JP2010242076A - Polyamide resin composition for film, and film composed thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin composition for a film which has matte texture, is less yellowish, and has a satisfactory film appearance, which has high water-vapor permeability, is highly effective in smoking treatment, diminishes troubles such as filter clogging, and has excellent suitability for continuous production, and to provide a film composed thereof. <P>SOLUTION: The polyamide resin composition for the film comprises a polyamide resin (A), a vinylamide polymer (B), and a crosslinked poly(N-vinyllactam) (C) with an average particle size of 10-70 μm, wherein the blending ratio of the polyamide resin (A) to the sum of the vinylamide polymer (B) and the crosslinked poly(N-vinyllactam) (C), (A):((B)+(C)), is 70:30 to 98:2 mass% and the blending ratio of the vinylamide polymer (B) to the crosslinked poly(N-vinyllactam) (C), (B)/(C), is 80/20 to 20/80 (mass ratio). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyamide composition for a film comprising a polyamide resin, a vinylamide polymer, and a crosslinked poly (N-vinyllactam), and a film comprising the same. More specifically, continuous productivity that has a matte texture, a little yellowishness, good film appearance, high water vapor permeability, excellent smoke treatment effect, and can reduce troubles such as filter clogging. The present invention relates to an excellent polyamide resin composition for film and a film comprising the same.

  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 excellent, since the hydrophilic compound is highly finely dispersed in the polyamide matrix, the film does not exhibit a matte texture and is unsatisfactory to give an image of high quality. Furthermore, although the polyamide film which mix | blended polyvinylpyrrolidone as a hydrophilic compound is disclosed, it is described that this hydrophilic compound is soluble in 20 degreeC water. According to our study, it has been found that the yellowness of the polyamide film containing the polyvinylpyrrolidone having such properties is extremely inferior, and the commercial value may be significantly impaired.

  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. If the amount of crosslinked polyvinyl pyrrolidone is increased, clogging of the filter frequently occurs and there is a problem in continuous productivity.

US Pat. No. 7,361,392 JP 2002-306059 A

  The object of the present invention is a continuous material that has a matte texture, has a little yellowishness and good film appearance, has a large water vapor permeability and excellent smoke treatment effect, and can reduce troubles such as filter clogging. The object is to provide a polyamide resin composition for a film excellent in productivity and a film comprising the same.

  As a result of intensive studies in view of these situations, the present inventors have found that a polyamide resin, a vinylamide polymer, and a crosslinked poly (N-vinyllactam) having a specific average diameter are blended at a specific ratio. The present inventors have found that a polyamide composition for use and a film comprising the same solve the above-mentioned problems, and have reached the present invention.

  That is, the present invention comprises (A) a polyamide resin, (B) a vinylamide polymer, and (C) a poly (N-vinyl lactam) crosslinked product having an average particle size of 10 to 70 μm, The blending ratio of the total amount of (A) polyamide resin, (B) vinylamide polymer and (C) crosslinked poly (N-vinyllactam) is (A): ((B) + (C)) = 70: 30-98: 2% by mass, and the blending ratio of (B) vinylamide polymer and (C) crosslinked poly (N-vinyllactam) is (B) / (C) = 80 / 20-20 / It is related with the polyamide resin composition for films characterized by being 80 (mass ratio).

Preferred embodiments of the polyamide resin composition for a film of the present invention and a film comprising the same are shown below. A plurality of preferred embodiments can be combined.
[1] 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 resin composition for a film, characterized in that
[2] The (A) polyamide resin is a homopolymer or copolymer having at least one selected from the group of caprolactam units, hexamethylene adipamide units, and dodecane lactam units as a constituent unit. Polyamide resin composition for film.
[3] (A) The polyamide resin is any one selected from the group consisting of a polyamide 6 polymer, a polyamide 6/66 copolymer, a polyamide 6/12 copolymer, and a polyamide 6/66/12 copolymer. A polyamide resin composition for film.
[4] A polyamide film comprising the polyamide resin composition for a film.
[5] A biaxially stretched polyamide film comprising the polyamide resin composition for a film.
[6] A smoked casing film comprising the polyamide resin composition for a film.
[7] Water vapor permeability measured at 40 ° C. and 90% RH is 1000 g / m ² · day or more, yellowness (YI) is 20 or less, and gloss (gloss value) is 70% or less. A film characterized by
[8] A smoked food characterized in that the smoked food is packaged with the above film.

Since the polyamide resin composition for a film of the present invention contains a vinylamide polymer and a crosslinked poly (N-vinyllactam) having a specific average particle size in a specific blending amount and ratio, The film has a good texture, has a yellowish appearance and a good film appearance, has a high water vapor permeability and excellent smoke treatment effect, can reduce troubles such as filter clogging, and is excellent in continuous productivity. have.
The film is easily penetrated by moisture containing smoked scents and flavor components and is suitable for smoked processing, while it is moderately impervious to gas, and further has a casing for clip processing, shearing processing, content filling, etc. Since it has sufficient strength to withstand processing, it is suitable as a smoked casing film.

Hereinafter, the present invention will be described in detail.
The polyamide resin composition of the present invention comprises (A) a polyamide resin, (B) a vinylamide polymer, and (C) a crosslinked poly (N-vinyllactam) having an average particle size of 10 to 70 μm. The proportion of the total amount of (A) polyamide resin, (B) vinylamide polymer and (C) cross-linked poly (N-vinyllactam) is (A): ((B) + (C)) = 70: 30 to 98: 2% by mass, and the blending ratio of (B) vinylamide polymer and (C) crosslinked poly (N-vinyllactam) is (B) / (C) = 80/20 ~ 20/80 (mass ratio).

  (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) 6T (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 azelamide (polyamide 109), polydecane methylene decanamide (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 MXD) ), 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 PAMI) ), Polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (polyamide dimethyl PACM12), polyisophorone adipamide (polyamide IPD6) ), 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 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, alicyclic such as aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine Aromatic monoamines such as monoamine, aniline, toluidine, diphenylamine, and naphthylamine, aliphatic diamines such as hexamethylenediamine, nonamethylenediamine, decamethylenediamine, and dodecamethylenediamine, and cycloaliphatic such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine Aromatic diamines such as diamine, m- / p-phenylenediamine, m- / p-metaxylylenediamine, acetic acid, propionic acid, butyric acid Alicyclic monocarboxylic acids such as valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, cyclohexanecarboxylic acid, Aromatic monocarboxylic acids such as benzoic acid, toluic acid, α- / β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid, adipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane Aliphatic dicarboxylic acids such as dicarboxylic acid and dodecane dicarboxylic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,3- / 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 1, Aromatics such as 4- / 2,6- / 2,7-naphthalenedicarboxylic acid And a carboxylate. 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. If the polymerization temperature is lower than the above value, the polymerization reactivity may be lowered and the polymerization reaction may be very slow. On the other hand, if the polymerization temperature is higher than the above value, side reactions will increase and the reaction control becomes difficult. There is a case.

  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′-azobisisobutyronitrile, 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-methylpropio) Tolyl), 2,2′-azobis (2-cyclopropylpropionitrile), 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-methyl) Propionamide), 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2 ′ Azobis [2-methyl-N- [2-hydroxyethyl] 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-me Azo compounds such as tilpropionamidine] 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 1,000 to 5,000,000, more preferably 50,000 to 4,000,000, and 100,000 to 3, More preferably, it is 000,000. When the mass 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.

  (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. Further, (B) the vinylamide polymer is not a crosslinked product.

  The (C) crosslinked poly (N-vinyl lactam) is a product obtained by further crosslinking a polymer having an average particle diameter of 10 to 70 μm and comprising 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) A crosslinked poly (N-vinyllactam) is crosslinked 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 method using a vinyl lactam monomer described in Japanese Patent Publication Nos. 54-30027, 3-39087, and Japanese Patent Publication Nos. 61-78808 and 61-78809 as a crosslinking agent and a solvent. 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. The (C) crosslinked poly (N-vinyl lactam) is obtained as a powder form having an average particle size of 5 μm to 5 mm, but the (C) crosslinked poly (N-vinyl lactam) used in the present invention is The average particle size is in the range of 10 to 70 μm, preferably 10 to 50 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. 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, a film surface shape having a high-quality matte appearance cannot be obtained. (C) When the particle size of the crosslinked poly (N-vinyllactam) does not conform to the above range, 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.

  In the polyamide resin composition of the present invention, the blending ratio of (A) polyamide resin, (B) vinylamide polymer, (C) crosslinked poly (N-vinyllactam) is (A) polyamide resin and (B) vinylamide. The ratio of the total amount of the polymer and (C) crosslinked poly (N-vinyllactam) is within the range of (A): ((B) + (C)) = 70:30 to 98: 2% by mass. Yes, preferably in the range of 75:25 to 97: 3% by mass, and more preferably in the range of 80:20 to 95: 5% by mass. When the blending amount of the (B) vinylamide polymer and the (C) crosslinked poly (N-vinyllactam) is less than the above value, a matte texture and a high-class feeling are imparted to the film appearance. In addition, the hydrophilicity is lost and the effects of the present invention do not appear. On the other hand, when the above value is exceeded, the (B) vinylamide polymer and the (C) poly (N-vinyl lactam) cross-linked product tend to easily fall off by operations such as water and oil treatment.

  Furthermore, in consideration of the balance performance of the whole film such as the matte view of the film and water vapor permeability, the blending ratio of (B) vinylamide polymer and (C) crosslinked poly (N-vinyllactam) is (B) / (C) = 80/20 to 20/80 (mass ratio), preferably 70/30 to 30/70 (mass ratio), and preferably 60/40 to 40/60 (mass ratio). Is more preferable. When the blending ratio of the (B) vinylamide polymer exceeds the above value, a matte texture cannot be imparted, the yellowness (YI) becomes high, and the film appearance is inferior. If it is less than 1, the water vapor permeability of the film may be reduced, and the continuous productivity during film formation is inferior.

  The blending method of (B) vinylamide polymer or (C) crosslinked poly (N-vinyllactam) into (A) polyamide resin is as follows: (A) polyamide resin, (B) vinylamide polymer, (C) poly It is manufactured by blending (N-vinyl lactam) cross-linked product with various additives as necessary and mixing them 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. The blending of the (B) vinylamide polymer or the (C) crosslinked poly (N-vinyl lactam) into the (A) polyamide resin may be performed simultaneously or separately. Furthermore, the blending method of the (B) vinylamide polymer and the (C) poly (N-vinyl lactam) crosslinked product may be different. In the present invention, the kneading method for melt-kneading in advance or the production method by the masterbatch method strongly strengthens the entanglement between the (B) vinylamide polymer or (C) poly (N-vinyllactam) crosslinking and the (A) polyamide resin. Can be desirable.

  In the polyamide resin composition of the present invention, various additives and modifiers that are usually blended in the resin composition, for example, a heat stabilizer, an ultraviolet absorber, light, and the like, as long as the properties of the obtained film are not impaired. Stabilizer, antioxidant, antistatic agent, lubricant, antiblocking agent, filler, tackifier, sealability improver, antifogging agent, crystal nucleating agent, mold release agent, plasticizer, crosslinking agent, foaming agent, Colorants (pigments, dyes, etc.), bending fatigue resistance improving materials, etc. can be added.

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

  The blending amount of the bisamide compound is preferably 0.01 to 0.5 parts by mass, more preferably 0.02 to 0.3 parts by mass with respect to 100 parts by mass of the (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 polyamide resin composition has an xylylene diene selected from amorphous polyamide, m-xylylenediamine, and p-xylylenediamine having no crystallization temperature in order to improve stretchability and barrier properties during film production. It is preferable to blend a semi-aromatic polyamide containing 70 mol% or more of a polyamide constituent unit derived from an 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. Other copolymerizable structural units are particularly preferably hexamethylene adipamide units, caprolactam units, and dodecane lactam units.

  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.

  Examples of other polyamide constituent units include 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 dodecamide copolymer copolymers thereof.

  Molecular chain of a polyamide structural unit derived from an amorphous polyamide having no crystallization temperature, 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 70 mol% or more is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass with respect to 100 parts by mass of the (A) polyamide resin. More preferably, it is 5-20 mass parts. If the blending amount is less than the above value, the effect of improving stretchability and barrier property may be small. On the other hand, if the blending amount exceeds the above value, the melt viscosity may be high and the production of the film may be difficult.

  In the present invention, a polyamide resin composition (hereinafter referred to as a raw material polyamide resin composition) comprising (A) a polyamide resin, (B) a vinylamide polymer, and (C) a crosslinked poly (N-vinyl lactam). )), A known film manufacturing method is applied to form a polyamide film. For example, a raw material polyamide resin composition is melt-kneaded with an extruder, extruded into a flat film shape with a T-die or a coat hanger die, cast on a casting roll surface, and cooled to produce a film. There is a tubular method for producing a film by air-cooling or water-cooling a tubular material melt-extruded into a cylindrical shape. The produced film can be used as a substantially non-oriented unstretched film, but is preferably a biaxially stretched film from the viewpoint of the strength and gas barrier properties of the obtained film.

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

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

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.

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

  The obtained polyamide film has a matte texture, has a small yellowish color and good film appearance, has a large water vapor permeability and excellent smoke treatment effect, and has a high utility value alone. By laminating the thermoplastic resin, it is possible to add more characteristics. Specifically, a thermoplastic resin layer can be laminated on at least one side of a polyamide film, and used as a laminated film.

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

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

  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.

  The thickness of the polyamide film may be appropriately determined depending on the application, and is not particularly limited. However, if the thickness of the polyamide film is too large, the strength of the polyamide film is improved, but the transparency and bending fatigue resistance are lowered and the thickness is too small. For example, in the case of a polyamide single layer film, it is preferably 5 to 100 μm, more preferably 10 to 80 μm, and more preferably 15 to 60 μm. More preferably it is. In the case of a laminated film, the thickness of the raw material polyamide resin composition layer is preferably 2 to 100 μm, more preferably 3 to 80 μm, and further preferably 5 to 60 μm.

  When the polyamide film is a stretched film, the shrinkage rate when immersed in hot water at 80 ° C. (hot water shrinkage rate) is preferably 5% or more in each direction, more preferably 8% or more, More preferably, it is 10% or more. Therefore, even after the bag product is cooled, the casing can be in close contact with the contents, and a final packaged product can be provided that is tight and has no wrinkles.

The polyamide film has a water vapor permeability measured at 40 ° C. and 90% RH (relative humidity) of preferably 1000 g / m ² · day or more, and more preferably 1200 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.

Further, the yellowness (YI) of the polyamide film is preferably 20 or less, and a film free from dullness with a color tone suitable for food packaging can be obtained.
Further, the gloss (gloss value) of the polyamide film is preferably 70% or less, and a high-quality film having a matte texture can be obtained due to the low gloss.

  The polyamide film of the present invention has good film formability and stretchability during film production, and has characteristics such as appropriate hot water shrinkage, creep property, toughness, gas barrier property, and dimensional stability. In addition, it exhibits excellent smoke properties and a high oxygen gas barrier property during storage, and is useful for long-term storage of smoke-treated food packages. In particular, oxygen-sensitive foods, processed livestock products such as ham, sausage, bacon, and meat, dairy products such as cheese, processed fishery products such as fish sausage, processed agricultural products such as konjac and seaweed, egg products, cooked foods, etc. It is suitable as a casing film for filling and packaging food or semi-fluid food.

  In the following, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples without departing from the gist of the present invention.

  In addition, the material used in the following examples and comparative examples, and the evaluation method of a film are 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) Vinylamide polymer (B-1) Poly (N-vinyl-2-pyrrolidone) polymer: Rubytech K90 manufactured by BASF Japan Ltd. (mass average molecular weight: 1,500,000)
(B-2) Poly (N-vinyl-2-pyrrolidone) polymer: BASF Japan, Ltd. RUBYTECH 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) crosslinked product: Ruby cloth (average particle size: 100 μm) manufactured by BASF Japan Ltd.

[Glossiness (Gloss)]
In accordance with ASTM D-523, the gloss (gloss value) was measured using a color computer SM-5-IS-2B manufactured by Suga Test Instruments Co., Ltd. When the gloss value was 70% or less, it was judged that a sufficient matte tone was obtained.

[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 20% or less, it was judged that a film having a small yellow color 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 1000 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.

[Continuous productivity]
Using the raw material resin composition, it is melted at an extrusion temperature of 260 ° C. in a 40 mmφ extruder equipped with a circular die, and taken off while being cooled with water at 20 ° C., and an unstretched film is continuously formed. Manufactured. The filter differential pressure during molding was measured over time, and it was determined that the filter was clogged when the increase was noticeable. The case where no increase in the differential pressure was observed within the test time of 8 hours was judged as good continuous productivity. A filter mesh having a size of 80/125/125/80/80/125/125/80 was used.

Example 1
(A) Polyamide resin (A-1), (B) vinylamide polymer (B-1), (C) crosslinked poly (N-vinyllactam) (C-1) in the proportions shown in Table 1. Is fed to a twin-screw extruder (TEX30 type, manufactured by Nippon Steel), melt-kneaded under the conditions of an extruder set temperature of 250 ° C. and a screw rotation speed of 100 rpm, granulated, dried, and polyamide resin A composition was obtained.

  Next, using a cylindrical mixer, a composition in which 0.08 parts by mass of ethylene bisstearylamide was blended with 100 parts by mass of the pellets of the polyamide resin composition was used, and a 40 mmφ equipped with a circular die An unstretched tubular polyamide film that is melted at an extrusion temperature of 260 ° C. and cooled with water at 20 ° C. while being taken up, and is substantially amorphous and not oriented. Got. Subsequently, stretching is performed at a stretching temperature of 160 ° C. and a stretching ratio (both longitudinal and lateral) of 3.0 times by a tubular stretching method in which the gas pressure is blown in the longitudinal and lateral directions in an inflation manner, and the folding width is 70 mm and the thickness is 25 μm. A cylindrical biaxially stretched polyamide film was obtained. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1. Table 1 shows the results of investigation on continuous productivity by the above method.

Examples 2-5
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 biaxially stretched polyamide film was obtained in the same manner as in Example 1. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1. Table 1 shows the results of investigation on continuous productivity by the above method.

Example 6
A biaxially stretched polyamide film was obtained in the same manner as in Example 2 except that (B) the vinylamide polymer (B-1) was changed to (B-2) in Example 2. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1. Table 1 shows the results of investigation on continuous productivity by the above method.

Example 7
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (A) the polyamide resin (A-1) was changed to (A-2) in Example 1. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1. Table 1 shows the results of investigation on continuous productivity by the above method.

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 biaxially stretched polyamide film was obtained. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1. Table 1 shows the results of investigation on continuous productivity by the above method.

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 biaxially stretched polyamide film was obtained in the same manner as in Example 1. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1. Table 1 shows the results of investigation on continuous productivity by the above method.

Comparative Examples 4-5
In Example 6, except that the blending amount of (B) vinylamide polymer (B-2), (C) crosslinked poly (N-vinyllactam) (C-1) was changed to the amount shown in Table 1, A biaxially stretched polyamide film was obtained in the same manner as in Example 6. Table 1 shows the results of investigation on continuous productivity by the above method.

Comparative Example 6
In Example 6, a biaxially stretched polyamide film was obtained in the same manner as in Example 6 except that (C) the crosslinked poly (N-vinyllactam) (C-1) was changed to (C-2). It was. Table 1 shows the results of investigation on continuous productivity by the above method.

Comparative Example 7
In Example 1, (B) the vinylamide polymer (B-1) was not used, (C) the poly (N-vinyllactam) crosslinked product (C-1) was changed to (C-2), and (C ) A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the amount of the crosslinked poly (N-vinyllactam) (C-2) was changed to the amount shown in Table 1. Table 1 shows the results of investigation on continuous productivity by the above method.

Comparative Example 8
In Example 6, the (C) poly (N-vinyl lactam) crosslinked product (C-1) was not used, and the blending amount of the (B) vinylamide polymer (B-2) was changed to the amount shown in Table 1. A biaxially stretched polyamide film was obtained in the same manner as in Example 6 except that. Table 1 shows the results of investigation on continuous productivity by the above method.

  As is apparent from Table 1, Comparative Example 1 in which the components (B) and (C) were not used was not matte and inferior in film appearance, and the water vapor permeability and smoked effect 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 comparative example 2 whose compounding quantity of (B) and (C) component is less than a prescription | regulation range is mat. The film appearance was inferior, not the tone, and the water vapor permeability and smoked effect were not sufficient. On the other hand, Comparative Example 3 in which the blending amounts of the components (B) and (C) exceeded the specified range had high yellowness and poor continuous productivity. Comparative Example 4 in which the mixing ratio of the components (B) and (C) is less than the specified range of the present invention is inferior in water vapor permeability and smoked effect, and the mixing ratio of the components (B) and (C) is specified in the present invention. In Comparative Example 5 exceeding the range, the yellowness was high, and no matte film was obtained. Furthermore, Comparative Example 6 using the component (C) having an average particle diameter other than those prescribed in the present invention was inferior in water vapor permeability and smoked effect, and inferior in continuous productivity. Moreover, Comparative Example 7 using only the component (C) had a low water vapor permeability, was inferior in the smoke effect, and was inferior in continuous productivity. Further, Comparative Example 8 using only the component (B) had a high yellowness, and a film having a matte texture could not be obtained.

  On the other hand, the films of Examples 1 to 7 obtained from the polyamide resin composition defined in the present invention have a matte texture, little yellowness, good film appearance, and water vapor permeability. It is clear that it has a large smoke treatment effect, less trouble with filter clogging, and excellent continuous productivity.

Claims (9)

  It consists of (A) polyamide resin, (B) vinylamide polymer, (C) poly (N-vinyl lactam) crosslinked body having an average particle size of 10 to 70 μm, The blending ratio of the total amount of (B) vinylamide polymer and (C) crosslinked poly (N-vinyl lactam) is (A): ((B) + (C)) = 70:30 to 98: 2 mass. %, And the blending ratio of (B) vinylamide polymer and (C) crosslinked poly (N-vinyllactam) is (B) / (C) = 80/20 to 20/80 (mass ratio). A polyamide resin composition for a film, characterized in that it exists.   (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 resin composition for a film according to claim 1.   (A) The polyamide resin is a homopolymer or copolymer having at least one selected from the group of caprolactam units, hexamethylene adipamide units and dodecane lactam units as a constituent unit. Or the polyamide resin composition for a film according to any one of 2;   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. The polyamide resin composition for a film according to claim 3.   A polyamide film comprising the polyamide resin composition for a film according to claim 1.   A biaxially stretched polyamide film comprising the polyamide resin composition for a film according to any one of claims 1 to 4.   A smoked casing film comprising the polyamide resin composition for a film according to claim 1. Water vapor permeability measured at 40 ° C. and 90% RH (relative humidity) is 1000 g / m ² · day or more, yellowness (YI) is 20 or less, and gloss (gloss value) is 70% or less. The film according to claim 5, wherein:   The smoked food is packaged with the film according to claim 1.