JP2010253933A - Laminated polyamide film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated polyamide film which is less yellowish and has good film appearance, high water vapor permeability, smoking treatment effect and elution resistance, and slidability. <P>SOLUTION: The laminated polyamide film includes at least two layers: an (a) layer made of (A1) polyamide resin composition containing 80- 98 mass% of (A) polyamide resin and 2-20 mass% of (B) vinyl amide polymer, and a (b) layer made of (A2) polyamide resin composition containing 70-98 mass% of (A) polyamide resin and (C) 2-30 mass% of poly (N- vinyl lactam) cross-linked body. The (b) layer made of (A2) polyamide resin composition is arranged on a foodstuff contact surface, and the (a) layer made of the (A1) polyamide resin composition is arranged on a side opposite the foodstuff contact surface with respect to the (b) layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention comprises (A) a layer comprising a polyamide resin composition (A1) comprising a polyamide resin and a vinylamide polymer, and (A2) comprising a polyamide resin composition comprising a polyamide resin and a poly (N-vinyl lactam) crosslinked product. (B) It is composed of at least two layers having a layer, (A2) a layer made of a polyamide resin composition (b) is arranged as an exposed surface layer, and (A1) a layer (a) made of a polyamide resin composition ( b) It is related with the polyamide-type laminated film arrange | positioned on the opposite side to the said exposed surface with respect to a layer. More specifically, the present invention relates to a polyamide-based laminated film having a little yellowishness and a good film appearance, a large water vapor permeability, and excellent smoke treatment effect, elution resistance and slipperiness.

  Processed meat products such as ham and sausage and cheese are smoked and cooked by heat treatment, and natural casings such as animal intestines and fiber brass casings in which viscose is coated and impregnated are used. However, the intestines of animals are uneven in shape and strength, and there is a difficulty in supplying certain demand. Fibrous casings are preferred because they give the appearance of a high-class appearance, but because the water vapor permeability is large, the mass loss of the contents is large, and the oxygen permeability is large. There are problems such as rot and mold generation, unpleasant odor, and hard touch, so that pretreatment such as soaking in water is necessary for use.

  On the other hand, polyamide films such as polyamide 6 and polyamide 66 used as a synthetic plastic casing have some smoke treatment effects under high humidity, mechanical strength, impact strength, dimensional stability, and oxygen barrier properties. It has the advantages of being good and allowing the contents to be stored for a long time. However, the smoked effect is very small compared to the fiber casing, which is insufficient for the smoked casing.

  As a technique for improving the smoked effect of these polyamide films, a film in which a specific amount of polyamide and a hydrophilic compound are mixed and the hydrophilic compound is dispersed in a specific length in a polyamide matrix has been proposed (Patent Document 1). reference). As the hydrophilic compound, polyvinyl pyrrolidone, polyvinyl alcohol, polyalkyloxazoline, polyalkylene glycol, polyvinyl alcohol ether, polyvinyl ether, and cellulose ether are disclosed. Although the water vapor permeability of the film is certainly excellent, when the film is processed by an operation such as water or oil treatment, the hydrophilic compound is easily removed from the film and the elution resistance is poor.

  Moreover, the casing film for foodstuffs which consists of a mixture of polyvinylpyrrolidone and a polyamide resin is disclosed (refer patent document 2). According to the example of this document, a film in which crosslinked polyvinylpyrrolidone is blended with polyamide is proposed. The film has a matte texture and is given a high-class image, but there is room for further improvement in terms of water vapor transmission rate, and there is no technical suggestion or disclosure regarding laminated films.

  Furthermore, a multilayer tubular film for transferring a smoked liquid food comprising a crosslinked polyvinylpyrrolidone and a polyamide resin is disclosed (see Patent Document 3). This document proposes a multilayer tubular film having an innermost layer in which crosslinked polyvinylpyrrolidone and a polyamide resin are blended. Since the multilayer tubular film uses cross-linked polyvinyl pyrrolidone, the compound is difficult to drop off from the film, so that the elution resistance is good and the smoked liquid food can be transferred. However, as disclosed in the Examples of the same document, since it has a polyolefin layer as a water vapor barrier layer, it has a problem that a desired smoke treatment cannot be performed, and the smoke effect is insufficient, and thus further improvement. There is room for. Furthermore, in the same document, neither technical suggestion nor disclosure regarding a laminated film that highly balances film appearance, elution resistance, slipperiness, water vapor permeability, and smoke treatment effect is made.

US Pat. No. 7,361,392 JP 2002-306059 A Japanese Patent Application No. 2005-515501

  An object of the present invention is to provide a polyamide-based laminated film having a small yellowishness and a good film appearance and having a high water vapor permeability and excellent smoke treatment effect, elution resistance and slipperiness.

  As a result of intensive studies in view of these actual conditions, the present inventors have found that a polyamide-based laminate having a layer made of a polyamide resin and a specific vinylamide polymer, and a layer made of a polyamide resin and a crosslinked poly (N-vinyllactam). The present inventors have found that a film can solve the above-mentioned problems and have reached the present invention.

  That is, the present invention comprises (A) a polyamide resin composition comprising (A) 80 to 98% by mass of a polyamide resin and (B) 2 to 20% by mass of a vinylamide polymer (A1) comprising a polyamide resin composition, (A) It is composed of 70 to 98% by mass of polyamide resin and 2 to 30% by mass of (C) crosslinked poly (N-vinyllactam) (A2) comprising at least two layers having (b) a layer made of a polyamide resin composition. (A2) The layer (b) made of the polyamide resin composition is disposed as an exposed surface layer, and the layer (a) made of (A1) the polyamide resin composition is opposite to the exposed surface with respect to the layer (b). The present invention provides a polyamide-based laminated film characterized by being arranged.

The preferable aspect of the polyamide-type laminated | multilayer film of this invention is shown below. A plurality of preferred embodiments can be combined.
[1] The (A) polyamide resin is any one selected from the group consisting of a polyamide 6 polymer, a polyamide 6/66 copolymer, a polyamide 6/12 copolymer, and a polyamide 6/66/12 copolymer. A polyamide-based laminated film characterized by
[2] The (B) vinylamide polymer is poly (N-vinyl-2-pyrrolidone), and the (C) crosslinked poly (N-vinyl lactam) is a crosslinked poly (N-vinyl-2-pyrrolidone). A polyamide-based laminated film characterized by being:
[3] (A2) A polyamide-based laminated film, wherein the polyamide resin (A) constituting the polyamide resin composition is a polyamide 6 polymer.
[4] A polyamide-based laminated film comprising 2 to 7 layers.
[5] A polyamide-based laminated film, which is a polyamide-based laminated biaxially stretched film that is stretched 2.0 times or more in the longitudinal and lateral directions.
[6] A polyamide-based laminated film, which is used as a film for transferring a smoked liquid food.
[7] The smoked food is packaged with the above film, (A2) the (b) layer made of the polyamide resin composition is disposed in the innermost layer in contact with the food, and (A1) the polyamide resin composition (a ) A packaged smoked food product characterized in that the layer is arranged outside the layer (b).

  The polyamide-based laminated film of the present invention comprises (A1) a layer comprising a polyamide resin and a vinylamide polymer, (A1) a layer comprising a polyamide resin composition, and (A2) a polyamide resin composition comprising a polyamide resin and a poly (N-vinyllactam) crosslinked product. (B) layer made of (A2) polyamide resin composition is disposed as an exposed surface (layer, and (a1) layer made of polyamide resin composition (b) ) Since it is a laminated film disposed on the opposite side of the exposed surface with respect to the layer, the film appearance is good with little yellowishness, and the water vapor permeability is large, resulting in smoke treatment effect, elution resistance, and slipperiness. Excellent film appearance, water vapor transmission rate and smoke treatment effect at the same time.The laminated film penetrates moisture containing smoke smoke and flavor components. It is easy and suitable for smoke processing. On the other hand, it is moderately impervious to gas and has enough strength to withstand casing processing such as clip processing, shearing processing, and filling of contents. For this reason, it is suitable as a film for transfer of smoked liquid food.

It is the perspective view and sectional drawing which show the example of the film of this invention used as packaging of smoked food. It is a perspective view which shows the example of the smoked food packaged with the multilayer film of this invention.

Hereinafter, the present invention will be described in detail.
The (A1) polyamide resin composition used in the present invention comprises (A) a polyamide resin 80 to 98% by mass and (B) a vinylamide polymer 2 to 20% by mass, and (A2) a polyamide resin. The composition comprises (A) 70 to 98% by mass of a polyamide resin and (C) 2 to 30% by mass of a crosslinked poly (N-vinyllactam).

  (A) The polyamide resin has an amide bond (—CONH—) in the main chain, and a melt polymerization, solution polymerization or solid phase using lactam, aminocarboxylic acid, or nylon salt composed of diamine and dicarboxylic acid as a raw material. It can be obtained by condensation polymerization or cocondensation polymerization by a known method such as polymerization.

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

  The diamine constituting the nylon salt includes ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, Tridecamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, heptacamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine, 2- / 3-methyl-1,5 -Pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methyl-1,9-nonanedia Aliphatic diamines such as 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, norbornane dimethylamine, tricyclodecanedimethylamine, and the like, m- / p-xyl Examples include aromatic diamines such as range amines. 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, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid. Aliphatic dicarboxylic acids such as acid, octadecane dicarboxylic acid, eicosane dicarboxylic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid Aromatic dicarboxylic acids such as dicarboxylic acid, isophthalic acid, terephthalic acid, and 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid. These can use 1 type (s) or 2 or more types.

  (A) In the polyamide resin, these lactams, aminocarboxylic acids, or single polymers or copolymers derived from nylon salts composed of diamines and dicarboxylic acids can be used alone or in the form of a mixture. Specific examples of the (A) polyamide resin used include polycaprolactam (polyamide 6), polyundecane lactam (polyamide 11), polydodecane lactam (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene azide Pamide (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) T (H)), polynonamethylene adipamide (polyamide 96), polynonamethylene azelamide (polyamide 99), polynonamethylene sebamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polynona Methylene terephthalamide (polyamide 9T), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), polydecamethylene Adipamide (polyamide 106), polydecamethylene azeamide (polyamide 109), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydecamethylene terephthalamide (polyamide) 10T), polydecamethylenehexahydroterephthalamide (polyamide 10T (H)), polydecamethylenenaphthalamide (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)), poly Dodecamethylene 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 IPD6) , Poly isophorone terephthalamide (polyamide IPDT), polyamide copolymer using these raw material monomers can be mentioned. 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 obtained film, polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer (of polyamide 6 and polyamide 66) Copolymer, hereinafter referred to as copolymer), 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, polyamide MXD Polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6 / IPD6 copolymer, polyamide 6 / IPDT copolymer, polyamide 6 / More preferably, it is a 66/12 copolymer. More preferred are polyamide 6, polyamide 6/66 copolymer, polyamide 6/12 copolymer, and polyamide 6/66/12 copolymer.

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

  In addition, there is no special restriction | limiting in the kind of the terminal group of (A) polyamide resin, its density | concentration, and molecular weight distribution. One or more of monoamines, diamines, monocarboxylic acids, and dicarboxylic acids can be added in combination as appropriate for molecular weight adjustment and melt stabilization during molding. For example, cycloaliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, etc. Aromatic monoamines such as monoamine, aniline, toluidine, diphenylamine, and naphthylamine, aliphatic diamines such as hexamethylenediamine, nonamethylenediamine, decamethylenediamine, and dodecamethylenediamine, cycloaliphatic diamines such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine Aromatic diamines such as diamine, m- / p-phenylenediamine, m- / p-xylylenediamine, acetic acid, propionic acid, butyric acid, Acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid and other aliphatic monocarboxylic acids, cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids, benzoic acid Aromatic monocarboxylic acids such as toluic acid, α- / β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid, adipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid , Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 1,4- Aromatic dicals such as / 2,6- / 2,7-naphthalenedicarboxylic acid It is phosphate and the like. These can use 1 type (s) or 2 or more types. The amount of these molecular weight regulators to be used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the relative viscosity of the finally obtained polyamide resin falls within the above range.

  For the (A) polyamide resin, the amount of water extraction measured according to the method for measuring the content of low molecular weight substances specified in JIS K-6920 is preferably 1.0% or less, 0.5% The following is more preferable. When the amount of water extraction is large, adhesion of oligomer components to the vicinity of the die is remarkable, and appearance defects are likely to occur due to generation of die lines and fish eyes due to these deposits. Furthermore, (A) the polyamide resin has a higher hygroscopicity than the olefin resin, and when a hygroscopic material is used, an oligomer is generated when the raw material is melt-extruded, and an oligomer is generated, making film production difficult. Therefore, it is preferable to dry in advance and make the water content 0.1% by mass or less.

  The (B) vinylamide polymer in the present invention is a polymer containing a structural unit represented by the following general formula (1).

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group, and X and Y each independently represent a hydrogen atom or an organic residue, provided that X and Y are bonded to form nitrogen. Including those having a heterocyclic structure including

In the general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group. Specific examples of the alkyl group that is an example of R ¹ , R ² , and R ³ are not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, An alkyl group having 1 to 4 carbon atoms such as a tert-butyl group is preferred. The alkyl group may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, or a sulfonic acid group, if necessary. In the general formula (1), X and Y each independently represent a hydrogen atom or an organic residue. Specific examples of the organic residue as examples of X and Y are not particularly limited, and examples thereof include a methyl group, an ethyl group, and a phenyl group. Alternatively, X and Y may be bonded to form a heterocyclic structure including a nitrogen atom. Such a heterocyclic structure is not particularly limited, and examples thereof include a heterocyclic structure possessed by cyclic N-vinylamides. The organic residue may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, or a sulfonic acid group, if necessary. Of the hydrogen atom represented by X and Y and the above organic residue, a hydrogen atom and a methyl group are preferred.

  The structural unit represented by the general formula (1) is derived from an N-vinylamide monomer. Specific examples of N-vinylamide monomers include N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylphthalamide, N-vinylsuccinamide. Examples include acid amides and N-vinylurea. Examples of those in which X and Y are bonded to form a heterocyclic structure including a nitrogen atom include N-vinyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, and N-vinyl. 2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinyl-7-methyl-ε-caprolactam, N-vinyloxazolidone, N-vinylimidazole, N-vinyl And cyclic N-vinylamides such as 2-methylimidazole and N-vinyl-4-methylimidazole. These can use 1 type (s) or 2 or more types. Among these monomers, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinyloxazolidone are preferable because they are easily available and have good polymerization reactivity.

  (B) The vinylamide polymer may copolymerize an N-vinylamide structural unit represented by the general formula (1) and a structural unit derived from another monomer. The other monomer is not particularly limited as long as it is copolymerizable with the N-vinylamide monomer represented by the general formula (1). For example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethacryl Monoethylenically unsaturated carboxylic acid monomers such as acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, and salts thereof (sodium salt) , Potassium salt, zinc salt, ammonium salt), methyl acrylate, ethyl acrylate, (iso) propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate , Ethyl methacrylate, (iso) propyl methacrylate, butyl methacrylate, methacrylate 2-ethylhexyl acid, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methoxyethyl acrylate, methoxy methacrylate Monomers containing carboxylic acid ester monomers such as ethyl, acrylic acid-2-hydroxyethoxyethyl, methacrylic acid-2-hydroxyethoxyethyl, and salts thereof (sodium salt, potassium salt, zinc salt, ammonium salt) Monomer, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, dimethyl maleate, diethyl fumarate, dimethyl itaconate, etc., acrylic acid-2-ethyl sulfonate, methacrylic acid-2- Sulfo Sulfoxyl group-containing unsaturated monomers such as ethyl acrylate, vinyl sulfonic acid, styrene sulfonic acid, acrylic acid- (3-sulfopropyl) ester, methacrylic acid (3-sulfopropyl) ester, acrylamidomethylpropane sulfonic acid, and salts thereof , Acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-isopropyl (meth) acrylamide, N-isopropyl methacrylamide, N-methylol acrylamide, N-methylol Methacrylamide, N, N'-dimethylacrylamide, N, N'-diethylacrylamide, N, N'-dimethylmethacrylamide, N, N'-diethylmethacrylamide, N, N'-dimethylol Single amounts of carboxylic acid amides such as rilamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-phenylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl acrylate, N, N- Basic unsaturated monomers such as dimethylaminopropyl methacrylate, N, N-dibutylaminoethyl acrylate, N, N-dibutylaminoethyl methacrylate, vinylpyridine, and salts or quaternized products thereof, anhydrous maleic acid Unsaturated carboxylic acid anhydrides such as acid, itaconic anhydride, citraconic anhydride, endobicyclo- [2,2,1] [2.2.1] -5-heptene-2,3-dicarboxylic acid anhydride, Vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl decanoate, vinyl stearate, vinyl hexanoate, vinyl octoate, vinyl palmitate, benzoate Vinyl ester monomers such as vinyl acid, vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, vinyl benzyl ether, allyl acetate, allyl chloride, allyl alcohol, allyl phenyl ether, allyl acetate, etc. Allyl monomer of ethylene Α-olefins such as propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, styrene, o / p-methyl Styrene monomers such as styrene, p-methoxystyrene, m-chlorostyrene, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl bromide, acrylonitrile, methacrylonitrile, etc. Unsaturated epoxy monomers such as vinyl cyanides, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, allyl glycidyl ether, and vinyl carbonate monomers such as vinyl ethylene carbonate Etc. These can use 1 type (s) or 2 or more types.

  The content of the N-vinylamide structural unit is not particularly limited, but it is preferably 50 mol% or more, more preferably 70 mol% or more based on the total structural unit of the (B) vinylamide polymer. Preferably, it is 80 mol% or more. If the content of the N-vinylamide-based structural unit is less than the above value, the effect of the present invention may not be exhibited because it is too hydrophobic.

  As the polymerization method, known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like can be used, and are not particularly limited. Although superposition | polymerization temperature is not specifically limited, It is preferable that it is 0-300 degreeC, It is more preferable that it is 10-200 degreeC, It is further more preferable that it is 25-150 degreeC. When the polymerization temperature is lower than the above value, the polymerization reactivity may be reduced and the polymerization reaction may be very slow. When the polymerization temperature is higher than the above value, side reactions may increase and reaction control may be difficult. is there.

  The solvent for the polymerization reaction is not particularly limited, but examples thereof include aliphatic hydrocarbons such as hexane and octane, alicyclic saturated hydrocarbons such as cyclohexane, alicyclic unsaturated hydrocarbons such as cyclohexene, benzene, and the like. , Aromatic hydrocarbons such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2- / 3-hexanone, 2- / 3- / 4-heptanone, ketones such as cyclopentanone and cyclohexanone, methyl acetate, Esters such as ethyl acetate, butyl acetate and γ-butyrolactone, halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride, hexachloroethane and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, dioxolane and tetrahydrofuran, Ethylene glycol Alkylene glycol ethers such as dimethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, lactones such as butyrolactone, valerolactone, caprolactone, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n− / s− / T-butanol, 1- / 2- / 3-pentanol, ethylene glycol, propylene glycol, 1,3-propanediol, diethylene glycol, triethylene glycol, ethylene glycol monoalkyl ether, alcohols of propylene glycol monoalkyl ether, Methoxymethanol, 2-methoxyethanol, 2-methoxypropanol, 3-methoxypropanol, 2-methoxybut Tanol, 3-methoxybutanol, 4-methoxybutanol, 2-ethoxyethanol, 2-ethoxypropanol, 3-ethoxypropanol, 2-ethoxybutanol, 3-ethoxybutanol, 4-ethoxybutanol, 2-isopropoxyethanol, 2- Isopropoxypropanol, 3-isopropoxypropanol, 2-isopropoxybutanol, 3-isopropoxybutanol, 4-isopropoxybutanol, 2- (n-propoxy) ethanol, 2- (n-propoxy) propanol, 3- (n -Propoxy) propanol, 2- (n-propoxy) butanol, 3- (n-propoxy) butanol, 4- (n-propoxy) butanol, 2- (n-butoxy) ethanol, 2- (n-butoxy) propanol, 3 (N-butoxy) propanol, 2- (n-butoxy) butanol, 3- (n-butoxy) butanol, 4- (n-butoxy) butanol, 2- (s-butoxy) ethanol, 2- (s-butoxy) Propanol, 3- (s-butoxy) propanol, 2- (s-butoxy) butanol, 3- (s-butoxy) butanol, 4- (s-butoxy) butanol, 2- (t-butoxy) ethanol, 2- ( monoalkoxy alcohols such as t-butoxy) propanol, 3- (t-butoxy) propanol, 2- (t-butoxy) butanol, 3- (t-butoxy) butanol and 4- (t-butoxy) butanol, dimethylformamide Amides such as N-methylpyrrolidone, butylamine, cyclohexylamine, pyridine, morpholine, 2 Amines such as aminoethanol, diethanolamine, triethanolamine, aminoethylethanolamine, sulfonic acid esters such as dimethyl sulfoxide, carbonates such as dimethyl carbonate and diethyl carbonate, alicyclic carbonates such as ethylene carbonate and propylene carbonate And water. These can use 1 type (s) or 2 or more types.

  Among these solvents, aromatic hydrocarbons, ketones, esters, ethers, alkylene glycol ethers, alcohols, amides, sulfones are preferred from the viewpoint of ease of purification and recovery of the produced copolymer. Preferred are acid esters, carbonates, alicyclic carbonates, water, ketones, esters, alkylene glycol ethers, alcohols, amides, sulfonate esters, carbonic acid esters More preferred are those selected from the group of esters, alicyclic carbonates and water polar solvents, ketones, esters, alkylene glycol ethers, alcohols, amides, alicyclic carbonates. More preferred are those selected from water, and particularly preferred are those selected from the group consisting of alcohols and water. .

  When performing the polymerization reaction, the concentration of all monomer components of (B) vinylamide polymer in the raw material mixture is not particularly limited, but the concentration of all monomer components of (B) vinylamide polymer is It is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass. If the monomer concentration is less than the above value, productivity may be poor.

  The polymerization reaction is usually performed using a polymerization initiator. The polymerization initiator is not particularly limited, but examples thereof include inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, Ketone peroxides such as methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5- Dihydroperoxide, 1,1,3,3, -tetramethylbutyl hydroperoxide, 2- (4-methylcyclohexyl) -propane hydroperoxide Hydroperoxides, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxy) p-diisopropylbenzene, α, α'-bis (T-butylperoxy) p-isopropylhexyne, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Dialkyl peroxides such as hexyne-3, t-butyl peroxyacetate, t-butyl peroxydiethyl acetate, t-butyl peroxylaurate, di-t-butylperoxyisophthalate, 2,5-dimethyl- 2,5-di (benzoylperoxy) hexane, t-butyl-peroxyisobutyrate, t-butylperoxypi Valate, t-butylperoxyneodecanoate, 2,4,4-trimethylpentyl-2-peroxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3 , 5,5-trimethylcyclohexanoate, t-butylperoxybenzoate, t-butylperoxymaleic acid, t-amylperoxyneodecanoate, t-amylperoxypivalate, t-amylperoxy-2- Ethyl hexanoate, t-amyl peroxy normal octoate, t-amyl peroxy acetate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate, cumyl peroxy neohexanoate, cumyl peroxy octoate , Cumylperoxyneodecanoate, t-hex Peroxyesters such as ruperoxypivalate, t-hexylperoxyneohexanoate, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, n-butyl-4,4-bis ( t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis ( peroxyketals such as t-butylperoxy) cyclohexane and 2,2-bis (t-butylperoxy) octane, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide 3,3,5-trimethylcyclohexanoyl -Diacyl peroxides such as oxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, dibenzoyl peroxide, di-n-propyl peroxydicarbonate, di- Isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-t-butyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy 2-ethylhexyl carbonate, t-amyl peroxyisopropyl Carbonate, t-amylperoxy 2-ethylhexyl carbonate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, diacetylperoxycarbonate Peroxydicarbonates such as dimyristyl peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di-allyl peroxydicarbonate, acetylcyclohexyl Other organic peroxides such as sulfonyl peroxide, t-butylperoxyallyl carbonate, 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobisisobutyrate, 2,2 '-Azobis (2-methylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2 '-Azobis (2-methylpropionitrile), 2,2'-azobis (2-silane Ropropylpropionitrile), 2,2′-azobis [2- (hydroxymethyl) propionitrile], 4,4′-azobis (4-cyanopentanoic acid), 1,1′-azobis (cyclohexane-1- Carbonitrile), 1,1′-azobis- (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methyl-N-2-propenylpropanamide), 1-[(1-cyano-1- Methyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis [2 -Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2′-azobis [2-methyl-N- [2-H Roxyethyl] propionamide], 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (N—N ′) -Dimethyleneisobutylamidine) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-methyl-2- Imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis { 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine], etc. Azotization Thing, and the like. These can use 1 type (s) or 2 or more types.

  The amount of the polymerization initiator used may vary depending on the type and polymerization method, but may be determined as appropriate so that the polymerization reaction proceeds rapidly and an appropriate degree of polymerization is obtained. Is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total monomer component of the (B) vinylamide polymer. More preferably, it is 0.1-3 mass parts. When the blending amount of the polymerization initiator is less than the above value, the polymerization reaction may be very slow. On the other hand, when it exceeds the above value, the side reaction may be increased.

  In the polymerization reaction, a molecular modifier may be used to adjust the mass average molecular weight of the polymer. Molecular modifiers include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, formic acid, ammonium formate, hydroxylammonium sulfate, hydroxylammonium phosphate, dibutyl sulfide, dioctyl sulfide, diphenyl sulfide, diisopropyl disulfide, dibutyl disulfide, dihexyl disulfide , Diacetyl disulfide, butyl mercaptan, hexyl mercaptan, dodecyl mercaptan, t-dodecyl mercaptan, bisulfite, disulfite, ethyl thioglycolate, 2-amino-3- (t-butyldithio) propionic acid, 3,3′- Dithiobis (2-aminopropionic acid) (cystine), 2,2′-dithiobenzoic acid, 4,4′-dithiobenzoic acid 3,3′-dithiodipropionic acid, 4,4′-dithiobisbutyric acid (3-carboxypropyl disulfide), 4,4′-dithiobis (2-aminobutyric acid), 4,4′-dithiobisphenylacetic acid, 2- Mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, mercaptoacetic acid, ethyl-2-mercaptoacetate, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol , Diethanol sulfide, thiodiglycol, ethylthioethanol, thiourea, dimethyl sulfoxide, allyl alcohol, allyl bromide, benzyl chloride, chloroform, tetrachloromethane and the like. These can use 1 type (s) or 2 or more types.

  The amount used of the molecular weight modifier is appropriately selected so that the mass average molecular weight of the polymer falls within the range described below, but generally (B) 100 parts by mass of all monomer components of the vinylamide polymer, It is preferable that it is 0-10 mass parts. When the amount used of the molecular weight modifier exceeds the above value, the polymerization reaction does not proceed sufficiently and the amount of residual monomers increases, and it may be easy to produce those whose mass average molecular weight does not reach 1,000. .

  Moreover, it is also possible to adjust pH of the reaction liquid during polymerization suitably by adding a pH adjuster. Examples of the pH adjuster include basic substances such as ammonia, triethylamine, triethanolamine, and sodium hydroxide solution, and acidic substances such as hydrochloric acid, lactic acid, oxalic acid, acetic acid, and formic acid.

  Further, a buffering chelating agent can be used. Specific examples thereof include tetrasodium pyrophosphate, disodium ethylenediaminetetraacetate, trisodium phosphate, calcium hydroxide, borax, disodium hydrogen phosphate-monosodium phosphate, sodium carbonate-sodium bicarbonate, etc. Is mentioned. These can use 1 type (s) or 2 or more types. The amount of the buffering chelating agent to be used is not particularly limited, but is preferably 0.001 to 1.0 part by mass with respect to 100 parts by mass of the total monomer component (B) vinylamide polymer. It is more preferable that it is 0.01-0.5 mass part, and it is further more preferable that it is 0.04-0.3 mass part. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. Examples of the method for purifying the N-vinylamide polymer produced by the polymerization reaction include a method for removing the solvent by reprecipitation, dialysis, centrifugation, drying under reduced pressure, and the like, but are not particularly limited.

  (B) The mass average molecular weight of the vinylamide polymer is preferably 10,000 to 5,000,000, more preferably 50,000 to 4,000,000, and 100,000 to 3,000. More preferably, it is 000,000. When the weight average molecular weight of the (B) vinylamide polymer is less than the above value, the yellowness is high, and it may not be possible to impart a matte texture or a high-class feeling to the film appearance. On the other hand, if the above value is exceeded, the water vapor permeation and smoke effect of the film may be insufficient. Further, (B) the vinylamide polymer is not a crosslinked product.

  (B) The vinylamide polymer is preferably a poly (N-vinyl-2-pyrrolidone) polymer, and the K value of the polymer is preferably 20 to 120, and preferably 30 to 100. More preferred. The K value correlates with the molecular weight of polyvinyl pyrrolidone, and is conventionally used to measure the molecular weight of polyvinyl pyrrolidone. Polyvinylpyrrolidone is used as an aqueous solution with a concentration of 1%, the relative viscosity thereof is measured, and the value of k is obtained by the Fickencher's formula.

logZ = C [75k2 / (1 + 1.5kC) + k]
Here, Z represents the relative viscosity of an aqueous solution having a concentration C, and C represents the concentration of the aqueous solution as a solution concentration. The K value is obtained by multiplying the obtained k value by 1000. The measurement is performed three times and the average value is used.

  (A1) In the polyamide resin composition, the blending ratio of (A) polyamide resin and (B) vinylamide polymer is such that the ratio of (A) polyamide resin and (B) vinylamide polymer is (A) :( B ) = 80: 20 to 98: 2% by mass, preferably 85:15 to 95: 5% by mass. (B) When the compounding quantity of a vinylamide type polymer is less than the said value, hydrophilicity cannot be provided and the effect of this invention is not expressed. On the other hand, when the above value is exceeded, the yellowness (YI) becomes high, and the (B) vinylamide polymer tends to easily fall off by operations such as water and oil treatment.

  (B) The blending method of the vinylamide polymer into the (A) polyamide resin is performed by blending (A) the polyamide resin and (B) the vinylamide polymer with various additives as necessary, and mixing them by a known method. Manufactured by doing. For example, using a tumbler or mixer, a dry blend method in which raw materials are directly added at the time of molding, and raw materials are melt kneaded in advance using a uniaxial or biaxial extruder Banbury mixer, kneader, mixing roll, etc. at a concentration used during molding. Examples thereof include a kneading method, or a master batch method in which a raw material is kneaded in advance at a high concentration using a single or twin screw extruder, and this is diluted during molding. In the present invention, a kneading method for melt-kneading in advance or a production method by a masterbatch method is preferable because the entanglement between the (B) vinylamide polymer and the (A) polyamide resin can be strengthened.

  (C) A crosslinked poly (N-vinyl lactam) is a polymer obtained by further crosslinking a polymer composed of a structural unit derived from an N-vinyl lactam monomer. Examples of N-vinyl lactam monomers used in the crosslinked product include N-vinyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-6- Examples include methyl-2-piperidone, N-vinyl-ε-caprolactam, and N-vinyl-7-methyl-ε-caprolactam. These can use 1 type (s) or 2 or more types.

  Among these, a crosslinked poly (N-vinyl-2-pyrrolidone) is preferable. In order to distinguish poly (N-vinyl-2-pyrrolidone) from poly (N-vinyl-2-pyrrolidone) (PVP), poly (N-vinyl) poly (2-pyrrolidone) polymer (PVPP), It may be called crosslinked poly (N-vinyl-2-pyrrolidone) or insoluble poly (N-vinyl-2-pyrrolidone).

  (C) The cross-linked poly (N-vinyl lactam) may be obtained by copolymerizing the N-vinyl lactam monomer and a structural unit derived from another monomer. Other monomers include vinyl esters such as vinyl acetate, styrene, acrylonitrile, acrylamide, methacrylamide, acrylic acid, methacrylic acid, acrylic alkyl ester, methacrylic alkyl ester, hydroxy acrylate, hydroxy methacrylate, 1-butene, Examples thereof include α-olefins such as 1-dodecene, 1-hexadecene, 1-eicosene and 1-triacontene, and vinyl halide monomers such as vinyl chloride, vinyl fluoride, chloroprene and vinylidene chloride. These can use 1 type (s) or 2 or more types.

  (C) The poly (N-vinyl lactam) crosslinked product is obtained by crosslinking a poly (N-vinyl lactam) polymer with a crosslinking agent. Examples of the crosslinking agent include N, N′-methylene-bisacrylamide, N, N′-ethylene-bisacrylamide, N, N′-divinylethyleneurea, N, N′-divinylpropyleneurea, and ethylidene-bis-3. -(N-vinylpyrrolidone), N, N'-divinyldiimidazolyl- (2,2 ') butane, 1,1'-bis- (3,3'-vinylbenzimidazolido-2-one) -1, Alkylene bisacrylamides such as 4-butane, ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol acrylate, tetraethylene glycol dimethacrylate, diethylene glycol acrylate, diethylene glycol methacrylate and other alkylene glycol di (meth) acrylates, divinyl base Zen, aromatic divinyl compounds such as divinyltoluene, triacrylic esters such as triallyl cyanurate, trimethylolpropane, 1-vinyl-3-ethylidenepyrrolidone, butanediol diacrylate, vinyl acrylate, allyl acrylate, methacrylic acid Examples include allyl, divinyldioxane, and pentaerythritol triallyl ether. Among these, N, N′-divinylethyleneurea and divinylbenzene are preferable. These can use 1 type (s) or 2 or more types.

  (C) The quantity of the crosslinking agent used at the time of manufacture of a poly (N-vinyl lactam) crosslinked body is 0.01-50 mass parts with respect to 100 mass parts of all the monomer components of poly (N-vinyl lactam). It is preferable that it is 0.1-20 mass parts. When the amount of the crosslinking agent used is less than the above value, the strength as a crosslinked product may be lowered. On the other hand, when it exceeds the above value, handling during polymerization may be difficult.

  (C) As a method for obtaining a crosslinked poly (N-vinyllactam), for example, radical polymerization using an azo or peroxide radical initiator, polymerization using UV, electron beam or radiation, ion polymerization , Popcorn polymerization (growth polymerization) method, and the like, among others, popcorn polymerization method (growth polymerization) is preferable. The popcorn polymerization (growth polymerization) method is a vinyl lactam monomer described in Japanese Patent Publication Nos. 54-30027, 3-39087, 61-78808 and 61-78809. A vinyl lactam monomer described in U.S. Pat. Nos. 2,938,017, 3,277,066, 3,759,880, and Japanese Patent Publication No. 58-42201 This is a method for obtaining a crosslinked product with an alkali compound such as an alkaline earth metal hydroxide. For the outline of both polymerization methods, Polymer Journal, vol 17, No. 1 1, pp 143-152 (1985).

  (C) The crosslinked poly (N-vinyllactam) is preferably a crosslinked poly (N-vinyl-2-pyrrolidone) obtained by a popcorn polymerization method. Popcorn polymerization can be carried out by a known method such as precipitation polymerization or bulk polymerization. (C) The cross-linked poly (N-vinyl lactam) is obtained in the form of a powder having an average particle size of 5 μm to 5 mm, but the cross-linked poly (N-vinyl lactam) has a particle size of 150 μm or more. It is preferable that the average particle diameter is substantially in the range of 10 to 100 μm, and more preferably in the range of 10 to 70 μm. When the average particle size exceeds the above value, a fish eye gel is generated and the film appearance is impaired, and the clogging of the filter due to the aggregate of the (C) crosslinked poly (N-vinyllactam) becomes remarkable, resulting in continuous productivity. May be inferior. On the other hand, when it is less than the above value, the (C) crosslinked poly (N-vinyllactam) is likely to aggregate, and on the contrary, a fish eye gel is generated. Moreover, even if aggregation can be prevented, it may be difficult to obtain a film surface shape exhibiting a high-quality matte appearance. (C) When the particle size of the crosslinked poly (N-vinyllactam) does not meet the above value, it is desirable to perform pulverization or classification in advance. In general, as a method for obtaining fine particles by physical means, it is obtained by mechanically dry-type and wet-grinding existing crosslinked particles having a large particle size. Examples of the apparatus used for pulverization include ultra visco mill, bead mill, agitator mill, roller mill, hammer mill, ball mill, vibration mill, auto fall mill, jet mill, atomizer and the like.

  (A2) In the polyamide resin composition, the blending ratio of (A) polyamide resin and (C) crosslinked poly (N-vinyllactam) is (A) polyamide resin and (C) crosslinked poly (N-vinyllactam). Is in the range of (A) :( C) = 70: 30 to 98: 2 mass%, preferably in the range of 75:25 to 97: 3 mass%, and 80:20 to 95 : More preferably within the range of 5% by mass. (C) When the compounding quantity of a poly (N-vinyl lactam) crosslinked body is less than the said value, hydrophilicity cannot be provided and the effect of this invention is not expressed. On the other hand, when the above value is exceeded, the (C) crosslinked poly (N-vinyllactam) tends to be easily dropped by an operation such as water or oil treatment.

  (C) The blending method of the poly (N-vinyl lactam) crosslinked product into the (A) polyamide resin is various additions to the (A) polyamide resin and (C) poly (N-vinyl lactam) crosslinked product as necessary. It is manufactured by blending the agent and mixing it by a known method. For example, using a tumbler or mixer, a dry blend method in which raw materials are directly added at the time of molding, and raw materials are melt kneaded in advance using a uniaxial or biaxial extruder Banbury mixer, kneader, mixing roll, etc. at a concentration used during molding. Examples thereof include a kneading method, or a master batch method in which a raw material is kneaded in advance at a high concentration using a single or twin screw extruder, and this is diluted during molding. In the present invention, a kneading method for melt-kneading in advance or a production method by a masterbatch method is preferable because it can strengthen the entanglement between the (C) crosslinked poly (N-vinyllactam) and the (A) polyamide resin.

  In the (A1) and (A2) polyamide resin compositions of the present invention, various additives and modifiers that are usually blended in the resin composition within a range that does not impair the properties of the obtained film, for example, heat stability Agent, ultraviolet absorber, light stabilizer, antioxidant, antistatic agent, lubricant, antiblocking agent, filler, tackifier, sealability improver, antifogging agent, crystal nucleating agent, mold release agent, plasticizer Various additives such as a crosslinking agent, a foaming agent, a colorant (pigment, dye, etc.) and a bending fatigue resistance improving material can be added.

  Furthermore, it is preferable to add a bisamide compound to the polyamide resin composition (A1) or (A2) from the viewpoint of improving transparency and slipperiness. Examples of the bisamide compound include N, N′-methylenebisstearic acid amide, N, N′-ethylene bisstearic acid amide, N, N′-ethylene bisbehenic acid amide, N, N′-dioctadecyl adipic acid amide, and the like. Can be mentioned. These can use 1 type (s) or 2 or more types.

  The blending amount of the bisamide compound is preferably 0.01 to 0.5 parts by mass, more preferably 0.02 to 0.3 parts by mass with respect to 100 parts by mass of the (A) polyamide resin. More preferably, the content is 0.03 to 0.2 parts by mass. If the blending amount is less than the above values, the effect of improving the transparency and slipperiness of the obtained film may be small. On the other hand, if it exceeds the above values, the printability of the film and the adhesiveness during laminating will decrease. There is a case.

  In addition, the (A1) and (A2) polyamide resin compositions include xylylene selected from amorphous polyamide, m-xylylenediamine, and p-xylylenediamine to improve stretchability and barrier properties during film production. It is preferable to blend a semi-aromatic polyamide containing 70 mol% or more of structural units derived from a range amine and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms in the molecular chain.

  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 mainly composed of an aromatic aminocarboxylic acid such as paraaminomethylbenzoic acid, paraaminoethylbenzoic acid, and metaaminomethylbenzoic acid, or an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid; There is a semi-aromatic polyamide having an aliphatic diamine as a main constituent unit, and it is preferable to blend a semi-aromatic polyamide having an aliphatic diamine and terephthalic acid and / or isophthalic acid as a polyamide constituent unit. As the aliphatic diamine unit used here, a 1,6-hexanediamine unit is preferably selected. The polyamide having an aliphatic diamine and terephthalic acid and / or isophthalic acid as a polyamide constituent unit may be a polymer in which the polyamide constituent unit is 100% by mass, but other constituent units such as lactam, aminocarboxylic acid, etc. It may be a copolymer composed of a polyamide constituent unit introduced by dicarboxylic acid other than acid, terephthalic acid and isophthalic acid and diamine. As other copolymerizable structural units, hexamethylene adipamide units, caprolactam units, and dodecane lactam units are particularly 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 thereof 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.

  Semi-aromatic containing 70 mol% or more of a polyamide structural unit derived from xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms in the molecular chain The polyamide is composed of a xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and a polyamide constituent unit derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, and the polyamide constituent unit is aromatic. Has a ring skeleton. In the semi-aromatic polyamide, it is also possible to copolymerize other polyamide constituent units other than the polyamide constituent units.

  In the semi-aromatic polyamide, as other polyamide structural units excluding the xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and a polyamide structural unit derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms Includes diamine units other than units derived from xylylenediamine, dicarboxylic acid units other than units derived from aliphatic dicarboxylic acids having 6 to 12 carbon atoms, and other units.

  Examples of diamine units other than those derived from xylylenediamine include hexamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2- / 3-methyl-1,5-pentane diamine, 2 -Aliphatic diamines such as methyl-1,8-octanediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methyl-1,9-nonanediamine, 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 (isophorone diamine Min), alicyclic diamines such as bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylamine, tricyclodecanedimethylamine, and aromatic diamines such as p-bis- (2-aminoethyl) benzene. Units. These can use 1 type (s) or 2 or more types.

  Examples of dicarboxylic acid units other than those derived from aliphatic dicarboxylic acids having 6 to 12 carbon atoms include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, tridecanedicarboxylic acid, octadecanedicarboxylic acid, and eicosanedicarboxylic acid. Examples thereof include units composed of acids, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. These can use 1 type (s) or 2 or more types. Examples of other units include lactams such as caprolactam and dodecane lactam, aliphatic aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid, and aminocarboxylic acids such as aromatic aminocarboxylic acid such as p-aminomethylbenzoic acid. Examples include units consisting of acids. These can use 1 type (s) or 2 or more types.

  Specific examples of semi-aromatic polyamides include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene pimeramide (polyamide MXD7), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide). MXD9), polymetaxylylene sepacamide (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene azelamide (polyamide PXD9), etc. Copolymer, metaxylylene / paraxylylene adipamide copolymer, metaxylylene / paraxylylene piperamide copolymer, metaxylylene / paraxylylene speramide copolymer, metaxylylene / paraxylylene azelamide copolymer , M-xylylene / para-xylylene cepa Kami-de copolymers, m-xylylene / para-xylylene dodeca amide copolymer of the copolymer.

  A molecule composed of amorphous polyamide having no clear melting point, xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. The blending amount of the semi-aromatic polyamide contained in the chain by 70 mol% or more is preferably 1 to 30 parts by mass and more preferably 3 to 25 parts by mass with respect to 100 parts by mass of the (A) polyamide resin. Preferably, the amount is 5 to 20 parts by mass. If the blending amount is less than the above values, the effect of improving stretchability and barrier properties may be small. On the other hand, if the blending amount exceeds the above values, the melt viscosity may be high and the production of the film may be difficult.

  The polyamide-based laminated film according to the present invention comprises (A) a polyamide resin and (B) a vinylamide polymer (A1) (a) a layer comprising a polyamide resin composition, and (A) a polyamide resin ( (C2) comprising a crosslinked poly (N-vinyllactam) (A2) comprising a polyamide resin composition (b) having at least two layers, and comprising (A2) a polyamide resin composition ( b) The layer is arranged as an exposed surface layer, and the (a1) layer made of the polyamide resin composition (A1) is arranged on the side opposite to the exposed surface with respect to the (b) layer.

  The polyamide-based laminated film of the present invention is a food packaging that has a portion that comes into contact with food products such as processed meat products such as ham, sausage, bacon, beef and turkey, processed fish products, kamaboko and chikuwa, cheese, etc. In this case, the exposed surface layer is a layer disposed at a location in contact with food, and is defined as the innermost layer (food contact surface) in the present invention. The polyamide-based laminated film of the present invention comprises (A) a polyamide resin and (C) a crosslinked poly (N-vinyllactam) in the same innermost layer. Is placed. (A) A polyamide resin and (B) a vinylamide polymer are contained. (A1) The layer (a) made of a polyamide resin composition comprises (A) a polyamide resin and (C) a poly (N-vinyl lactam) crosslinked. (B) layer in the direction opposite to the exposed surface, that is, the surface in contact with food (food contact surface) with respect to the layer (b) made of the polyamide resin composition (A2) containing the body And / or between the layer (b) and the layer (a) and in contact with the other layers.

  Furthermore, the polyamide-based laminate film of the present invention can be more preferably used as a film for transferring smoked liquid foods, and is disposed on the innermost layer (food contact surface) of the polyamide-based laminate film (A2) polyamide resin composition (B) When treated with a liquid smoked liquid from the surface in contact with the food of layer (b), the film surface has an appropriate surface roughness, so that it is possible to uniformly permeate and absorb the silkworm preparation, and polyamide A sufficient amount of the soot preparation can be retained in the laminated film, and the slipperiness is excellent. Moreover, (b) layer (A2) which consists of a polyamide resin composition is arrange | positioned in the innermost layer (food contact surface), When it contacts with the film by operation, such as water and oil treatment, The amount of elution can be suppressed. Furthermore, from the viewpoint of food hygiene, it is preferable that (A2) the polyamide resin constituting the polyamide resin composition (A2) is a polyamide 6 polymer.

  After that, by filling the polyamide-based laminated film with food such as meat and performing heat treatment such as cooking, it is possible to easily obtain a high-quality smoked food by uniformly and sufficiently transferring the koji preparation to the food. However, if the (a) layer made of the (A1) polyamide resin composition is not included, the water vapor permeability of the polyamide-based laminated film becomes small, and the above-mentioned smoked effect is not sufficiently exhibited.

  The polyamide-based laminated film according to the present invention is produced by using a (A1) or (A2) polyamide resin composition to produce a substantially amorphous and non-oriented unstretched laminated film by a method such as a coextrusion method. To do. 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 laminated biaxially stretched film from the viewpoint of the strength of the resulting film and the gas barrier. As a method for forming a raw film for a stretched film, the coextrusion T-die method and the coextrusion water-cooled inflation method are particularly excellent in terms of continuous stretchability.

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

  The stretching ratio of the laminated film varies depending on the intended use, but in the tenter biaxial stretching method and the tubular method, it is usually preferably 2.0 to 4.5 times in both the longitudinal direction and the transverse direction, 2.5 to It is more preferable that it is 4.0 times. When the draw ratio is less than the above value, the effect of improving the operation stability (stretchability) does not appear remarkably, and the strength and barrier properties of the resulting film may be inferior. On the other hand, if the above value is exceeded, the film may tear or break during stretching. The stretching temperature is preferably 30 to 210 ° C, and more preferably 50 to 200 ° C.

  The film stretched by the above method can be subsequently heat treated. Dimensional stability at room temperature can be imparted by heat treatment. The heat treatment temperature in this case is preferably selected in a range where 110 ° C. is the lower limit and the upper limit is 5 ° C. lower than the melting point of the resin composition. A stretched film can be obtained. The stretched film that has been sufficiently heat-set by the heat treatment operation can be cooled and wound up according to a conventional method.

  Furthermore, the obtained polyamide-based laminated film can be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, and acid treatment in order to improve 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 polyamide film is preferably subjected to a corona treatment in order to improve the adhesion with processed meat that is an object to be packaged.

  Further, the total number of layers in the polyamide-based laminated film according to the present invention is not particularly limited, and (A1) a layer made of a polyamide resin composition (A1) and (A) a layer (b) made of a polyamide resin composition As long as it is a laminated film of at least two layers including Judging from the mechanism of the film or laminate manufacturing apparatus, it is 8 layers or less, and preferably 2 to 7 layers.

  The polyamide-based laminated film of the present invention has little yellowness and good film appearance, has a large water vapor permeability, is excellent in smoke treatment effect, elution resistance, and slipperiness, and has a high utility value alone. In order to give a further function or to obtain an economically advantageous laminated film in addition to the two layers (b) and (b), a base material layer made of another thermoplastic resin is placed on the outer side of the laminated film, that is, , On the opposite side of the exposed surface.

  Other thermoplastic resins include 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 Polymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer ( Polyolefin resins such as EEA), 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] -5-heptene-2 , 3-dicarboxylic acid and other carboxyl groups and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2,2,1] -5 With compounds containing functional groups such as epoxy groups such as acid anhydride groups such as heptene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl itaconate Modified polyolefin resin, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), polyester resins such as liquid crystal polyester (LCP), Polyethers such as polyacetal (POM) and polyphenylene oxide (PPO), polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polyphenylene sulfide (PPS), polythioethersulfone (PTES) and other poly Polyketone resins such as thioether resins, polyetheretherketone (PEEK), polyallyletherketone (PAEK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer Polynitrile resins such as coalescence (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), polymethyl methacrylate ( PMMA), polymethacrylate resins such as polyethyl methacrylate (PEMA), polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride Polymers, polyvinyl chloride resins such as vinylidene chloride / methyl acrylate copolymer, cellulose resins such as cellulose acetate and cellulose butyrate, polycarbonate resins such as polycarbonate (PC), thermoplastic polyimide (PI), polyamideimide ( PAI , Polyimide resins such as polyetherimide, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoro Ethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), Fluorine resin such as tetrafluoroethylene / fluoro (alkyl vinyl ether) copolymer (PFA), thermoplastic polyurethane resin, polyurethane elastomer, polyester elastomer, polyamide elastomer, etc. That. In the polyamide-based laminated film of the present invention, it is also preferable to further laminate a polyolefin-based resin.

  It is also possible to laminate any substrate other than thermoplastic resin, such as paper, metal-based material, non-stretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metal cotton, wood, etc. is there. 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.

  The thickness of the polyamide-based laminated film according to the present invention is not particularly limited as long as it is appropriately determined depending on the application, but is preferably 5 to 200 μm, more preferably 10 to 150 μm, and more preferably 12 to 100 μm. Further preferred. If the total thickness is less than the above value, the balance between gas barrier properties and bending fatigue resistance may be deteriorated. On the other hand, if it exceeds the above value, the film may be hardened. Polyamide-based laminated film, the thickness of each layer is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the laminated film, use, etc., the thickness of each layer, It is determined in consideration of the gas barrier properties, mechanical properties, flexibility, transparency, etc. of the polyamide-based laminated film. In general, the thickness of the (a) layer and (b) layer is the thickness of the entire laminated film. It is preferable that it is 3 to 90% with respect to each. Considering the water vapor transmission rate, the thickness of the layer (a) is preferably 5 to 70%, more preferably 10 to 50% with respect to the total thickness of the polyamide-based laminated film.

  When the polyamide-based laminated film is a stretched film, the shrinkage rate (hot water shrinkage rate) when immersed in hot water at 80 ° C. is preferably 5% or more in each of the vertical and horizontal directions, and more preferably 8% or more. Preferably, it is 10% or more. When the hot water shrinkage rate is equal to or higher than the above value, the casing can be tightly adhered to the contents even after the cocoon product is cooled, and a final packaged product that is tight without wrinkles can be provided.

The polyamide-based laminated film has a water vapor permeability measured at 40 ° C. and 90% RH (relative humidity) of preferably 600 g / m ² · day or more, and more preferably 700 g / m ² · day or more. . When the water vapor permeability is equal to or higher than the above-described value, it is possible to prevent the contents from being spoiled by oxygen and the loss of moisture during long-term storage of the packaged food, and to maintain the flavor of the contents. Furthermore, it is preferable that the yellow degree (YI) in a polyamide-type laminated | multilayer film is 10 or less, and the suitable film without the dullness of a color tone for food packaging is obtained.

  The polyamide-based laminated film of the present invention has little yellowishness and good film appearance, has a large water vapor permeability and excellent smoke treatment effect, elution resistance and slipperiness, and has a film appearance and water vapor permeability and smoke treatment effect. Highly compatible. The laminated film easily permeates moisture containing smoked scents and flavor components and is suitable for smoked processing, while it is moderately impervious to gas, and further, such as clip processing, shearing processing, content filling, etc. Since it has sufficient strength to withstand casing processing, it is suitable as a film for transferring smoked liquid food.

The example of the polyamide-type laminated film of the 2nd side surface of this invention is shown with a schematic diagram and a photograph. FIG. 1 is a perspective view and a sectional view showing an example of the film of the present invention used as a package for smoked food, and FIG. 2 is a perspective view showing an example of the smoked food packaged with the multilayer film of the present invention.
As shown in FIG. 1, the laminated film 2 that wraps the food 1 inside includes, for example, a (a) layer and a (b) layer, the (b) layer is a food contact surface, and the (a) layer is (B) On the opposite side of the food from the layer.

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

  In addition, the evaluation method of the material used in the following Examples and Comparative Examples and various films is shown.

[Materials Used in Examples and Comparative Examples]
(A) Polyamide resin (A-1) Polyamide 6/66 copolymer: UBE NYLON 5033B manufactured by Ube Industries, Ltd., relative viscosity 4.0, melting point 198 ° C.
(A-2) Polyamide 6 polymer: UBE NYLON1022B, relative viscosity 3.35, melting point 220 ° C., manufactured by Ube Industries, Ltd.

(B-1) Poly (N-vinyl-2-pyrrolidone) polymer: BASF Japan, Ltd. product Rubitec K90 (mass average molecular weight: 1,500,000)
(B-2) Poly (N-vinyl-2-pyrrolidone) polymer: BASF Japan KK RUBITEC K30 (mass average molecular weight: 50,000)

(C) Crosslinked poly (N-vinyllactam) (C-1) Crosslinked poly (N-vinyl-2-pyrrolidone): Polyplaston XL-10 (average particle size: 30 μm) manufactured by ISP Japan Co., Ltd.
(C-2) Poly (N-vinyl-2-pyrrolidone) cross-linked product: BASF Japan, Ltd. Ruby Cross (average particle size: 100 μm)

[Yellowness (YI)]
Samples of 5.0 cm length and 5.0 cm width were cut out from the evaluation film, respectively, and four of the same samples were stacked. Using a color computer SM-5-IS-2B manufactured by Suga Test Instruments Co., Ltd., the yellowness ( YI) was measured. When the YI value was 10 or less, it was judged that a film having a small yellowishness was obtained.

[Oxygen permeability]
According to ASTM D-3985, it was measured under conditions of 23 ° C. and 0% RH (relative humidity) using MOCON-OX-TRAN 2/20 manufactured by Modern Control Co., Ltd.

[Water vapor permeability]
According to ASTM F-1770, measurement was performed under the conditions of 40 ° C. and 90% RH (relative humidity) using a moisture permeability measuring device MAS1000 manufactured by MAS. When the water vapor permeability was 600 g / m ² · day or more, it was judged that the water vapor permeability was excellent.

[Smoked evaluation test]
About 300 g of pork sausage raw material consisting of 70% by mass of pork, 20% by mass of water, 7% by mass of starch and 3% by mass of salt was filled in a tube-shaped film, and both ends were sealed with clips to obtain respective packages. Each obtained package is dried in a smoke chamber at a temperature of 60 ° C. and a humidity of 10 to 30% RH (relative humidity) for 15 minutes, and then at a temperature of 60 ° C. and a humidity of 40 to 60% RH (relative humidity). Smoke treatment was performed for 90 minutes at a lower temperature and immediately cooled in 5 to 10 ° C. cooling water for 10 minutes. The smoke effect of the obtained package was determined by a sensory test (panel test) for confirming the smoke effect.
The sensory test (panel test) was evaluated as follows.
0: No smoke property is observed (no smoke effect).
1: Smoke is slightly recognized.
2: Smoke is clearly recognized.
3: Smoke is strongly recognized.
4: Smoke is very strong.

[Elution resistance]
Based on the polyeco-elution test (evaporation residue test method), tests were conducted using n-heptane and water as the leaching solution. 300 ml of test solution (If heptane was used as the leaching solution, 300 ml of n-heptane was transferred to an eggplant-shaped flask and concentrated under reduced pressure to a few ml, and the flask was washed twice with about 5 ml of heptane each time. Solution is used, and the film is immersed in the test solution, treated with n-heptane at a temperature of 25 ° C. for 60 minutes, with water at a temperature of 95 ° C. for 30 minutes, and previously dried at 105 ° C. and made of quartz of known weight. Take in an evaporating dish and evaporate to dryness on a water bath. Subsequently, after drying at 105 degreeC for 2 hours, it cools in a desiccator. After cooling, the sample was weighed to determine the weight difference a (mg) before and after the evaporating dish, and the amount of evaporation residue was determined by the following equation.
Evaporation residue (μg / ml) = ((a−b) × 1000) / sample collected (ml)
However, b: Blank test value obtained for the same amount of leaching solution as the test solution (ml)
The case where the evaporation residue using n-heptane and water as the leaching solution was 30 μg / ml or less was judged as suitable for dissolution resistance.

[Sliding]
The obtained cylindrical laminated biaxially stretched film was cut open, and the dynamic friction coefficient between the film innermost layer surfaces was measured at 23 ° C. and 50% RH according to ASTM D-1894. The measurement was performed 5 times, and the average value was obtained. When the dynamic friction coefficient was 0.5 or less, it was judged that the slipperiness of the film was excellent.

Example 1
(A) Polyamide resin (A-1), (B) Vinylamide polymer (B-1) blended in the proportions shown in Table 1 are twin screw extruders (TEX30 manufactured by Nippon Steel Works) And melt-kneaded under conditions of an extruder set temperature of 250 ° C. and a screw rotation speed of 100 rpm, and granulated and dried to obtain (A1) a polyamide resin composition (A1-1).
Similarly, a blend of (A) polyamide resin (A-1) and (C) crosslinked poly (N-vinyllactam) (C-1) in the proportions shown in Table 1 is a twin-screw extruder ((stock) ) Nippon Steel Works TEX30 type), melt-kneaded under the conditions of an extruder set temperature of 250 ° C. and a screw rotation speed of 100 rpm, granulated and dried. (A2) Polyamide resin composition (A2-1) Got.
Similarly, a blend of (A) polyamide resin (A-2) and (C) crosslinked poly (N-vinyllactam) (C-1) in the proportions shown in Table 1 is a twin-screw extruder ((stock) ) Nippon Steel Works TEX30 type), melt-kneaded under the conditions of an extruder set temperature of 250 ° C. and a screw rotation speed of 100 rpm, granulated and dried. (A2) Polyamide resin composition (A2-2) Got.
(A1) Polyamide resin composition (A1-1), (A2) Polyamide resin composition (A2-1), (A2-2) 100 parts by mass of ethylenebisstearylamide 0.08 parts by mass (A1-1) and (A2-1) were extruded at 240 ° C. and (A2-2) in a 40 mmφ extruder equipped with a circular three-layer die using the composition blended using a mold mixer. ) Are melted separately at an extrusion temperature of 260 ° C., and taken up while being cooled with water at 20 ° C., and (A1) a layer made of the polyamide resin composition (A1-1) is (a) layer, (A2) When the layer made of the polyamide resin composition (A2-1) is the (b) layer and the layer (A2) the polyamide resin composition (A2-2) is the (b ′) layer, the layer structure is (b) / (A) / (b ′) substantially amorphous and non-oriented laminated unstretched film I got a film.
Subsequently, stretching is 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 the gas is pressurized and blown in the longitudinal and lateral directions at the same time, and the folding width is 70 mm. (B) A cylindrical laminated biaxially stretched film of / (a) / (b ′) = 10/15/10 μm was obtained. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Examples 2-3
In Example 1, except that the blending amount of (B) vinylamide polymer (B-1), (C) crosslinked poly (N-vinyllactam) (C-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. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Example 4
In Example 1, a laminated biaxially stretched film was obtained in the same manner as in Example 1 except that (C) the crosslinked poly (N-vinyllactam) (C-1) was changed to (C-2). It was. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Example 5
In Example 1, except that (A2) the polyamide resin composition (A2-1) was changed to (A) polyamide 6/66 copolymer (A-1), the same method as in Example 1 ( A1) A layer made of polyamide resin composition (A1-1) is (a) layer, (A2) a layer made of polyamide resin composition (A2-2) is (b) layer, and (A) polyamide resin (A-1) ) Was used as a layer (c) to obtain a cylindrical laminated biaxially stretched film of (c) / (a) / (b) = 10/15/10 μm. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 1
In Example 1, except that (B) vinylamide polymer (B-1) and (C) cross-linked poly (N-vinyllactam) (C-1) were not used, the same method as in Example 1 was used. 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 2-3
In Example 1, except that the blending amount of (B) vinylamide polymer (B-1), (C) crosslinked poly (N-vinyllactam) (C-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. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 4
In Example 4, a laminated biaxially stretched film was obtained in the same manner as in Example 4 except that (B) the vinylamide polymer (B-1) was not used. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 5
In Example 4, except that (B) the vinylamide polymer (B-1) is changed to (B-2) and the (C) poly (N-vinyllactam) crosslinked product (C-2) is not used, A laminated biaxially stretched film was obtained in the same manner as in Example 4. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

Comparative Example 6
In Example 1, except that (A1) the polyamide resin composition (A1-1) was changed to (A1-3) and changed to the layer configuration shown in Table 1, the biaxially laminated structure was the same as in Example 1. A stretched film was obtained. The physical property measurement results of the laminated biaxially stretched film are shown in Table 1.

As is clear from Table 1, the laminated film of Comparative Example 1 which does not use (B) vinylamide polymer (B-1) and (C) crosslinked poly (N-vinyllactam) (C-1) has a water vapor permeability. The smoked effect and slipperiness were not sufficient. Moreover, even if it uses together (B) and (C) component, the ratio is other than prescription | regulation of this invention, and the laminated film of the comparative example 2 whose compounding quantity of (B) and (C) component is less than a prescription | regulation range. The water vapor permeability, smoked effect, and slipperiness were not sufficient. The laminated film of Comparative Example 3 in which the blending amounts of the components (B) and (C) exceeded the specified range had high yellowness and poor elution resistance. (C) The laminated film of Comparative Example 4 using only the poly (N-vinyllactam) crosslinked product (C-2) component had a low water vapor permeability, and the smoked effect was not sufficient. Furthermore, the laminated film of Comparative Example 5 using only the component (B) vinylamide polymer (B-2) had a high yellowness and was inferior in elution resistance and slipperiness. (A) Laminated film of Comparative Example 6 in which (b) layer made of polyamide resin composition (A2) containing polyamide resin and (C) crosslinked poly (N-vinyllactam) is not disposed in the innermost layer The smoked effect and slipperiness were not sufficient.
On the other hand, the laminated films of Examples 1 to 5 defined in the present invention have little yellowness and good film appearance, and have a large water vapor permeability and excellent smoke treatment effect, elution resistance, and slipperiness. it is obvious.

Claims (8)

  (A) Polyamide resin 80 to 98% by mass and (B) 2 to 20% by mass of vinylamide polymer (A1) (a) layer made of polyamide resin composition, (A) Polyamide resin 70 to 98% by mass % And (C) a poly (N-vinyllactam) cross-linked product of 2 to 30% by mass (A2) comprising a polyamide resin composition (b) having at least two layers, (A2) polyamide The (b) layer comprising the resin composition is disposed as an exposed surface layer, and the (a1) layer comprising the (A1) polyamide resin composition is disposed on the side opposite to the exposed surface with respect to the (b) layer. Characteristic polyamide-based laminated film.   (A) The polyamide resin is any 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 polyamide-based laminated film according to claim 1.   (B) The vinylamide polymer is poly (N-vinyl-2-pyrrolidone), and (C) the crosslinked poly (N-vinyllactam) is a crosslinked poly (N-vinyl-2-pyrrolidone). The polyamide-based laminated film according to claim 1 or 2.   The polyamide-based laminated film according to any one of claims 1 to 3, wherein (A2) the polyamide resin constituting the polyamide resin composition (A2) in the laminated film is a polyamide 6 polymer.   It consists of 2-7 layers, The polyamide-type laminated | multilayer film in any one of Claim 1 to 4 characterized by the above-mentioned.   The polyamide-based laminated film according to any one of claims 1 to 5, wherein the polyamide-based laminated biaxially stretched film is stretched 2.0 times or more in the longitudinal and lateral directions.   The polyamide-based laminated film according to any one of claims 1 to 6, wherein the polyamide-based laminated film is used as a smoked liquid food transfer film.   A smoked food is packaged with the film according to any one of claims 1 to 7, and (A2) the polyamide resin composition (b) is disposed in the innermost layer in contact with the food, and (A1) a polyamide resin The packaged smoked food characterized by the (a) layer which consists of a composition being arrange | positioned on the outer side with respect to the (b) layer.

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