a relative viscosity ηr of 3.36, a terminal amino group concentration [X] of 55 μeq / g, and a terminal carboxyl group concentration [Y] of 35 μeq / g. [X] and [Y] are [X] − [Y] = 20> 0.2 × 10000 / ((ηr− (18−x) / 10) × M) = 0.2 × 10000 / ((3 .36− (18−5) / 10) × 113) = 8.6 μeq / g. [X] = 55> 1.1 × 10000 / ((ηr− (18−x) / 10) × M) = 1.1 × 10000 / ((3.36− (18−5) / 10) × 113) = 47 μeq / g.

Production Example (1-2) Polymer (A-2)
In Production Example (1-1), except that 37.6 g (1/400 eq / mol caprolactam) of isophorone diamine was changed to 51.3 g (1/200 eq / mol caprolactam) of 1,6-hexanediamine, Production Example A polymer (A-2) was obtained by the same method as (1-1).

  The polymer (A-2) had a relative viscosity ηr of 3.19, a terminal amino group concentration [X] of 68 μeq / g, and a terminal carboxyl group concentration [Y] of 27 μeq / g. [X] and [Y] are [X] − [Y] = 41> 0.2 × 10000 / ((ηr− (18−x) / 10) × M) = 0.2 × 10000 / ((3 19− (18−5) / 10) × 113) = 9.4 μeq / g. [X] = 68> 1.1 × 10000 / ((ηr− (18−x) / 10) × M) = 1.1 × 10000 / ((3.19− (18−5) / 10) × 113) = 52 μeq / g.

Production Example (1-3) Polymer (A-3)
In Production Example (1-1), 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. A polymer (A-3) was obtained in the same manner as in Production Example (1-1) except that the mixture was changed to 46.6 g (1/300 eq / mol caprolactam) with hexanediamine.

  The relative viscosity ηr of the polymer (A-3) was 3.60, the terminal amino group concentration [X] was 52 μeq / g, and the terminal carboxyl group concentration [Y] was 25 μeq / g. [X] and [Y] are [X] − [Y] = 27> 0.2 × 10000 / ((ηr− (18−x) / 10) × M) = 0.2 × 10000 / ((3 .60− (18−5) / 10) × 113) = 7.7 μeq / g. [X] = 52> 1.1 × 10000 / ((ηr− (18−x) / 10) × M) = 1.1 × 10000 / ((3.60− (18−5) / 10) × 113) = 42 μeq / g.

Production Example (1-4) Polymer (A-4)
Production Example (1-1) except that 37.6 g (1/400 eq / mol caprolactam) of isophoronediamine was changed to 15.2 g (1/700 eq / mol caprolactam) of acetic acid in Production Example (1-1). In the same manner as above, a polymer (A-4) was obtained.

  The relative viscosity ηr of the polymer (A-4) was 3.45, the terminal amino group concentration [X] was 31 μeq / g, and the terminal carboxyl group concentration [Y] was 41 μeq / g. [X] and [Y] are [X] − [Y] = − 10 <0.2 × 10000 / ((ηr− (18−x) / 10) × M) = 0.2 × 10000 / (( 3.45− (18−5) / 10) × 113) = 8.2 μeq / g. [X] = 31 <1.1 × 10000 / ((ηr− (18−x) / 10) × M) = 1.1 × 10000 / ((3.45− (18−5) / 10) × 113 = 45 μeq / g

(2) Polymer composition containing polymer (B1) The polymer composition (B1-1) and the polymer composition (B1-2) were used as the polymer (B1).

Production Example (2-1) Polymer Composition (B1-1)
The polymer composition (B1-1) was manufactured by Asahi Denka Co., Ltd. Adekastab AX-71 (monostearyl phosphate 50 mol% and phosphoric acid as a heat stabilizer with respect to 100 parts by mass of the polyglycolic acid homopolymer. Distearyl (50 mol%) was added at a rate of 0.03 parts by mass.

The melt viscosity of the polymer composition (B1-1) measured at a temperature (Tm + 20 ° C.) 20 ° C. higher than the melting point Tm of the polymer composition (B1-1) and a shear rate of 122 sec ⁻¹ is 1,600 Pa · s. there were.

Production Example (2-2) Polymer Composition (B1-2)
As the polymer (B1), at the time of synthesis of the polyglycolic acid homopolymer, 100 parts by mass of the polyglycolic acid homopolymer is reacted with 0.5 part by mass of N, N-2,6-diisopropylphenylcarbodiimide, What sealed the carboxyl group terminal of polyglycolic acid was used. As a heat stabilizer, the polymer composition (B1-2) is Adekastab AX-71 (monostearyl phosphate 50 mol% and diphosphate phosphate as a heat stabilizer with respect to 100 parts by mass of the polymer (B1). Stearyl 50 mol%) was added at a ratio of 0.03 parts by mass.

The melt viscosity of the polymer composition (B1-2) measured at a temperature (Tm + 20 ° C.) 20 ° C. higher than the melting point Tm of the polymer composition (B1-2) and a shear rate of 122 sec ⁻¹ is 1,200 Pa · s. there were.

(3) Polymer (B2)
As the polymer (B2), polybutylene terephthalate (hereinafter referred to as polymer (B2-1)) (manufactured by Mitsubishi Engineering Plastics Co., Ltd., NOVADURAN 5020) was used.

(4) Production Example of Polymer Composition Containing Polymer (C) and Polymer (C) (4-1) Polymer (C-1)
A polyester polyether block copolymer having polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 2,000 as a soft segment, wherein the polytetramethylene ether glycol segment in the copolymer 100 parts by mass of a polyester elastomer having a content of 65% by mass, 0.5 parts by mass of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), and 2,5-dimethyl-2,5- 0.05 parts by mass of bis (t-butylperoxy) hexane (Nippon Yushi Co., Ltd., Perhexa 25B) is mixed in advance, and supplied to a biaxial melt kneader (Nippon Steel Works, Ltd., model: TEX44). After melt-kneading at a cylinder temperature of 190 to 230 ° C. and extruding the molten resin into strands, Was introduced into a water tank, cooled, using cut, the pellets of the modified polyester elastomer obtained by vacuum drying the polymer (C) (hereinafter. Referred to as polymer (C-1)). In the polymer (C-1), the amount of modification measured by infrared absorption spectrum was 0.34.
(4-2) Polymer composition (C-2)
As the polymer (C), a polymer composition (manufactured by Toray DuPont, Hytrel 4275) containing an unmodified polyester elastomer (hereinafter referred to as polymer (C-2)) was used.

(5) Polymer composition (A-1), polymer composition (B1-1), polymer (B2-1), and mixture of polymer (C-1) Polymer (A-1) described later and Generated from the film production test of each resin single composition of polymer composition (A-1), polymer composition (B1-1), polymer (B2-1) and polymer (C-1) containing silica. Ear trim end materials were mixed to obtain a mixture (D-1). The composition of the mixture (D-1) is
Polymer composition (A-1) 50 mass%,
25.5% by mass of the polymer composition (B1-1),
8.5% by mass of polymer (B2-1),
16% by mass of polymer (C-1)
It is.

(6) Adhesive resin (6-1) Adhesive resin (E-1)
Maleic acid-modified polyethylene: Mitsui Chemicals, Admer NF528, MFR 2.2 g / 10 min (190 ° C., under 2160 g load), melting point 120 ° C.
(6-2) Adhesive resin (E-2)
Ethylene / glycidyl methacrylate / vinyl acetate copolymer: manufactured by Sumitomo Chemical Co., Ltd., Bond First 2B, MFR 3.0 g / 10 min (under 190 ° C. and 2160 g load), melting point 95 ° C.

(7) Barrier resin (7-1) Barrier resin (F-1)
Saponified ethylene / vinyl acetate copolymer (EVOH): manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol DC3203, ethylene content 32 mol%
(7-2) Barrier resin (F-2)
Polymetaxylylene adipamide (polyamide MXD6): manufactured by Mitsubishi Gas Chemical Co., Ltd., MX-nylon 6011

[Various evaluation methods for films, etc.]
[Relative viscosity]
In JIS K-6920, it measured on 96 mass% sulfuric acid on the conditions of a polyamide (polymer (A)) density | concentration of 1 mass%, and the temperature of 25 degreeC.

[Terminal carboxyl group concentration]
A predetermined amount of polyamide (polymer (A)) sample is put into a three-neck pear-shaped flask, and after adding 40 mL of benzyl alcohol, it is 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 (polymer (A)) sample in a conical flask with a stopcock, add 40 mL of a previously prepared solvent phenol / methanol (volume ratio 9/1), and stir and dissolve with a magnetic stirrer. Then, titration was performed with 0.05 N hydrochloric acid using thymol blue as an indicator to determine the terminal amino group concentration.

[Oxygen gas permeability]
According to the method defined in JIS K-7126 (isobaric method), using a gas permeation measuring device (MOCON-OX-TRAN 2/20, manufactured by Modern Control Co., Ltd.), 23 ° C., relative humidity (RH) The oxygen gas permeability was measured under the conditions of 80% and 100%, and based on the measured value and the film thickness, the oxygen gas permeability coefficient (unit: ml / (m ² · day · MPa) / (one sheet thickness) )) Was calculated.

[Delamination strength]
An organic solvent is soaked into the edge of a film with a width of 15 mm, slightly swollen, and the part peeled off between the layers is used as a grip part, and then in a 20 ° C. and 65% relative humidity (RH) atmosphere. Using a material testing machine (manufactured by Shimadzu Corporation, Autograph), a T peel test was performed under the conditions of a tensile speed of 200 mm / min, and the delamination strength was measured. It was judged that the delamination resistance was excellent when the delamination strength was 1.8 N / cm or more.

[Delamination strength after boil treatment]
The laminated film (200 mm long, 200 mm wide) obtained by the method described in each example was dipped in water heated to 90 ° C. for 30 minutes while being fixed to the frame, and boiled. After the treatment, the film was taken out, and the delamination strength of the laminated film after the boil treatment was measured by the above method. When the delamination strength of the laminated film after the boil treatment was 1.0 N / cm or more, it was judged that the durability of the delamination strength after the treatment in a high-temperature and high-humidity atmosphere was excellent.

Example 1
0.15 parts by mass of silica (manufactured by Fuji Silysia Chemical Co., Ltd., Cicilia 310, specific surface area 300 m ² / g, average particle size 1.4 μm), N, N with respect to 100 parts by mass of polymer (A-1) The polymer composition (A-1) containing 0.08 parts by mass of '-ethylenebisstearic acid amide, 75 parts by mass of the polymer composition (B1-1) and 25 parts by mass of the polymer (B2-1). A polyester polymer composition (hereinafter referred to as a polyester polymer composition (B-1)) and 100 parts by mass of the polymer (C-1) were used, and a 40 mmφ extrusion equipped with a circular five-layer die. The polymer composition (A-1) was extruded at 240 ° C., the polyester polymer composition (B-1) was extruded at 260 ° C., and the polymer (C-1) was extruded at 210 ° C. Pull separately while melting separately and cooling with 20 ° C water. Take
A layer made of the polymer composition (A-1) is changed to a resin layer (a),
A layer made of the polyester polymer composition (B-1) is a resin layer (b),
The layer made of the polymer (C-1) is replaced with a resin layer (c).
A laminated unstretched film having a layer structure of (a) / [e: (c)] / (b) / [e: (c)] / (a) which is substantially amorphous and not oriented. Obtained. Subsequently, stretching was performed at a stretching temperature of 150 ° 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. Release both ends of the film from the clip, trim the ears and wind them up. (A) / (c) / (b) / (c) / (a) = 5/1/3/1/5 μm laminated biaxial A stretched film was obtained. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Example 2
A laminated biaxially stretched film was obtained in the same manner as in Example 1 except that the polymer (A-1) was changed to the polymer (A-2) in Example 1. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Example 3
A laminated biaxially stretched film was obtained in the same manner as in Example 1 except that the polymer (A-1) was changed to the polymer (A-3) in Example 1. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Example 4
In Example 1, the polymer composition (B1-1) in the polyester polymer composition (B-1) was changed to the polymer composition (B1-2), and the polyester polymer composition (B- A laminated biaxially stretched film was obtained in the same manner as in Example 1 except that 2). The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Examples 5-6
In Example 1, the content ratio of the polymer composition (B1-1) and the polymer composition (B2-1) in the polyester-based polymer composition (B-1) was changed to the amount shown in Table 1, A laminated biaxially stretched film was obtained in the same manner as in Example 1 except that the polyester polymer composition (B-3) and the polyester polymer composition (B-4) were used. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Example 7
100 parts by mass of the polymer composition (A-1), 100 parts by mass of the polyester polymer composition (B-1), 100 parts by mass of the polymer (C-1), and 100 parts by mass of the mixture (D-1). Using a 40 mmφ extruder equipped with a circular seven-layer die, the polymer composition (A-1) was extruded at 240 ° C., the polymer (B-1) was extruded at 260 ° C., and the polymer (C -1) is melted separately at an extrusion temperature of 210 ° C., and the mixture (D-1) is melted separately at an extrusion temperature of 260 ° C.
A layer made of the polymer composition (A-1) is changed to a resin layer (a),
A layer made of the polyester polymer composition (B-1) is a resin layer (b),
A layer made of the polymer (C-1) is changed to a resin layer (c),
A layer made of the mixture (D-1) is changed to a resin layer (d),
And the layer structure is substantially amorphous with (a) / [e: (d) / (c)] / (b) / [e: (c) / (d)] / (a). A laminated unstretched film was obtained. Subsequently, stretching was performed at a stretching temperature of 150 ° 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. Release both ends of the film from the clip, trim the ear and wind it up, and (a) / [e: (d) / (c)] / (b) / [e: (c) / (d)] / ( a) A laminated biaxially stretched film having a thickness of 3/2/1/3/1/2/3 μm was obtained. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 1
In Example 1, the laminated biaxially stretched film of the layer structure shown in Table 1 was obtained by the same method as Example 1 except not using a polymer (C-1). The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 2
A laminated biaxially stretched film was obtained in the same manner as in Example 1, except that the polymer (C-1) was changed to the polymer composition (C-2) in Example 1. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 3
A laminated biaxially stretched film was obtained in the same manner as in Example 1 except that the polymer (C-1) was changed to the adhesive resin (E-1) in Example 1. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 4
In Example 1, a laminated biaxially stretched film was obtained in the same manner as in Example 1 except that the polymer (C-1) was changed to the adhesive resin (E-2). The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 5
A laminated biaxially stretched film was obtained in the same manner as in Example 1 except that the polymer (A-1) was changed to the polymer (A-4) in Example 1. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 6
In Example 1, except having changed into the composition (B-5) which does not use the polymer (B2-1) in a polyester-type polymer composition (B-1), it is the same method as Example 1. A laminated biaxially stretched film was obtained. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 7
In Example 1, the same method as Example 1 except having changed into the composition (B-6) which does not use the polymer composition (B1-1) in a polyester-type polymer composition (B-1). A laminated biaxially stretched film was obtained. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Examples 8-9
In Example 1, the content ratio of the polymer composition (B1-1) and the polymer (B2-1) in the polyester polymer composition (B-1) was changed to the amount shown in Table 1, and the composition was changed. A laminated biaxially stretched film was obtained in the same manner as in Example 1 except that (B-7) and the composition (B-8) were used. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 10
In Example 1, the polymer (C-1) was not used, the polyester polymer composition (B-1) was changed to the barrier resin (F-1), and the extrusion temperature of (F-1) was 230. A laminated biaxially stretched film having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the temperature was changed to ° C. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 11
In Example 1, the polymer (C-1) was not used, the polyester polymer composition (B-1) was changed to the barrier resin (F-2), and the extrusion temperature of (F-2) was 280. A laminated biaxially stretched film having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the temperature was changed to ° C. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

  As is apparent from Table 1, Comparative Example 1 in which the resin layer (c) is not disposed is inferior in the initial delamination strength, and the resin layer (c) is not disposed and a resin layer made of an unmodified polyester elastomer is used. The arranged Comparative Example 2 was also inferior in the initial delamination strength. Furthermore, Comparative Examples 3 and 4 using an adhesive resin other than those specified in the present invention were inferior in durability of delamination strength after the boil treatment. Comparative Example 5 using a polyamide that does not satisfy the condition of the end group concentration defined in the present invention has a high initial delamination strength, but has a low delamination strength after the boil treatment and durability of delamination strength. It was not excellent. The comparative example 6 which has not arrange | positioned the resin layer (b) containing a polymer (B2) is inferior to the durability of the initial delamination strength and delamination strength, and the resin layer (b) containing a polymer (B1) Comparative Example 7 in which no) was disposed was inferior in gas barrier properties. Comparative Example 8 in which the content of the polymer (B2) is less than the specified range of the present invention is inferior in the durability of the initial delamination strength and delamination strength, and the content of the polymer (B1) is in accordance with the present invention. Comparative Example 9 less than the specified range was inferior in gas barrier properties.

  Comparative Examples 10 and 11 in which the barrier resin was changed were inferior in gas barrier properties under high humidity.

  On the other hand, the films of the present invention of Examples 1 to 7 defined in the present invention have gas barrier properties under high humidity, delamination resistance, particularly durability of delamination strength after treatment in a high temperature and high humidity atmosphere. It is clear that it is excellent.

Claims (9)

A resin layer (a) mainly composed of a polyamide polymer (A);
A resin layer (b) mainly composed of a polyglycolic acid polymer (B1) and an aromatic polyester polymer (B2);
Resin layer (e) containing polymer (C)
Is a film including a resin layer (S) laminated,
The polymer (A) is represented by the following formula (1):
[X] − [Y] ≧ 0.2 × 10000 / ((ηr− (18−x) / 10) × M) (1)
([X] is the terminal amino group concentration per 1 g of the polymer (A) (μeq / g) (eq is equivalent),
[Y] is a terminal carboxyl group concentration (μeq / g) per 1 g of the polymer (A) (eq is equivalent),
x = [CH ₂ ] / [NHCO] ([CH ₂ ] is the number of methylene groups in the polymer (A), [NHCO] is the number of amide groups in the polymer (A),
ηr is a relative viscosity measured in JIS K-6920 in 96% by weight sulfuric acid in the polymer (A) concentration of 1% by weight at 25 ° C., and ηr> (18−x) / 10.
M represents the mass per mole of the structural repeating unit of the polymer (A). )
The filling,
The polymer (C) is a modified polyester elastomer polymer graft-modified with an α, β-ethylenically unsaturated carboxylic acid (excluding the polymer (B2)).
The resin layer (e) is a resin layer (c) containing the polymer (C) as a main component, or
The resin layer (c) and the polymer layer (d) (provided that the polymer (A), the polymer (B1), the polymer (B2), and the polymer (C) are the main components) (A), (b) and (c) are excluded.)
Mass ratio of the polymer (B1) and the polymer (B2) to the total amount of 100% by mass of the polymer (B1) and the polymer (B2) (polymer (B1) / polymer (B2)) Is 60/40 to 90/10, in units of mass%,
The resin layer (e) is laminated between the resin layer (a) and the resin layer (b) in contact with the resin layer (a) and the resin layer (b),
The film, wherein the resin layer (c) constituting the laminated resin layer (e) is in contact with the resin layer (a) and / or the resin layer (b). The polymer (A) is 60 to 100% by mass in the resin layer (a),
The total of the polymer (B1) and the polymer (B2) is 60 to 100% by mass in the resin layer (b).
The polymer (C) is 70 to 100% by mass in the resin layer (a).
The total of the polymer (A), the polymer (B1), the polymer (B2) and the polymer (C) is 70 to 100% by mass in the resin layer (d).
The film according to claim 1. In the resin layer (d),
The total of the polymer (B1) and the polymer (B2) with respect to 100% by mass of the total amount of the polymer (B1), the polymer (B2) and the polymer (C), and the polymer ( The mass ratio of C) (total of polymer (B1) and polymer (B2) / polymer (C)) is 15 to 85/85 to 15 in terms of mass%. The film described. The polymer (A) is represented by the following formula (2)
[X] ≧ 1.1 × 10000 / ((ηr− (18−x) / 10) × M) (2)
The film in any one of Claims 1-3 which satisfy | fills.   The polymer (A) is at least one selected from the group consisting of polyamide 6 polymer, polyamide 6/66 copolymer, polyamide 6/12 copolymer, and polyamide 6/66/12 copolymer. The film in any one of Claims 1-4.   The polymer (A) is a polyamide polymer produced by adding at least one compound selected from the group consisting of aliphatic diamines, alicyclic diannes, and polyamines during polymerization. 6. The film according to any one of 5 above. The polymer (B1) is represented by the following formula (3):

The film in any one of Claims 1-6 which contains the repeating unit represented by 60 mass% or more in the said polymer (B1).   The film according to any one of claims 1 to 7, wherein the number of laminated resin layers (S) is 3 to 8.   The film according to claim 1, wherein the film is used for food packaging.