JP2018070786A - Matte-like barrier polyamide film and manufacturing method therefor - Google Patents
Matte-like barrier polyamide film and manufacturing method therefor Download PDFInfo
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- JP2018070786A JP2018070786A JP2016213124A JP2016213124A JP2018070786A JP 2018070786 A JP2018070786 A JP 2018070786A JP 2016213124 A JP2016213124 A JP 2016213124A JP 2016213124 A JP2016213124 A JP 2016213124A JP 2018070786 A JP2018070786 A JP 2018070786A
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- polyamide
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- 230000004888 barrier function Effects 0.000 title claims abstract description 133
- 239000004952 Polyamide Substances 0.000 title claims abstract description 114
- 229920002647 polyamide Polymers 0.000 title claims abstract description 114
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 40
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 26
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract description 26
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
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- 238000009998 heat setting Methods 0.000 claims description 14
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- -1 poly Hexamethylene sebacamide Polymers 0.000 description 10
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 7
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
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- 238000002425 crystallisation Methods 0.000 description 4
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 229940127554 medical product Drugs 0.000 description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 239000004014 plasticizer Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
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- 238000007639 printing Methods 0.000 description 2
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- 238000004381 surface treatment Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
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- 239000003431 cross linking reagent Substances 0.000 description 1
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- 239000003651 drinking water Substances 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
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- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Packages (AREA)
- Wrappers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
本発明は、シリカを含有するポリアミド樹脂からなるポリアミドフィルムとバリア層を含む複層構成のマット調バリアポリアミドフィルムに関するものである。 The present invention relates to a mat-like barrier polyamide film having a multilayer structure including a polyamide film made of a polyamide resin containing silica and a barrier layer.
ポリアミド樹脂フィルムは、良好な機械的特性、熱的特性及び透明性を有しているため、包装用途、特に食品包装用途に広く用いられている。近年、用途の多様化の中の一用途として、意匠性を高めるために、フィルム表面に細かな凹凸を設けてすりガラス状としたマット調フィルムが求められている。このようなマット調とすることにより、フィルム表面の光沢をなくして（艶消し）内容物をぼかし、さらには和紙風合いを付与することにより、高級感のある包装体が得られる。フィルムにマット調を付与する手段のひとつとしては、フィルムを構成する樹脂中に無機粒子や有機合成樹脂などを含有させる方法が挙げられる。また、内容物の保存性を高める観点から、酸素バリア性の向上が求められている。 Polyamide resin films have good mechanical properties, thermal properties, and transparency, and are therefore widely used for packaging applications, particularly food packaging applications. In recent years, as one application among the diversification of applications, a matte-like film in which fine irregularities are provided on the film surface to form a ground glass has been demanded in order to improve design properties. By using such a matte tone, the gloss of the film surface is eliminated (matte), the content is blurred, and further, a Japanese paper texture is imparted, whereby a high-quality packaging can be obtained. As one of means for imparting a matte tone to the film, a method of incorporating inorganic particles, organic synthetic resin, or the like into the resin constituting the film can be mentioned. Moreover, the improvement of oxygen barrier property is calculated | required from a viewpoint of improving the preservability of the contents.
特許文献１には、特定のシリカを一定量添加することによってフィルムの表面を艶消し状にする方法、塩化ビニリデン系共重合体や、高水素結合性樹脂に無機層状化合物を配合した樹脂層を積層することによって酸素バリア性を付与する方法が記載されている。 Patent Document 1 includes a method of matting the surface of a film by adding a certain amount of specific silica, a vinylidene chloride copolymer, and a resin layer in which an inorganic layered compound is blended with a high hydrogen bonding resin. A method for providing oxygen barrier properties by laminating is described.
特許文献１においては、表面がマット調であり、酸素バリア性のあるフィルムを得ることができるが、シリカ粒子を含むものであるため、機械的特性については十分に満足できるものではなかった。つまり、シリカなどのフィラーを含有する場合、未延伸フィルムの延伸時に延伸応力が高くなり、このため、フィラーと密着している樹脂が延伸応力にて剥離し、空隙が発生する。そして、この空隙が多数発生したり、大きな空隙が発生して空隙率が高くなると、フィルムの衝撃強度や強伸度が著しく低下する。また、延伸応力が高くなると、ボーイング現象（延伸前のフィルムにフィルムの進行方向に対して直角にマークした直線が延伸・熱処理終了後、中央部が遅れた形の弓型に変形する現象）が大きくなり、長さ方向、幅方向の熱収縮率が大きいフィルムとなる。マット調バリアフィルムにおける衝撃強度と寸法安定性の両立は非常に困難なものであった。 In Patent Document 1, a film having a matte surface and an oxygen barrier property can be obtained. However, since it contains silica particles, the mechanical properties are not fully satisfactory. That is, when a filler such as silica is contained, the stretching stress becomes high when the unstretched film is stretched. For this reason, the resin that is in close contact with the filler peels off due to the stretching stress, and voids are generated. When a large number of voids are generated or large voids are generated and the void ratio is increased, the impact strength and the strong elongation of the film are remarkably lowered. In addition, when the stretching stress increases, the bowing phenomenon (a phenomenon in which a straight line marked perpendicular to the film traveling direction on the unstretched film deforms into a bow shape with a delayed center after stretching and heat treatment). The film becomes large and has a large thermal shrinkage in the length direction and the width direction. It was very difficult to achieve both impact strength and dimensional stability in the matte barrier film.
本発明は、シリカを含有するポリアミド樹脂からなるポリアミドフィルムであって、表面が艶消し状態であるマット調を有し、かつ衝撃強度と寸法安定性、酸素バリア性と水蒸気バリア性にも優れたマット調ガスバリアポリアミドフィルムおよびその製造方法を提供することを目的とするものである。 The present invention is a polyamide film made of silica-containing polyamide resin, has a matte surface with a matte surface, and is excellent in impact strength, dimensional stability, oxygen barrier property and water vapor barrier property. An object of the present invention is to provide a mat-like gas barrier polyamide film and a method for producing the same.
本発明者は上記課題を解決するために検討した結果、シリカを含有するポリアミド樹脂からなる未延伸フィルムを、特定の吸水率となるように吸水させ、特定の予熱・延伸温度・熱固定温度条件の下で同時二軸延伸することで、延伸応力を低減できることを見出した。これにより、フィルム中に生じる空隙を減少させることができ、また、ボーイング現象を低下させることができ、衝撃強度が高く、寸法安定性に優れたマット調ポリアミドフィルムを得ることができることを見出した。さらに、このフィルム上にポリ塩化ビニリデン系共重合体からなるバリア層や蒸着層を形成することによって、酸素バリア性及び水蒸気バリア性に優れたマット調バリアポリアミドフィルムを得ることができることを見出した。 As a result of studying the present inventors to solve the above-mentioned problems, an unstretched film made of a polyamide resin containing silica is allowed to absorb water so as to have a specific water absorption rate, and a specific preheating / stretching temperature / heat setting temperature condition. It was found that the stretching stress can be reduced by simultaneously biaxially stretching under. As a result, it has been found that the voids generated in the film can be reduced, the bowing phenomenon can be reduced, a matte polyamide film having high impact strength and excellent dimensional stability can be obtained. Furthermore, it has been found that a matte-like barrier polyamide film excellent in oxygen barrier property and water vapor barrier property can be obtained by forming a barrier layer or a vapor deposition layer comprising a polyvinylidene chloride copolymer on this film.
本発明の要旨は次のとおりである。
（イ）シリカを含有するポリアミド樹脂からなるポリアミドフィルム（Ｘ）とバリア層（Ｙ）を含む複層構成のポリアミドフィルムであって、
下記（１）〜（６）の条件を同時に満たすことを特徴とするマット調バリアポリアミドフィルム。
（１）光沢度が５０％以下
（２）フィルムの空隙率が０．１〜５％
（３）２０℃条件下で測定される衝撃強度が０．３５Ｊ以上
（４）フィルムの幅方向（ＴＤ方向）に対して４５度の方向と１３５度の方向における熱水収縮率の差が２．０％以下
（５）酸素透過度が、２０℃、６５％ＲＨ下で、１００ｍｌ／ｍ２・ｄａｙ・ＭＰａ以下
（６）水蒸気透過度が、４０℃、９０％ＲＨ下で、２０ｇ／ｍ２・ｄａｙ以下
（ロ）バリア層（Ｙ）がポリ塩化ビニリデン系共重合体にて形成されてなる、（イ）記載のマット調バリアポリアミドフィルム。
（ハ）（イ）又は（ロ）に記載のマット調バリアポリアミドフィルムを製造する方法であって、（１）、（２）の工程を順に行うことを特徴とするマット調バリアポリアミドフィルムの製造方法。
（１）未延伸フィルムの水分率が３〜９％になるように温水槽で吸水させた後、未延伸フィルムの少なくとも一方の面にポリ塩化ビニリデン系共重合体を含有するバリア層形成用塗料を塗布する。
（２）予熱温度１８０〜２５０℃で予熱を行い、温度１７０〜２３０℃で延伸を行い、さらに温度１８０〜２３０℃で熱固定を行う。
The gist of the present invention is as follows.
(A) A polyamide film having a multilayer structure comprising a polyamide film (X) comprising a polyamide resin containing silica and a barrier layer (Y),
A mat-like barrier polyamide film characterized by simultaneously satisfying the following conditions (1) to (6):
(1) Glossiness is 50% or less (2) Porosity of film is 0.1 to 5%
(3) Impact strength measured at 20 ° C. is 0.35 J or more. (4) The difference in hot water shrinkage between the direction of 45 degrees and the direction of 135 degrees with respect to the film width direction (TD direction) is 2. 0.05% or less (5) Oxygen permeability at 20 ° C. under 65% RH, 100 ml / m 2 · day · MPa or less (6) Water vapor permeability at 40 ° C. under 90% RH, 20 g / m 2 · day or less
(B) The matte barrier polyamide film according to (a), wherein the barrier layer (Y) is formed of a polyvinylidene chloride copolymer.
(C) A method for producing a matte-like barrier polyamide film as described in (a) or (b), wherein the steps (1) and (2) are sequentially performed. Method.
(1) A barrier layer-forming coating material comprising a polyvinylidene chloride copolymer on at least one surface of an unstretched film after water absorption in a hot water tank so that the moisture content of the unstretched film is 3 to 9%. Apply.
(2) Preheating is performed at a preheating temperature of 180 to 250 ° C., stretching is performed at a temperature of 170 to 230 ° C., and heat setting is further performed at a temperature of 180 to 230 ° C.
本発明のマット調バリアポリアミドフィルムは、表面が艶消し状態であるマット調を有し、かつ衝撃強度と寸法安定性に優れ、バリア性能として、酸素バリア性と水蒸気バリア性に優れたものである。このため、本発明のフィルムは、意匠性と機械的特性、内容物保存性の特性に優れており、食品や医療品をはじめとする各種包装用途に用いることができる。また、本発明のマット調バリアポリアミドフィルムの製造方法によると、本発明のフィルムを生産性よく得ることが可能となる。 The matte barrier polyamide film of the present invention has a matte surface with a matte surface, is excellent in impact strength and dimensional stability, and has excellent oxygen barrier properties and water vapor barrier properties as barrier performance. . For this reason, the film of this invention is excellent in the design property, the mechanical characteristic, and the characteristic of the content preservation property, and can be used for various packaging uses including a foodstuff and a medical product. Moreover, according to the method for producing a matte-like barrier polyamide film of the present invention, the film of the present invention can be obtained with high productivity.
以下、本発明について詳細に説明する。
〔ポリアミドフィルム（Ｘ）〕
本発明のマット調バリアポリアミドフィルムのポリアミドフィルム（Ｘ）は、シリカを含有するポリアミド樹脂からなるものである。
Hereinafter, the present invention will be described in detail.
[Polyamide film (X)]
The polyamide film (X) of the matte-like barrier polyamide film of the present invention is made of a polyamide resin containing silica.
本発明において、ポリアミド樹脂とは、その分子内にアミド結合（−ＣＯＮＨ−）を有する溶融成形可能な熱可塑性樹脂であり、ポリカプラミド（ナイロン６）、ポリヘキサメチレンアジパミド（ナイロン６６）、ポリヘキサメチレンセバカミド（ナイロン６１０）、ポリアミノウンデカミド（ナイロン１１）、ポリラウリルアミド（ナイロン１２）および、これらの共重合体、混合物等が挙げられるが、特にナイロン６が好ましい。また、ポリアミドには、フィルムの性能を損なわない範囲においてタルク、シリカ、アルミナ、マグネシア、炭酸カルシウム、エチレンビスステアリルアミド、ステアリン酸カルシウム等の滑剤や、顔料、熱安定剤、酸化防止剤、耐候剤、難燃剤、可塑剤、離型剤を配合することもできる。 In the present invention, the polyamide resin is a melt-moldable thermoplastic resin having an amide bond (—CONH—) in the molecule, such as polycoupleramide (nylon 6), polyhexamethylene adipamide (nylon 66), poly Hexamethylene sebacamide (nylon 610), polyaminoundecamide (nylon 11), polylauryl amide (nylon 12), and copolymers and mixtures thereof may be mentioned, with nylon 6 being particularly preferred. In addition, the polyamide has a lubricant, such as talc, silica, alumina, magnesia, calcium carbonate, ethylene bisstearylamide, calcium stearate, pigments, heat stabilizers, antioxidants, weathering agents, as long as the performance of the film is not impaired. A flame retardant, a plasticizer, and a mold release agent can also be mix | blended.
ポリアミド樹脂の分子量の指標となる相対粘度は、機械物性の面から１．５〜５．０の範囲が好ましく、２．５〜４．０の範囲がより好ましい。ここで、相対粘度は９６質量％硫酸中、濃度１ｇ/ｄｌ、温度２５℃で測定された値である。 The relative viscosity that serves as an index of the molecular weight of the polyamide resin is preferably in the range of 1.5 to 5.0, more preferably in the range of 2.5 to 4.0 from the viewpoint of mechanical properties. Here, the relative viscosity is a value measured in 96% by mass sulfuric acid at a concentration of 1 g / dl and a temperature of 25 ° C.
本発明において、マット調バリアポリアミドフィルムのフィルム表面光沢度を５０％以下とするためにはポリアミド樹脂中にシリカを添加する必要がある。 In the present invention, it is necessary to add silica to the polyamide resin in order to make the film surface glossiness of the matte-like barrier polyamide film 50% or less.
シリカを添加する方法としては、ポリアミド樹脂の重合開始前または重合開始後の任意の時期に内部添加する方法、ポリアミド樹脂とシリカを押出機中で溶融混錬する方法、ポリアミド樹脂とシリカをドライブレンドする方法が挙げられる。中でも、シリカのポリアミド樹脂への添加は、フィルム中でのシリカの分散性の観点から、重合開始時または重合開始後の任意の時期に内部添加する方法が好ましい。 As a method of adding silica, a method of internally adding before or after the start of polymerization of polyamide resin, a method of melt-kneading polyamide resin and silica in an extruder, a dry blend of polyamide resin and silica The method of doing is mentioned. Among these, addition of silica to the polyamide resin is preferably performed by a method of internal addition at the start of polymerization or at any time after the start of polymerization from the viewpoint of dispersibility of silica in the film.
シリカには、分散性や耐候性、耐熱性、ポリマーとの密着性等を向上させるために、無機処理や有機処理などの表面処理を施してもよい。 Silica may be subjected to a surface treatment such as an inorganic treatment or an organic treatment in order to improve dispersibility, weather resistance, heat resistance, adhesion to a polymer, and the like.
本発明のポリアミドフィルム（Ｘ）中のシリカの含有量は、０．１〜１２質量％であることが好ましく、より好ましくは０．５〜１０質量％、さらに好ましくは１．５〜７質量％である。ポリアミドフィルム（Ｘ）中のシリカの含有量が０．１質量％未満の場合、フィルム表面の光沢度が高くなり、表面が艶消し状態であるマット調を有するものとすることが困難となる。一方、含有量が１２質量％を超える場合、空隙の発生が多大になり、衝撃強度を含む機械的特性が低下する。 The content of silica in the polyamide film (X) of the present invention is preferably 0.1 to 12% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1.5 to 7% by mass. It is. When the content of silica in the polyamide film (X) is less than 0.1% by mass, the glossiness of the film surface becomes high, and it becomes difficult to have a matte tone in which the surface is matte. On the other hand, when the content exceeds 12% by mass, voids are greatly generated, and mechanical properties including impact strength are deteriorated.
シリカの平均粒子径は１．０〜５．０μｍの範囲であることが好ましい。１．０μｍより小さいと、フィルム表面の突起を形成することが困難となるため、マット調が低下する。一方、５．０μｍを超えると、フィルム中の空隙が多大になり、衝撃強度を含む機械的特性低下の原因となるため好ましくない。 The average particle diameter of silica is preferably in the range of 1.0 to 5.0 μm. If it is smaller than 1.0 μm, it becomes difficult to form protrusions on the film surface, so that the matte tone is lowered. On the other hand, if it exceeds 5.0 μm, voids in the film become enormous, which causes a decrease in mechanical properties including impact strength.
〔バリア層（Ｙ）〕
本発明のマット調バリアポリアミドフィルムは、ポリアミドフィルム（Ｘ）とバリア層（Ｙ）を含む複層構成のポリアミドフィルムであり、バリア層（Ｙ）は、ポリアミドフィルム（Ｘ）の少なくとも一方の面に設けられるものである。バリア層（Ｙ）は、ポリ塩化ビニリデン系共重合体で形成されてなるものであることが好適である。
[Barrier layer (Y)]
The matte-like barrier polyamide film of the present invention is a polyamide film having a multilayer structure including a polyamide film (X) and a barrier layer (Y), and the barrier layer (Y) is formed on at least one surface of the polyamide film (X). It is provided. The barrier layer (Y) is preferably formed of a polyvinylidene chloride copolymer.
ポリ塩化ビニリデン系共重合体は、原料としての塩化ビニリデン５０〜９９質量％と塩化ビニリデンと共重合可能な１種以上の他の単量体を公知の乳化重合方法によって重合され、媒体へ分散状態であるラッテクスとして得られるものであることが好ましい。共重合可能な他の単量体の割合が１質量％未満であると樹脂内部の可塑化が不十分となり被膜の造膜性が低下し、また他の単量体の割合が５０質量％を超えるとガスバリア性が低下するため、ともに好ましくない。また、塩化ビニリデンの比率が高いほど結晶融点が高いポリ塩化ビニリデン系共重合体が得られるので、塩化ビニリデン比率を上記上限に近い比率、例えば、塩化ビニリデンが９５〜９９質量％の範囲で重合することによりポリ塩化ビニリデン系共重合体を得ることができる。 Polyvinylidene chloride copolymer is prepared by polymerizing 50 to 99% by mass of vinylidene chloride as a raw material and one or more other monomers copolymerizable with vinylidene chloride by a known emulsion polymerization method, and dispersing it in a medium It is preferable that it is obtained as a latex. If the proportion of the other monomer that can be copolymerized is less than 1% by mass, plasticization inside the resin is insufficient, and the film-forming property of the film is lowered, and the proportion of the other monomer is 50% by mass. When it exceeds, gas barrier property will fall, and it is unpreferable for both. In addition, since a polyvinylidene chloride copolymer having a higher crystal melting point is obtained as the ratio of vinylidene chloride is higher, the vinylidene chloride ratio is polymerized in a ratio close to the above upper limit, for example, in the range of 95 to 99% by mass of vinylidene chloride. Thus, a polyvinylidene chloride copolymer can be obtained.
塩化ビニリデンと共重合可能な単量体としては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、２−エチルへキシルアクリレート、２−ヒドロキシエチルアクリレート等のアクリル酸エステル、メタクリル酸メチル、メタクリル酸グリシジル等のメタクリル酸エステル、アクリロニトリル、メタクリロニトリル等のニトリル類、アクリル酸、メタクリル酸、イタコン酸、マレイン酸等の不飽和カルボン酸、塩化ビニルが挙げられる。これらの単量体は単独で用いてもよいし、併用してもよい。 Examples of the monomer copolymerizable with vinylidene chloride include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate, methyl methacrylate, and methacrylic acid. Examples thereof include methacrylic acid esters such as glycidyl acid, nitriles such as acrylonitrile and methacrylonitrile, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, and vinyl chloride. These monomers may be used alone or in combination.
ポリ塩化ビニリデン系共重合体は、水中に分散した状態でバリア層形成用塗料（ラテックス）として用いられ、ポリアミドフィルム（Ｘ）の少なくとも片面にコートされる。バリア層形成用塗料中のポリ塩化ビニリデン系共重合体の平均粒径は０．０５〜０．５μｍであることが好ましく、０．０７〜０．３μｍであることが特に好ましい。ポリ塩化ビニリデン系共重合体には、本発明の効果を損なわない範囲で、例えばアンチブロッキング剤、架橋剤、撥水剤、帯電防止剤などの各種添加剤を併用しても良い。 The polyvinylidene chloride copolymer is used as a barrier layer-forming paint (latex) in a state of being dispersed in water, and is coated on at least one surface of the polyamide film (X). The average particle size of the polyvinylidene chloride copolymer in the barrier layer-forming coating material is preferably 0.05 to 0.5 μm, and particularly preferably 0.07 to 0.3 μm. The polyvinylidene chloride copolymer may be used in combination with various additives such as an antiblocking agent, a crosslinking agent, a water repellent, and an antistatic agent, as long as the effects of the present invention are not impaired.
コートの方法は特に限定されるものではなく、例えば、グラビアロール法、リバースロール法、エアーナイフ法、リバースグラビア法、マイヤーバー法、インバースロール法、またはこれらの組み合わせによる各種コート方式や、各種噴霧方式などを採用することができる。
ポリアミドフィルム（Ｘ）には、コートの直前でコロナ放電処理などが行われても良い。
The method of coating is not particularly limited. For example, gravure roll method, reverse roll method, air knife method, reverse gravure method, Mayer bar method, inverse roll method, or a combination thereof, or various sprays A method etc. can be adopted.
The polyamide film (X) may be subjected to corona discharge treatment immediately before coating.
ポリ塩化ビニリデン系共重合体で形成されるバリア層（Ｙ）の厚みは、０．５μｍ〜３．５μｍの範囲が好ましく、さらに好ましくは０．７μｍ〜３．０μｍの範囲であり、特に好ましくは１．０μｍ〜２．５μｍの範囲である。このバリア層（Ｙ）が０．５μｍよりも薄いと十分なバリア性（酸素バリア性や水蒸気バリア性）が発現しにくい。一方、バリア層（Ｙ）が３．５μｍよりも厚いと、効果が飽和するばかりでなく、フィルムの物性が損なわれることがある。 The thickness of the barrier layer (Y) formed of the polyvinylidene chloride copolymer is preferably in the range of 0.5 μm to 3.5 μm, more preferably in the range of 0.7 μm to 3.0 μm, particularly preferably. It is in the range of 1.0 μm to 2.5 μm. When this barrier layer (Y) is thinner than 0.5 μm, sufficient barrier properties (oxygen barrier properties and water vapor barrier properties) are hardly exhibited. On the other hand, when the barrier layer (Y) is thicker than 3.5 μm, not only the effect is saturated but also the physical properties of the film may be impaired.
ポリアミドフィルム（Ｘ）とバリア層（Ｙ）との密着強力は、０．３Ｎ／ｃｍ以上であることが好ましい。密着強力がこの値よりも低いと、ボイル処理やレトルト処理時にポリアミドフィルム（Ｘ）とバリア層（Ｙ）とが剥離したり、十分なシール強力が出なくなったりする可能性がある。 The adhesion strength between the polyamide film (X) and the barrier layer (Y) is preferably 0.3 N / cm or more. If the adhesion strength is lower than this value, the polyamide film (X) and the barrier layer (Y) may be peeled off during the boil treatment or retort treatment, or sufficient sealing strength may not be obtained.
このようにして得られる、バリア層（Ｙ）が積層された構造のマット調バリアポリアミドフィルムは、ポリアミドフィルムとしての優れた強度、機械的物性に加えて、優れた酸素バリア性、水蒸気バリア性に優れるため、包装材料として好適に使用できる。 The mat-like barrier polyamide film having the structure in which the barrier layer (Y) is laminated in this way has excellent oxygen barrier properties and water vapor barrier properties in addition to excellent strength and mechanical properties as a polyamide film. Since it is excellent, it can be suitably used as a packaging material.
また、バリア層（Ｙ）は、蒸着層であってもよい。蒸着層には無機物または有機物からなる化合物が用いられる。無機物としてはアルミニウムなどの金属やアルミニウム、珪素、マグネシウム、チタンなどの無機酸化物が用いられる。
このような無機物の層を形成する方法としては、真空蒸着法、スパッタリング法、化学的気相成長（ＣＶＤ）法、物理的気相成長（ＰＶＤ）法などが挙げられる。特に真空蒸着法が実用性に優れている。
Further, the barrier layer (Y) may be a vapor deposition layer. A compound made of an inorganic substance or an organic substance is used for the vapor deposition layer. As the inorganic substance, a metal such as aluminum or an inorganic oxide such as aluminum, silicon, magnesium, or titanium is used.
Examples of a method for forming such an inorganic layer include a vacuum deposition method, a sputtering method, a chemical vapor deposition (CVD) method, and a physical vapor deposition (PVD) method. In particular, the vacuum deposition method is excellent in practicality.
ポリアミドフィルム（Ｘ）に蒸着加工を施す際には、ポリアミドフィルム（Ｘ）と蒸着層との接着性を高めるために、ポリアミド樹脂層に、予め、コロナ処理、プラズマ処理または無機あるいは有機化合物によるコーティング処理などを行ってもよい。
真空蒸着の場合には、蒸着原材料として、アルミニウム（Ａｌ）、アルミナ（Ａｌ２Ｏ３）、珪素（Ｓｉ）、シリカ（ＳｉＯ２）またはこれらの組合せが用いられる。原料の加熱方法としては、抵抗加熱法、高周波誘導加熱法、電子ビーム加熱法、レーザー加熱法などがあげられる。また、加熱の際に酸素などのガスを並存させたり、オゾンを添加したり、イオンアシスト法を採用したりすることもできる。
When the polyamide film (X) is subjected to vapor deposition, in order to improve the adhesion between the polyamide film (X) and the vapor deposition layer, the polyamide resin layer is previously coated with corona treatment, plasma treatment or inorganic or organic compound. Processing may be performed.
In the case of vacuum deposition, aluminum (Al), alumina (Al 2 O 3 ), silicon (Si), silica (SiO 2 ), or a combination thereof is used as a deposition raw material. Examples of the method for heating the raw material include resistance heating, high frequency induction heating, electron beam heating, and laser heating. Further, a gas such as oxygen can coexist during heating, ozone can be added, or an ion assist method can be employed.
蒸着層からなるバリア層（Ｙ）の厚みは、１〜１０００ｎｍ程度が好ましい。１ｎｍ以下ではバリア性（酸素バリア性や水蒸気バリア性）が発現せず、１０００ｎｍ以上では加工したフィルム全体としての可塑性が失われ、実用性が低下する。 As for the thickness of the barrier layer (Y) which consists of a vapor deposition layer, about 1-1000 nm is preferable. If it is 1 nm or less, the barrier properties (oxygen barrier property and water vapor barrier property) are not exhibited, and if it is 1000 nm or more, the plasticity of the processed film as a whole is lost and the practicality is lowered.
〔ポリアミドフィルムの特性〕
本発明のマット調バリアポリアミドフィルムは、上記した（１）〜（６）の特性値を全て満足するものである。
まず、光沢度は、５０％以下であることが必要であり、４０％以下であることがより好ましく、３０％以下であることがさらに好ましい。光沢度が５０％を超えると、表面が艶消し状態であるマット調とすることができず、目的とする高級感や和紙風合いが得られない。
[Characteristics of polyamide film]
The matte-like barrier polyamide film of the present invention satisfies all the above-mentioned characteristic values (1) to (6).
First, the glossiness needs to be 50% or less, more preferably 40% or less, and further preferably 30% or less. If the glossiness exceeds 50%, the matte tone cannot be obtained with a matte surface, and the desired high-quality feeling and Japanese paper texture cannot be obtained.
本発明のマット調バリアポリアミドフィルムの空隙率は、０．１〜５％であることが必要であり、好ましくは０．１〜４％であり、更に好ましくは０．３〜３％である。フィルム中の空隙率が０．１％未満の場合、空隙が少なく、シリカの配合のみでは必要とする光沢度を得られない場合がある。一方、フィルム中の空隙率が５％を超えると、衝撃強度や強伸度が低下し、さらには延伸工程及び二次加工工程で破断が生じやすくなる。 The porosity of the matte-like barrier polyamide film of the present invention needs to be 0.1 to 5%, preferably 0.1 to 4%, and more preferably 0.3 to 3%. When the porosity in the film is less than 0.1%, there are few voids, and the required gloss may not be obtained only by blending silica. On the other hand, when the porosity in the film exceeds 5%, the impact strength and the high elongation decrease, and further, breakage easily occurs in the stretching process and the secondary processing process.
本発明のマット調バリアポリアミドフィルムの衝撃強度は、２０℃条件下で測定される衝撃強度が０．３５Ｊ以上であることが必要であり、好ましくは０．４Ｊ以上であり、更に好ましくは０．４５Ｊ以上である。衝撃強度が０．３５Ｊより小さいと、印刷工程等の二次加工工程で破断が生じ易く、十分な実用性を兼ね備えていないため使用困難である。また、製袋後に落下することでフィルムが破袋したり、フィルムにクラックが生じたりして、内容物がこぼれる懸念がある。 The impact strength of the matte-like barrier polyamide film of the present invention is required to be not less than 0.35J, preferably not less than 0.4J, more preferably not less than 0.3J, as measured at 20 ° C. 45J or more. If the impact strength is less than 0.35 J, it is easy to break in the secondary processing step such as the printing step, and it is difficult to use because it does not have sufficient practicality. Moreover, there is a concern that the film may be broken by falling after the bag making, or the film may be cracked to spill the contents.
さらには、本発明のマット調バリアポリアミドフィルムは、フィルムの幅方向（ＴＤ方向）に対して４５度の方向と１３５度の方向における熱水収縮率の差（以下、「熱水収縮率の斜め差」と略することがある）が２．０％以下である必要があり、１．８％以下であることが好ましく、１．６％以下であることがより好ましい。 Furthermore, the matte-like barrier polyamide film of the present invention has a difference in hot water shrinkage between the direction of 45 degrees and the direction of 135 degrees with respect to the width direction (TD direction) of the film (hereinafter referred to as “diagonal of hot water shrinkage” May be abbreviated as “difference”) is 2.0% or less, preferably 1.8% or less, and more preferably 1.6% or less.
本発明における「熱水収縮率の斜め差」は以下のようにして測定するものである。
まず、フィルムの幅方向（ＴＤ方向）を特定し、幅方向を０度とした時に、０度に対し４５度と１３５度の方向を長さ方向としてそれぞれ短冊状の試験片をカットする。試験片の寸法は幅１０ｍｍ×長さ１００ｍｍとする。得られた４５度方向の試験片および１３５度方向の試験片について、それぞれ１００℃熱水中で５分間ボイル処理した後、２３℃、５０％ＲＨ下、２時間放置した後の長さ方向の寸法を測定し、下記式により４５度方向の試験片の熱水収縮率、１３５度方向の試験片の熱水収縮率を求める。さらに両方向の試験片の熱水収縮率より、熱水収縮率の斜め差を算出する。
The “diagonal difference in hot water shrinkage” in the present invention is measured as follows.
First, the width direction (TD direction) of the film is specified, and when the width direction is set to 0 degree, strip-shaped test pieces are cut with the directions of 45 degrees and 135 degrees as the length direction with respect to 0 degrees. The test piece has a width of 10 mm and a length of 100 mm. The obtained 45 degree test piece and 135 degree direction test piece were each boiled in 100 ° C. hot water for 5 minutes and then left at 23 ° C. and 50% RH for 2 hours. The dimensions are measured, and the hot water shrinkage rate of the test piece in the 45 ° direction and the hot water shrinkage rate of the test piece in the 135 ° direction are obtained by the following formulas. Furthermore, the diagonal difference of the hot water shrinkage is calculated from the hot water shrinkage of the test pieces in both directions.
なお、原長とは熱水処理を行う前の試験片の長さであり、本発明においては（Ｌ０４５）、（Ｌ０１３５）ともに１００ｍｍである。
４５度方向の熱水収縮率（％）＝｛原長（Ｌ０４５）−処理後長（Ｌ４５）｝／原長（Ｌ０４５）×１００
１３５度方向の熱水収縮率（％）＝｛原長（Ｌ０１３５）−処理後長（Ｌ１３５）｝／原長（Ｌ０１３５）×１００
熱水収縮率の斜め差（％）＝｜（４５度方向の熱水収縮率）−（１３５度方向の熱水収縮率）｜
The original length is the length of the test piece before performing the hot water treatment. In the present invention, both (L0 45 ) and (L0 135 ) are 100 mm.
Hot water shrinkage (%) in the 45 degree direction = {original length (L0 45 ) −post-treatment length (L 45 )} / original length (L0 45 ) × 100
Hot water shrinkage (%) in the direction of 135 degrees = {original length (L0 135 ) −post-treatment length (L 135 )} / original length (L0 135 ) × 100
Diagonal difference in hot water shrinkage rate (%) = | (hot water shrinkage rate in 45 ° direction) − (hot water shrinkage rate in 135 ° direction) |
熱水収縮率の斜め差が２．０％を超えると、得られるマット調バリアポリアミドフィルムの寸法安定性が不足し、印刷時の色合わせにズレを生じる。また、包装袋とした際、雰囲気の温度や湿度の影響によりひねりや反りを生じ平面性に劣る。また、内容物充填時に充填機の掴み部で掴みミスが生じたり、シール不良が生じたりする。さらには、包装袋の歪みに起因し、外部から衝撃を受けた際の破袋率が高まる。 When the diagonal difference of the hot water shrinkage ratio exceeds 2.0%, the dimensional stability of the resulting matte-like barrier polyamide film is insufficient, resulting in deviation in color matching during printing. Moreover, when it is set as a packaging bag, it is twisted and warped due to the influence of the temperature and humidity of the atmosphere, resulting in poor flatness. Further, when filling the contents, a gripping error may occur at the gripping portion of the filling machine, or a sealing failure may occur. Furthermore, due to the distortion of the packaging bag, the bag breaking rate upon impact from the outside increases.
本発明のマット調バリアポリアミドフィルムの酸素透過度は、２０℃、６５％ＲＨ下で、１００ｍｌ／ｍ２・ｄａｙ・ＭＰａ以下であることが必要であり、中でも８０ｍｌ／ｍ２・ｄａｙ・ＭＰａ以下であることが好ましい。 The oxygen permeability of the matte-like barrier polyamide film of the present invention is required to be 100 ml / m 2 · day · MPa or less at 20 ° C. and 65% RH, particularly 80 ml / m 2 · day · MPa or less. It is preferable that
さらに、本発明のマット調バリアポリアミドフィルムの水蒸気透過度は、４０℃、９０％ＲＨ下で、２０ｇ／ｍ２・ｄａｙ以下であることが必要であり、中でも１５ｇ／ｍ２・ｄａｙ以下であることが好ましい。
本発明のマット調バリアポリアミドフィルムの酸素透過度と水蒸気透過度が上記の値を満足しない場合、内容物保存性に劣るものとなり、食品、医療品および薬品等の包装用途に用いることが困難となる。
Furthermore, the water vapor permeability of the matte-like barrier polyamide film of the present invention is required to be 20 g / m 2 · day or less at 40 ° C. and 90% RH, and more preferably 15 g / m 2 · day or less. It is preferable.
If the oxygen permeability and water vapor permeability of the matte-like barrier polyamide film of the present invention do not satisfy the above values, the contents will be inferior in storage stability, and difficult to use for food, medical products and medicine packaging applications. Become.
また、本発明のマット調バリアポリアミドフィルムの引張強度については、フィルムの長さ方向（ＭＤ）と幅方向（ＴＤ）共に１７５ＭＰａ以上であることが好ましい。フィルムの引張強度が１７５ＭＰａ未満であると、食品、医療品および薬品等の包装用として求められる強度が不足するという不都合が生じやすくなる。 The tensile strength of the matte-like barrier polyamide film of the present invention is preferably 175 MPa or more in both the length direction (MD) and the width direction (TD) of the film. When the tensile strength of the film is less than 175 MPa, the problem that the strength required for packaging foods, medical products, medicines and the like is insufficient tends to occur.
本発明のマット調バリアポリアミドフィルムの引張伸度については、フィルムの長さ方向（ＭＤ）と幅方向（ＴＤ）共に６５％以上であることが好ましい。フィルムの引張伸度が６５％未満であると、引張強度と同様に、食品、医療品および薬品等の包装用として求められる強度が不足するという不都合が生じやすくなる。 The tensile elongation of the matte-like barrier polyamide film of the present invention is preferably 65% or more in both the length direction (MD) and the width direction (TD) of the film. If the tensile elongation of the film is less than 65%, the inconvenience that the strength required for packaging foods, medical products, medicines and the like is insufficient as well as the tensile strength tends to occur.
本発明のマット調バリアポリアミドフィルムの厚みは、衝撃強度及び寸法安定性が両立できれば特に限定されないが、１０〜３０μｍが好ましく、１２〜１８μｍであることがより好ましい。厚みが１０μｍ未満であると衝撃強度が非常に低くなりやすく、一方、厚みが３０μｍを超えるとコスト高となるため好ましくない。 The thickness of the matte-like barrier polyamide film of the present invention is not particularly limited as long as both impact strength and dimensional stability can be achieved, but is preferably 10 to 30 μm, and more preferably 12 to 18 μm. If the thickness is less than 10 μm, the impact strength tends to be very low. On the other hand, if the thickness exceeds 30 μm, the cost increases, which is not preferable.
次に、本発明のマット調バリアポリアミドフィルムの製造方法について説明する。
前記したように、シリカ等の無機粒子を含有するポリアミド樹脂を用いて製膜すると、未延伸フィルムの延伸時に延伸応力が高くなり、空隙の発生やボーイング現象の増大につながるものとなる。本発明においては、このような現象を解消すべく、ポリアミドフィルム（Ｘ）の製造において、（１−ａ）未延伸フィルムを特定の水分率となるように調整した後、未延伸のフィルムの少なくとも一方の面にポリ塩化ビニリデン系共重合体を含有するバリア層形成用塗料を塗布すること、（１−ｂ）特定の温度条件で延伸を行うことを重要なポイントとするものである。そして、このような（１−ａ）、（１−ｂ）の条件を見出したことによって、前記したような特性値を満足するポリアミドフィルムを得ることが可能となった。
Next, a method for producing the matte-like barrier polyamide film of the present invention will be described.
As described above, when a film is formed using a polyamide resin containing inorganic particles such as silica, the stretching stress increases when the unstretched film is stretched, leading to the generation of voids and an increase in the bowing phenomenon. In the present invention, in order to eliminate such a phenomenon, in the production of the polyamide film (X), (1-a) after adjusting the unstretched film to have a specific moisture content, at least the unstretched film It is important to apply a coating for forming a barrier layer containing a polyvinylidene chloride copolymer on one surface, and (1-b) to perform stretching under specific temperature conditions. And it became possible to obtain the polyamide film which satisfy | fills the above characteristic values by having discovered the conditions of such (1-a) and (1-b).
ポリアミドフィルム（Ｘ）の製造方法としては、チューブラー法、テンター式同時二軸延伸法、テンター式逐次二軸延伸法が一般に知られている。チューブラー法は装置の設備コストが他の方法より安い点で有利であるが、フィルムの厚み精度を高めることが難しく、品質安定性や寸法安定性の面でもテンター式二軸延伸法の方が優れている。本発明のマット調バリアポリアミドフィルムを製造する方法としては、テンター式同時二軸延伸法が好ましい。 As a method for producing the polyamide film (X), a tubular method, a tenter type simultaneous biaxial stretching method, and a tenter type sequential biaxial stretching method are generally known. The tubular method is advantageous in that the equipment cost of the equipment is cheaper than other methods, but it is difficult to increase the film thickness accuracy, and the tenter-type biaxial stretching method is also better in terms of quality stability and dimensional stability. Are better. As a method for producing the matte barrier polyamide film of the present invention, a tenter simultaneous biaxial stretching method is preferred.
まず、ホッパーに原料樹脂ペレットを供給し、溶融押出機で可塑化溶融し、溶融した樹脂を押出機の先端に取り付けられたＴダイよりシート状に押し出し、キャストロールで冷却固化する。このとき、空気によりポリアミド樹脂をキャストロールに押し付けて未延伸フィルムを得る。 First, raw material resin pellets are supplied to a hopper, plasticized and melted with a melt extruder, and the melted resin is extruded into a sheet form from a T-die attached to the tip of the extruder, and cooled and solidified with a cast roll. At this time, the polyamide resin is pressed against the cast roll with air to obtain an unstretched film.
そして、（１−ａ）の条件で未延伸フィルムの水分率の調整と、バリア層形成用塗料の塗布を行う。具体的には、未延伸フィルムの水分率が３〜９％になるように温水漕で吸水させる。温水槽の温度は４５〜９０℃とすることが好ましい。４５℃未満ではポリアミドへの吸水速度が遅いため吸水時間を長くする必要があり不経済である。９０℃を超えると、ポリアミドの結晶化が進み、延伸が困難になる。さらには、温度が高いことでフィルムのコシがなくなり、温水層でのフィルムシワが発生し易く、操業性が著しく低下する。 And adjustment of the moisture content of an unstretched film and application | coating of the coating material for barrier layer formation are performed on the conditions of (1-a). Specifically, water is absorbed by a hot water bottle so that the moisture content of the unstretched film is 3 to 9%. The temperature of the hot water tank is preferably 45 to 90 ° C. If it is less than 45 ° C., the water absorption rate to the polyamide is slow, so it is necessary to lengthen the water absorption time, which is uneconomical. If it exceeds 90 ° C, crystallization of the polyamide proceeds and stretching becomes difficult. Furthermore, since the temperature is high, the stiffness of the film is eliminated, film wrinkles in the hot water layer are likely to occur, and the operability is significantly reduced.
吸水工程による未延伸フィルムの水分率は３〜９％とすることが必要であり、中でも３．５〜８．５％とすることが好ましい。水分率が３％未満であると、可塑剤となる水分が少ないため、延伸応力が高くなる。そのため、ボーイングが大きくなるため、熱水収縮率斜め差が大きくなる。また、フィルム中の空隙率が高くなるため、フィルムの衝撃強度が低下したり、切断が多発する。一方、水分率が９％を超えると、幅方向（ＴＤ方向）での吸水率が不均一となり、フィルムの厚み不良が発生する。さらには延伸で必要とするフィルム温度が得られにくくなるため、ネック延伸が発生したり、切断が多発する。 The moisture content of the unstretched film in the water absorption step needs to be 3 to 9%, and preferably 3.5 to 8.5%. If the moisture content is less than 3%, the amount of moisture that becomes a plasticizer is small, so that the stretching stress becomes high. Therefore, since bowing becomes large, a hot water shrinkage | contraction diagonal difference becomes large. Moreover, since the porosity in a film becomes high, the impact strength of a film falls or a cutting | disconnection occurs frequently. On the other hand, if the moisture content exceeds 9%, the water absorption in the width direction (TD direction) becomes non-uniform, resulting in poor film thickness. Furthermore, since it becomes difficult to obtain the film temperature required for stretching, neck stretching occurs or cutting frequently occurs.
次に、未延伸のフィルムの少なくとも一方の面にポリ塩化ビニリデン系共重合体を含有するバリア層形成用塗料（ラテックス）を塗布する。具体的には、未延伸フィルムにバリア層形成用塗料を塗布したのち、そのまま延伸処理と皮膜形成処理を同時に施す方法や、塗布したのちドライヤーなどによる熱風の吹き付けや赤外線照射などによりバリア層形成用塗料の水分を蒸発乾燥、熱融着させる工程を経たうえで、延伸処理と皮膜形成処理を同時に施す方法などを用いることができる。延伸処理前にあらかじめポリ塩化ビニリデン系共重合体の結晶化を促進させることができる後者の方法が、耐ブラッシング性の点でより好ましい。
また、バリア層形成用塗料の塗布によるバリア層（Ｙ）の形成については、延伸工程前のインラインコートではなく、延伸・巻き取り・スリット後の工程でコートを行なうポストコートにてバリア層（Ｙ）を形成しても良い。ただし、コスト面、ポリアミドフィルム（Ｘ）とバリア層（Ｙ）との密着性を考慮すると、延伸工程処理前にバリア層形成用塗料を塗布し、延伸処理にてポリ塩化ビニリデン系共重合体の皮膜を形成するインラインコートの方が好ましい。
Next, a barrier layer-forming coating material (latex) containing a polyvinylidene chloride copolymer is applied to at least one surface of the unstretched film. Specifically, after applying the barrier layer-forming coating to an unstretched film, the method of simultaneously applying the stretching process and the film-forming process as it is, or applying the coating layer for the barrier layer by spraying hot air with a drier etc. A method of performing a stretching process and a film forming process simultaneously after evaporating and drying the moisture of the paint and heat-sealing can be used. The latter method, which can promote the crystallization of the polyvinylidene chloride copolymer in advance before the stretching treatment, is more preferable in terms of brushing resistance.
In addition, for the formation of the barrier layer (Y) by applying the coating material for forming the barrier layer, the barrier layer (Y ) May be formed. However, in consideration of the cost and the adhesion between the polyamide film (X) and the barrier layer (Y), a coating for forming the barrier layer is applied before the stretching process, and the polyvinylidene chloride copolymer is coated by the stretching process. An in-line coat that forms a film is preferred.
バリア層形成用塗料の水分を蒸発乾燥させる工程の温度は、７０℃〜１５０℃であることが好ましく、より好ましくはポリ塩化ビニリデン系共重合体の造膜性が良い８０℃〜１２０℃の範囲である。乾燥温度が７０℃未満であると造膜性が低下し、また１５０℃を超えると、バリア層形成用塗料の温度上昇が激しく突沸などの現象が生じて、均一な皮膜が得られにくくなる。水分蒸発乾燥工程は異なる温度分布に区切られていてもよく、そのなかの最高温度を示す処理工程にかける時間は、未延伸フィルムやポリ塩化ビニリデン系共重合体の厚み、バリア層形成用塗料の固形分量や比熱などによって、任意に選択される。その時間は、通常は０．０１〜１２０秒、好ましくは１〜８０秒である。０．０１秒未満であるとバリア層形成用塗料の水分蒸発性に劣ったり、あるいはポリ塩化ビニリデン系共重合体の造膜が不十分であったりする傾向がある。また１２０秒を超えると、場合によってはポリアミドフィルム（Ｘ）の結晶化が促進されすぎることにより延伸フィルム製造が不可能となったり、バリア層（Ｙ）との密着性に不利となったりする傾向がある。 The temperature of the step of evaporating and drying the moisture of the coating for forming the barrier layer is preferably 70 ° C. to 150 ° C., more preferably in the range of 80 ° C. to 120 ° C. where the film forming property of the polyvinylidene chloride copolymer is good. It is. When the drying temperature is less than 70 ° C., the film-forming property is deteriorated, and when it exceeds 150 ° C., the temperature of the coating material for forming the barrier layer is excessively increased and a phenomenon such as bumping occurs, making it difficult to obtain a uniform film. The moisture evaporation drying process may be divided into different temperature distributions, and the time taken for the treatment process showing the highest temperature among them is the thickness of the unstretched film or polyvinylidene chloride copolymer, the barrier layer forming coating It is arbitrarily selected depending on the solid content and specific heat. The time is usually 0.01 to 120 seconds, preferably 1 to 80 seconds. If it is less than 0.01 seconds, the water layer evaporating property of the coating material for forming the barrier layer tends to be poor, or the film formation of the polyvinylidene chloride copolymer tends to be insufficient. Further, if it exceeds 120 seconds, in some cases, the crystallization of the polyamide film (X) is promoted too much, so that it is impossible to produce a stretched film, or the adhesiveness to the barrier layer (Y) tends to be disadvantageous. There is.
ポリ塩化ビニリデン系共重合体のバリア層形成用塗料をポリアミドフィルム（Ｘ）に塗布する方法は、特に限定されないが、グラビアロールコーティング、リバースロールコーティング、ワイヤーバーコーティング、エアーナイフコーティング、ダイコーティング、カーテンダイコーティング等の通常の方法を用いることができる。 The method for applying the polyvinylidene chloride copolymer barrier layer-forming coating to the polyamide film (X) is not particularly limited, but gravure roll coating, reverse roll coating, wire bar coating, air knife coating, die coating, curtain Usual methods such as die coating can be used.
次に、（１−ｂ）の条件で延伸を行う。吸水処理が施され、水分率が３〜９％であり、ポリ塩化ビニリデン系共重合体の皮膜が形成された未延伸フィルムを、フィルムの端部をクリップで把持して、ＭＤ方向とＴＤ方向にそれぞれ２．０〜４．０倍に延伸することが好ましい。延伸倍率は、中でも２．５〜３．８倍であることが好ましく、ＭＤ方向の延伸倍率とＴＤ方向の延伸倍率の比（ＴＤ／ＭＤ）は、０．９〜１．２であることが好ましい。 Next, it extends | stretches on the conditions of (1-b). An unstretched film that has been subjected to water absorption treatment, has a moisture content of 3 to 9%, and is coated with a polyvinylidene chloride copolymer film, grips the edges of the film with clips, MD direction and TD direction It is preferable to stretch 2.0 to 4.0 times. The draw ratio is preferably 2.5 to 3.8 times, and the ratio of the draw ratio in the MD direction to the draw ratio in the TD direction (TD / MD) is preferably 0.9 to 1.2. preferable.
そして、延伸する際の予熱温度は１８０〜２５０℃とすることが必要であり、中でも２００〜２４５℃とすることが好ましく、さらに好ましくは２１０〜２４０℃である。予熱温度が１８０℃未満では、フィルム中の水分を蒸発させる熱量が少なくなる。そのため、延伸応力が高くなり、ボーイングが大きくなったり、空隙率が高くなったりする。また、延伸に必要とするフィルム温度が得られにくくなるため、ネック延伸が発生したり、切断が多発したりする。２５０℃を超えた場合、吸水した水分の蒸発速度が速くなりすぎる。そのため、フィルム温度が高くなりすぎるため、ポリアミドの結晶化が進み延伸が困難になる。 And the preheating temperature at the time of extending | stretching needs to be 180-250 degreeC, It is preferable to set it as 200-245 degreeC among these, More preferably, it is 210-240 degreeC. When the preheating temperature is less than 180 ° C., the amount of heat for evaporating moisture in the film is reduced. For this reason, the stretching stress increases, the bowing increases, and the porosity increases. Moreover, since it becomes difficult to obtain the film temperature required for stretching, neck stretching occurs or cutting frequently occurs. When the temperature exceeds 250 ° C., the evaporation rate of absorbed water becomes too fast. Therefore, since the film temperature becomes too high, crystallization of the polyamide proceeds and stretching becomes difficult.
なお、ポリアミドフィルムを上記の温度に予熱するには、延伸機の予熱ゾーンを走行するフィルムに吹き付ける熱風の温度を上記の温度範囲に設定することによって行うことが好ましい。そして、ポリアミドフィルムが予熱ゾーンを走行する時間（予熱時間）は、０．５〜５秒間とすることが好ましい。 In addition, in order to preheat a polyamide film to said temperature, it is preferable to carry out by setting the temperature of the hot air sprayed on the film which drive | works the preheating zone of a extending machine to said temperature range. And it is preferable that the time (preheating time) for which the polyamide film travels in the preheating zone is 0.5 to 5 seconds.
延伸温度については、１７０〜２３０℃が必要であり、１８０〜２２０℃とすることが好ましく、さらに好ましくは１９０〜２１０℃である。延伸温度が１７０℃未満では、ＴＤ方向で均一なフィルム温度が得られにくく、ネック延伸や厚み不良が発生したり、切断が多発したりする。一方、延伸温度が２３０℃を超えた場合、フィルム温度が高くなりすぎるためドロー延伸となり、分子配向がされにくいため衝撃強度や強伸度が低下する。 About extending | stretching temperature, 170-230 degreeC is required, It is preferable to set it as 180-220 degreeC, More preferably, it is 190-210 degreeC. When the stretching temperature is less than 170 ° C., it is difficult to obtain a uniform film temperature in the TD direction, and neck stretching or poor thickness occurs, or cutting frequently occurs. On the other hand, when the stretching temperature exceeds 230 ° C., the film temperature becomes too high, so that draw stretching is performed, and the molecular orientation is difficult to be performed, so that the impact strength and the strong elongation decrease.
そして、二軸延伸されたフィルムを引き続き熱処理して二軸配向を固定させる。この熱固定の温度条件は、温度１８０〜２３０℃が必要であり、好ましくは１９５〜２２０℃であり、さらに好ましくは２０５〜２１５℃である。熱固定の処理時間は１〜１０秒間とすることが好ましく、幅方向の弛緩率は０．３〜７％の範囲とすることが好ましい。このような熱固定（弛緩熱処理）を行うことによって、マット調バリアポリアミドフィルムの寸法安定性を高めることができる。 The biaxially stretched film is subsequently heat treated to fix the biaxial orientation. The temperature condition for this heat setting requires a temperature of 180 to 230 ° C, preferably 195 to 220 ° C, more preferably 205 to 215 ° C. The heat fixing treatment time is preferably 1 to 10 seconds, and the relaxation rate in the width direction is preferably in the range of 0.3 to 7%. By performing such heat setting (relaxation heat treatment), the dimensional stability of the matte-like barrier polyamide film can be enhanced.
熱固定の処理温度が１８０℃未満であるとフィルムの寸法安定性の悪化、熱水収縮率の斜め差が２．５％を超えたり、ポリ塩化ビニリデン系共重合体からなるバリア層（Ｙ）の溶解融着性が劣ることによるバリア性の低下、ポリアミドフィルム（Ｘ）とバリア層（Ｙ）の密着性が低下する。一方、熱固定の処理温度が２３０℃を超えるとフィルムの熱劣化が発生し、衝撃強度や強伸度が低下する。さらには熱固定処理中に溶断するなどのトラブルにより操業性が低下したり、ポリ塩化ビニリデン系共重合体の結晶核がすべて溶解されてしまい、耐ブラッシング効果に劣るものとなる。 When the heat setting treatment temperature is less than 180 ° C., the dimensional stability of the film deteriorates, the oblique difference in hot water shrinkage exceeds 2.5%, or the barrier layer (Y) made of a polyvinylidene chloride copolymer The barrier property is lowered due to inferior dissolution and fusion property, and the adhesion between the polyamide film (X) and the barrier layer (Y) is lowered. On the other hand, when the heat setting treatment temperature exceeds 230 ° C., thermal deterioration of the film occurs, and impact strength and high elongation decrease. Furthermore, due to troubles such as fusing during heat setting treatment, the operability is lowered, or all the crystal nuclei of the polyvinylidene chloride copolymer are dissolved, resulting in poor brushing resistance.
上記のような延伸温度、熱固定温度とするには、延伸機の延伸ゾーンや熱固定ゾーンを走行するフィルムに吹き付ける熱風の温度を上記の温度範囲に設定することによって行うことが好ましい。 In order to set the stretching temperature and heat setting temperature as described above, it is preferable to set the temperature of the hot air blown to the film running in the stretching zone or heat setting zone of the stretching machine within the above temperature range.
本発明のマット調バリアポリアミドフィルムのポリアミドフィルム（Ｘ）またはバリア層（Ｙ）に、必要に応じて、コロナ放電処理等の表面処理を施してもよい。 A surface treatment such as a corona discharge treatment may be applied to the polyamide film (X) or the barrier layer (Y) of the matte-like barrier polyamide film of the present invention, if necessary.
本発明のマット調バリアポリアミドフィルムは、シーラント等の樹脂層を積層することにより、種々の積層フィルムとすることができる。 The matte-like barrier polyamide film of the present invention can be made into various laminated films by laminating a resin layer such as a sealant.
シーラントとして用いる樹脂としては、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、ポリエチレン／ポリプロピレン共重合体、エチレン−酢酸ビニル共重合体、アイオノマー樹脂、エチレン−アクリル酸／メタクリル酸共重合体、エチレン−アクリル酸／メタクリル酸エステル共重合体、ポリ酢酸ビニル系樹脂等が挙げられ、ヒートシール強度や材質そのものの強度が高いポリエチレン、ポリプロピレン、ポリエチレン／ポリプロピレン共重合体等のポリオレフィン樹脂が好ましい。これらの樹脂は、単独で用いても、また他の樹脂と共重合や溶融混合して用いても、さらに酸変性等が施されていてもよい。 The resin used as the sealant is low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polyethylene / polypropylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid. / Methacrylic acid copolymer, ethylene-acrylic acid / methacrylic ester copolymer, polyvinyl acetate resin, etc., polyethylene, polypropylene, polyethylene / polypropylene copolymer, etc. with high heat seal strength and material strength The polyolefin resin is preferred. These resins may be used alone, or may be copolymerized or melt-mixed with other resins, or may be further acid-modified.
シーラント層をマット調バリアポリアミドフィルムにラミネートする方法としては、シーラント樹脂からなるフィルムまたはシートを、接着剤を介して、マット調ガスバリアポリアミドフィルムにラミネートする方法や、シーラント樹脂をマット調ガスバリアポリアミドフィルムに押出ラミネートする方法等が挙げられる。前者の方法においては、シーラント樹脂からなるフィルムまたはシートは、未延伸状態であっても低倍率の延伸状態でもよいが、実用的には、未延伸状態であることが好ましい。
なお、マット調バリアポリアミドフィルムに接着剤を塗布する際には、ポリアミドフィルム（Ｘ）またはバリア層（Ｙ）のどちらの面でもかまわないが、ラミネート後のフィルムを包装袋に加工した際に、ポリアミドフィルム（Ｘ）が外側となるように、バリア層（Ｙ）の面に接着剤を塗布するほうが好ましい。
As a method of laminating the sealant layer to the matte-like barrier polyamide film, a film or sheet made of a sealant resin is laminated to the matte-like gas barrier polyamide film via an adhesive, or the sealant resin is applied to the matte-like gas barrier polyamide film. Examples include extrusion lamination. In the former method, the film or sheet made of the sealant resin may be in an unstretched state or in a stretched state at a low magnification, but practically preferably in an unstretched state.
When applying the adhesive to the matte-like barrier polyamide film, either the polyamide film (X) or the barrier layer (Y) may be used, but when the laminated film is processed into a packaging bag, It is preferable to apply an adhesive to the surface of the barrier layer (Y) so that the polyamide film (X) is on the outside.
シーラント層の厚みは、特に限定されないが、２０〜１００μｍであることが好ましく、４０〜７０μｍであることがより好ましい。 Although the thickness of a sealant layer is not specifically limited, It is preferable that it is 20-100 micrometers, and it is more preferable that it is 40-70 micrometers.
本発明のマット調バリアポリアミドフィルムを用いて包装用袋を作製することができ、この包装用袋は、例えば、飲食品、果物、ジュ−ス、飲料水、酒、調理食品、水産練り製品、冷凍食品、肉製品、煮物、餅、液体ス−プ、調味料、その他の各種の飲食料品、液体洗剤、化粧品、化成品といった内容物を充填包装することができる。 A packaging bag can be produced by using the matte-like barrier polyamide film of the present invention. This packaging bag is, for example, a food / beverage product, fruit, juice, drinking water, liquor, cooked food, marine product, frozen product Contents such as foods, meat products, boiled foods, rice cakes, liquid soups, seasonings, other various foods and drinks, liquid detergents, cosmetics, and chemical products can be filled and packaged.
次に、実施例により、本発明をさらに具体的に説明する。なお、実施例および比較例の評価に用いた原料および測定方法は次のとおりである。 Next, the present invention will be described more specifically with reference to examples. In addition, the raw material and measurement method which were used for evaluation of an Example and a comparative example are as follows.
（１）光沢度（％）
得られた複層構成のポリアミドフィルムの表面を、村上色彩技術研究所社製（ＧＲＯＳＳ ＭＥＴＥＲ ＧＭ−２６ ＰＲＯ）を用い、ＪＩＳ Ｋ ７１０５に準じて、入射角２０°で測定した。
（２）空隙率（％）
得られた複層構成のポリアミドフィルムを用い、イオンポリッシング（ＩＰ）によりフィルム断面を作製し、ＦＥ−ＳＥＭにて断面観察を実施した。そのＳＥＭ画像を、画像解析ソフト（ＩｍａｇｅＪ．）を用いて、画像処理（閾値９５設定の自動２値化処理）を施し、フィルム全体の断面の空隙面積の総和を算出し、下記式より空隙率（％）を求めた。
空隙率（％）＝（空隙面積の総和（μｍ２）／フィルム全体の断面積（μｍ２））×１００
（３）衝撃強度（Ｊ）
得られた複層構成のポリアミドフィルムを用い、フィルムインパクトテスター（東洋精機社製）を使用し、２０℃の雰囲気下で、直径７ｃｍのリング状フィルムの打ち抜きに要した衝撃強度を測定することにより行った。測定には、重量３０ｋｇ、直径１２．７ｍｍ（０．５インチ）のインパクトヘッドを用いた。
(1) Glossiness (%)
The surface of the obtained polyamide film having a multilayer structure was measured at an incident angle of 20 ° according to JIS K 7105, using MURAKAMI Color Technology Laboratory Co., Ltd. (GROSS METER GM-26 PRO).
(2) Porosity (%)
Using the obtained polyamide film having a multilayer structure, a cross section of the film was prepared by ion polishing (IP), and the cross section was observed by FE-SEM. The SEM image is subjected to image processing (automatic binarization processing with a threshold value 95 setting) using image analysis software (ImageJ.), And the total void area of the cross section of the entire film is calculated. (%) Was calculated.
Porosity (%) = (total void area (μm 2 ) / cross-sectional area of the entire film (μm 2 )) × 100
(3) Impact strength (J)
By measuring the impact strength required for punching a ring-shaped film having a diameter of 7 cm in an atmosphere of 20 ° C. using a film impact tester (manufactured by Toyo Seiki Co., Ltd.) using the obtained polyamide film having a multilayer structure. went. For the measurement, an impact head having a weight of 30 kg and a diameter of 12.7 mm (0.5 inch) was used.
（４）熱水収縮率の斜め差
前記の方法で測定、算出した。
（５）酸素透過度
得られた複層構成のポリアミドフィルムを用い、モコン社製酸素バリア測定器（ＯＸ−ＴＲＡＮ ２／２０ＭＨ）を用いて、ＪＩＳ Ｋ７１２６−２法に基づいて、温度２０℃、相対湿度６５％の雰囲気下における酸素透過度を測定した。
（６）水蒸気透過度
得られた複層構成のポリアミドフィルムを用い、ＪＩＳ Ｋ−７１２９に記載の方法に準じて、温度４０℃、湿度９０％ＲＨにおいて、モコン社製ＰＥＲＭＡＴＲＡＮ−Ｗ ３／３３により水蒸気透過度を測定した。単位はｇ／（ｍ２・ｄａｙ）。
(4) Diagonal difference in hot water shrinkage rate Measured and calculated by the method described above.
(5) Oxygen permeability Using the obtained polyamide film having a multilayer structure, using an oxygen barrier measuring device (OX-TRAN 2 / 20MH) manufactured by Mocon, based on JIS K7126-2 method, a temperature of 20 ° C, The oxygen permeability was measured in an atmosphere with a relative humidity of 65%.
(6) Water vapor transmission rate According to the method described in JIS K-7129, at a temperature of 40 ° C. and a humidity of 90% RH, PERMATRAN-W 3/33 manufactured by Mocon Co. The water vapor transmission rate was measured. The unit is g / (m 2 · day).
（７）製造方法における水分率（％）
吸水後の未延伸フィルムから切り出したサンプル片の質量Ｗと、それを減圧下８０℃で２４時間乾燥した後の質量Ｗｄから次式により求めた。
水分率（％）＝（Ｗ−Ｗｄ）／Ｗ×１００
（８）引張強伸度
得られた複層構成のポリアミドフィルムを用い、オートグラフＡＧ-1（島津製作所社製）を用いて測定した。試験片は幅１０ｍｍ、長さ１５０ｍｍの短冊状で、使用セルは１００ｋｇ、試験速度は５００ｍｍ／ｍｉｎ、チャック間隔は１００ｍｍであった。
引張強度、引張伸度ともに、試験片は、フィルムの長さ方向（ＭＤ）と幅方向（ＴＤ）についてそれぞれ採取した。
(7) Moisture content (%) in the production method
It calculated | required by following Formula from the mass Wd of the sample piece cut out from the unstretched film after water absorption, and the mass Wd after drying it at 80 degreeC under pressure reduction for 24 hours.
Moisture content (%) = (W−Wd) / W × 100
(8) Tensile strength / elongation The obtained polyamide film having a multilayer structure was measured using Autograph AG-1 (manufactured by Shimadzu Corporation). The test piece was a strip having a width of 10 mm and a length of 150 mm, the cell used was 100 kg, the test speed was 500 mm / min, and the chuck interval was 100 mm.
For both tensile strength and tensile elongation, specimens were collected in the length direction (MD) and width direction (TD) of the film, respectively.
（９）厚み測定
得られた複層構成のポリアミドフィルムを用い、０．５μｍ以上の厚みは、市販のデジタル厚み計（接触式厚み計、商品名：超高精度デシマイクロヘッド ＭＨ−１５Ｍ、日本光学社製）により測定した。一方、０．５μｍ未満の厚みは、重量分析法（一定面積のフィルムの重量測定値をその面積で除し、更に組成物の比重で除した）により測定した。
（１０）延伸性
各例で示す製造条件にて２４時間連続して製造を行った際の生産性を評価した。その際の延伸時に生じたフィルムの破断回数が１回以下の場合は○、切断回数が２〜４回の場合を△、切断回数が５回以上の場合を×と評価した。評価×の条件については、操業性が非常に低く、製品の安定生産は困難である。
(9) Thickness measurement Using the obtained multilayered polyamide film, the thickness of 0.5 μm or more is a commercially available digital thickness gauge (contact thickness gauge, trade name: Ultra High Precision Deci Microhead MH-15M, Japan (Optical Co., Ltd.). On the other hand, the thickness of less than 0.5 μm was measured by gravimetric analysis (the weight measured value of a film of a certain area was divided by the area and further divided by the specific gravity of the composition).
(10) Stretchability Productivity was evaluated when production was continuously performed for 24 hours under the production conditions shown in each example. In the case where the number of breaks of the film produced at the time of stretching was 1 or less, it was evaluated as ○, when the number of cuts was 2 to 4 was evaluated as Δ, and when the number of cuts was 5 or more, it was evaluated as ×. Regarding the condition of evaluation x, the operability is very low, and stable production of the product is difficult.
[使用原料]
[シリカ含有マスターチップ（Ｍ１）]
容積３０リットルのオートクレーブに、１０ｋｇのε−カプロラクタムと、１ｋｇの水と、５００ｇのシリカ（富士シリシア化学社製、製品名：サイリシア３１０Ｐ、平均粒径２．７μｍ）を投入し、１００℃に保持して、その温度で反応系内が均一になるまで撹拌した。引き続き、撹拌しながら２６０℃に加熱し、１．５ＭＰａの圧力を１時間維持し、さらに１時間かけて常圧まで放圧し、さらに１時間重合した。重合が終了した時点で、上記反応生成物をストランド状に払い出し、冷却、固化後、切断して、ポリアミド樹脂からなるペレットを得た。次いで、このペレットを９５℃の乾熱で８時間精錬し、未反応モノマー等を除去した後、乾燥した。得られたポリアミド樹脂の相対粘度は２．７、シリカ含有量は５．２質量％であった。
[Raw materials]
[Silica-containing master chip (M1)]
10 kg of ε-caprolactam, 1 kg of water, and 500 g of silica (manufactured by Fuji Silysia Chemical Co., Ltd., product name: Silicia 310P, average particle size of 2.7 μm) are put into a 30 liter autoclave and maintained at 100 ° C. The reaction system was stirred at that temperature until the reaction system became uniform. Subsequently, the mixture was heated to 260 ° C. with stirring, maintained at a pressure of 1.5 MPa for 1 hour, released to normal pressure over an additional hour, and polymerized for an additional hour. When the polymerization was completed, the reaction product was discharged into a strand, cooled, solidified, and then cut to obtain a polyamide resin pellet. Next, the pellets were refined with dry heat at 95 ° C. for 8 hours to remove unreacted monomers and the like, and then dried. The relative viscosity of the obtained polyamide resin was 2.7, and the silica content was 5.2% by mass.
[シリカマスターチップ（Ｍ２）]
容積３０リットルのオートクレーブに、１０ｋｇのε−カプロラクタムと、１ｋｇの水と、１．５ｋｇのシリカ（富士シリシア化学社製、製品名：サイリシア３１０Ｐ、平均粒径２．７μｍ）を投入し、１００℃に保持して、その温度で反応系内が均一になるまで撹拌した。引き続き、撹拌しながら２６０℃に加熱し、１．５ＭＰａの圧力を１時間維持し、さらに１時間かけて常圧まで放圧し、さらに１．５時間重合した。重合が終了した時点で、上記反応生成物をストランド状に払い出し、冷却、固化後、切断して、ポリアミド樹脂からなるペレットを得た。次いで、このペレットを９５℃の乾熱で８時間精錬し、未反応モノマー等を除去した後、乾燥した。得られたポリアミド樹脂の相対粘度は２．６、シリカ含有量は１５．６質量％であった。
[Silica master chip (M2)]
10 kg of ε-caprolactam, 1 kg of water, and 1.5 kg of silica (manufactured by Fuji Silysia Chemical Co., Ltd., product name: Silicia 310P, average particle size of 2.7 μm) are put into an autoclave having a volume of 30 liters, and 100 ° C. The mixture was stirred at that temperature until the reaction system became homogeneous. Subsequently, the mixture was heated to 260 ° C. with stirring, maintained at a pressure of 1.5 MPa for 1 hour, released to normal pressure over an additional hour, and polymerized for an additional 1.5 hours. When the polymerization was completed, the reaction product was discharged into a strand, cooled, solidified, and then cut to obtain a polyamide resin pellet. Next, the pellets were refined with dry heat at 95 ° C. for 8 hours to remove unreacted monomers and the like, and then dried. The relative viscosity of the obtained polyamide resin was 2.6, and the silica content was 15.6% by mass.
・バリア層形成用塗料（ラテックス）（１）
ガラスライニングを施した耐圧反応容器中に水８５質量部、アルキルスルホン酸ソーダ０．１５質量部および過硫酸ソーダ０．１０質量部を仕込み、脱気した後内容物の温度を５５℃に保った。これとは別の容器に塩化ビニリデン９７質量部とアクリル酸メチル２質量部とアクリル酸１質量部を計量混合してモノマー混合物を作製した。前記反応容器中にモノマー混合物の１０質量部を仕込み攪拌下反応を進行させた。反応容器の内圧が降下することにより反応がほとんど進行したことを確認した後、１５質量％水溶液のアルキルスルホン酸ソーダ１０質量部を圧入し、その後、モノマー混合物の残り全量を１５時間にわたって連続して定量添加した。得られたモノマー混合物に、２０℃における液表面張力が４２ｍＮ／ｍとなるように１５質量％水溶液のアルキルスルホン酸ソーダを加え、バリア層形成用塗料（Ｉ）を得た。
・ Barrier layer forming paint (latex) (1)
85 parts by weight of water, 0.15 parts by weight of sodium alkyl sulfonate and 0.10 parts by weight of sodium persulfate were charged into a pressure-resistant reaction vessel subjected to glass lining, and after degassing, the temperature of the contents was maintained at 55 ° C. . In a separate container, 97 parts by mass of vinylidene chloride, 2 parts by mass of methyl acrylate, and 1 part by mass of acrylic acid were weighed and mixed to prepare a monomer mixture. In the reaction vessel, 10 parts by mass of the monomer mixture was charged and the reaction was allowed to proceed with stirring. After confirming that the reaction almost proceeded by lowering the internal pressure of the reaction vessel, 10 parts by weight of sodium alkyl sulfonate in 15% by weight aqueous solution was injected, and then the remaining amount of the monomer mixture was continuously added for 15 hours. A fixed amount was added. To the obtained monomer mixture, 15% by mass aqueous sodium alkyl sulfonate was added so that the liquid surface tension at 20 ° C. was 42 mN / m, to obtain a barrier layer forming coating material (I).
・バリア層形成用塗料（ラテックス）（２）
旭化成ケミカルズ社製のＬ５３６Ｂ（固形分濃度５０質量％）のポリ塩化ビニリデンラテックス
・ Barrier layer forming paint (latex) (2)
L536B (solid content concentration: 50% by mass) polyvinylidene chloride latex manufactured by Asahi Kasei Chemicals
実施例１
ナイロン６樹脂（ユニチカ社製、商品名：Ａ１０３０ＢＲＦ、相対粘度３．１）に、表１で示すシリカ含有量になるように、シリカ含有マスターチップＭ１を混合し、シリンダ温度２６０℃に設定した単軸押出機に供給し、Ｔダイより押出し、設定温度２０℃の冷却ロールに接触させて、厚さ１５０μｍの未延伸フィルムを得た。得られた未延伸フィルムが、水分率３．５％となるように、６５℃に調整した温水層に浸漬した。
次いで、未延伸フィルムの片面に、バリア層形成用塗料（１）をエアーナイフコーティング法により塗布し、温度１１０℃の赤外線照射機により３０秒間乾燥処理を行って、バリア層形成用塗料中の水分を蒸発乾燥した。
Example 1
A silica-containing master chip M1 was mixed with nylon 6 resin (manufactured by Unitika Ltd., trade name: A1030BRF, relative viscosity 3.1) so that the silica content shown in Table 1 was obtained, and the cylinder temperature was set to 260 ° C. The unstretched film with a thickness of 150 μm was obtained by feeding to a shaft extruder, extruding from a T-die, and contacting with a cooling roll having a set temperature of 20 ° C. The obtained unstretched film was immersed in a hot water layer adjusted to 65 ° C. so that the moisture content was 3.5%.
Next, the barrier layer-forming paint (1) is applied to one side of the unstretched film by an air knife coating method, and dried for 30 seconds with an infrared irradiator at a temperature of 110 ° C. Was evaporated to dryness.
次に、このバリア層形成用塗料（１）を塗布した未延伸フィルムに２３０℃の熱風を１秒間吹き付けることにより予熱を行い、温度２００℃に調整したテンター式の同時２軸延伸機でＭＤ方向に３倍、ＴＤ方向に３．３倍延伸した。続いて、延伸シートに２１０℃の熱風を３秒間吹き付けながら、ＴＤ方向に５％弛緩して、熱固定処理を行った。そして、冷却を行い、厚さ１５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。 Next, the unstretched film coated with this barrier layer-forming coating (1) was preheated by blowing hot air at 230 ° C. for 1 second, and was adjusted in the MD direction by a tenter type simultaneous biaxial stretching machine adjusted to a temperature of 200 ° C. 3 times and 3.3 times in the TD direction. Subsequently, while hot air at 210 ° C. was blown on the stretched sheet for 3 seconds, it was relaxed by 5% in the TD direction to perform heat setting treatment. And it cooled and obtained the polyamide film of the multilayer structure which consists of a 15-micrometer-thick polyamide film (X) and a 1.2-micrometer-thick barrier layer (Y).
実施例２〜９、比較例５〜１１
未延伸シートの水分率、予熱温度、延伸温度、熱固定温度を表１に示す値に変更した以外は、実施例１と同様にして厚さ１５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Examples 2-9, Comparative Examples 5-11
A polyamide film (X) having a thickness of 15 μm and a thickness of 1.2 μm were obtained in the same manner as in Example 1 except that the moisture content, preheating temperature, stretching temperature, and heat setting temperature of the unstretched sheet were changed to the values shown in Table 1. A polyamide film having a multilayer structure composed of the barrier layer (Y) was obtained.
実施例１０
表１で示すシリカ含有量になるように、シリカ含有マスターチップＭ１の混合量を変更した以外は、実施例２と同様にして厚さ１５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Example 10
A polyamide film (X) having a thickness of 15 μm and a barrier layer having a thickness of 1.2 μm were obtained in the same manner as in Example 2 except that the mixing amount of the silica-containing master chip M1 was changed so as to obtain the silica content shown in Table 1. A polyamide film having a multilayer structure composed of (Y) was obtained.
実施例１１、１２、比較例１２
シリカ含有マスターチップＭ２を用い、表１に示すシリカ含有量となるように、シリカ含有マスターチップＭ２の混合量を変更した以外は、実施例２と同様にして厚さ１５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Examples 11 and 12, Comparative Example 12
A polyamide film (X) having a thickness of 15 μm was used in the same manner as in Example 2 except that the mixing amount of the silica-containing master chip M2 was changed using the silica-containing master chip M2 so that the silica content shown in Table 1 was obtained. A polyamide film having a multilayer structure composed of a barrier layer (Y) having a thickness of 1.2 μm was obtained.
実施例１３
未延伸シートの厚みを２５０μｍとなるように変更した以外は、実施例２と同様に行い、厚さ２５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Example 13
Except for changing the thickness of the unstretched sheet to 250 μm, the same procedure as in Example 2 was performed, and a multilayer structure comprising a polyamide film (X) having a thickness of 25 μm and a barrier layer (Y) having a thickness of 1.2 μm was used. A polyamide film was obtained.
実施例１４
バリア層形成用塗料（２）を使用した以外は、実施例２と同様に行い、厚さ１５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Example 14
A polyamide film having a multilayer structure comprising a polyamide film (X) having a thickness of 15 μm and a barrier layer (Y) having a thickness of 1.2 μm is carried out in the same manner as in Example 2 except that the coating material for forming a barrier layer (2) is used. Got.
実施例１５〜１８、比較例１５
バリア層（Ｙ）の厚みを、表１にした以外は、実施例２と同様に行い、厚さ１５μｍのポリアミドフィルム（Ｘ）、バリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Examples 15-18, Comparative Example 15
Except for changing the thickness of the barrier layer (Y) to Table 1, it was carried out in the same manner as in Example 2 to obtain a polyamide film (X) having a thickness of 15 μm and a polyamide film having a multilayer structure composed of the barrier layer (Y). .
比較例１
シリカ含有マスターチップＭ１を混合しなかった以外は、実施例２と同様にして厚さ１５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Comparative Example 1
A polyamide film having a multilayer structure composed of a polyamide film (X) having a thickness of 15 μm and a barrier layer (Y) having a thickness of 1.2 μm was obtained in the same manner as in Example 2 except that the silica-containing master chip M1 was not mixed. It was.
比較例２
未延伸フィルムに、バリア層形成用塗料（１）を塗布しなかった以外は、実施例２と同様にして厚さ１５μｍのポリアミドフィルムを得た。
Comparative Example 2
A polyamide film having a thickness of 15 μm was obtained in the same manner as in Example 2, except that the barrier layer-forming coating material (1) was not applied to the unstretched film.
比較例３
未延伸シートを温水層に浸漬することなく延伸を行った以外は、実施例１と同様に行い、厚さ１５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Comparative Example 3
A multilayer comprising a polyamide film (X) having a thickness of 15 μm and a barrier layer (Y) having a thickness of 1.2 μm, except that the unstretched sheet was stretched without being immersed in the warm water layer. A polyamide film having a constitution was obtained.
比較例４
未延伸シートの厚みを２５０μｍとなるように変更した以外は、比較例３と同様に行い、厚さ２５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Comparative Example 4
Except for changing the thickness of the unstretched sheet to 250 μm, the same procedure as in Comparative Example 3 was performed, and a multilayer structure comprising a polyamide film (X) having a thickness of 25 μm and a barrier layer (Y) having a thickness of 1.2 μm was used. A polyamide film was obtained.
比較例１３
ナイロン６樹脂（ユニチカ社製、商品名：Ａ１０３０ＢＲＦ、相対粘度３．１）に、表１で示すシリカ含有量になる様にシリカ含有マスターチップＭ１を混合し、シリンダ温度２６０℃に設定した単軸押出機に供給し、Ｔダイより押出し、設定温度２０℃の冷却ロールに接触させて、厚さ１５０μｍの未延伸シートを得た。次に、この未延伸フィルムを周速の異なる加熱ローラ群からなる縦延伸機により、温度５５℃、延伸倍率２．５でＭＤ方向に延伸した。次に、縦延伸したフィルムに、バリア層形成用塗料（１）をエアーナイフコーティング法により塗布し、温度１１０℃の赤外線照射機により３０秒間乾燥処理を行って、バリア層形成用塗料中の水分を蒸発乾燥した。
Comparative Example 13
A single shaft in which a silica-containing master chip M1 is mixed with nylon 6 resin (manufactured by Unitika, trade name: A1030BRF, relative viscosity 3.1) so that the silica content shown in Table 1 is obtained, and the cylinder temperature is set to 260 ° C. It was supplied to an extruder, extruded from a T die, and contacted with a cooling roll having a set temperature of 20 ° C. to obtain an unstretched sheet having a thickness of 150 μm. Next, this unstretched film was stretched in the MD direction at a temperature of 55 ° C. and a stretch ratio of 2.5 by a longitudinal stretching machine composed of heating roller groups having different peripheral speeds. Next, the barrier layer-forming paint (1) is applied to the longitudinally stretched film by an air knife coating method, and dried for 30 seconds with an infrared irradiator at a temperature of 110 ° C. Was evaporated to dryness.
次に、このバリア層形成用塗料（１）を塗布したフィルムをテンターに導入し、予熱部にて６０℃の熱風を１秒間吹き付けることにより予熱を行い、温度８０℃に調整した延伸部にて延伸倍率４倍でＴＤ方向に延伸した。続いて、延伸シートに２１０℃の熱風を３秒間吹き付けながら、ＴＤ方向に５％弛緩して、熱固定処理を行った。そして、冷却を行い、厚さ１５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。 Next, the film coated with the barrier layer-forming paint (1) is introduced into a tenter, preheated by blowing hot air of 60 ° C. for 1 second in the preheating portion, and then stretched at a temperature adjusted to 80 ° C. The film was stretched in the TD direction at a stretch ratio of 4 times. Subsequently, while hot air at 210 ° C. was blown on the stretched sheet for 3 seconds, it was relaxed by 5% in the TD direction to perform heat setting treatment. And it cooled and obtained the polyamide film of the multilayer structure which consists of a 15-micrometer-thick polyamide film (X) and a 1.2-micrometer-thick barrier layer (Y).
比較例１４
延伸倍率を、ＭＤ方向３倍、ＴＤ方向３．３倍に変更した以外は比較例１３と同様に行い、厚さ１５μｍのポリアミドフィルム（Ｘ）、厚み１．２μｍのバリア層（Ｙ）から成る複層構成のポリアミドフィルムを得た。
Comparative Example 14
Except that the draw ratio was changed to 3 times in the MD direction and 3.3 times in the TD direction, the same procedure as in Comparative Example 13 was performed, and the polyamide film (X) having a thickness of 15 μm and the barrier layer (Y) having a thickness of 1.2 μm were formed. A polyamide film having a multilayer structure was obtained.
実施例１〜１８、比較例１〜１５における製造条件と、得られた複層構成のポリアミドフィルムの特性値、延伸性の評価結果を表１に示す。 Table 1 shows the production conditions in Examples 1 to 18 and Comparative Examples 1 to 15, the characteristic values of the obtained polyamide film having a multilayer structure, and the evaluation results of stretchability.
実施例１〜１８においては特定の製造条件を満足するものであったため、得られた複層構成のポリアミドフィルムは、本発明で規定する特性値（１）〜（６）の全てを満足するものであり、表面が艶消し状態であるマット調を有し、かつ、衝撃強度、寸法安定性、酸素バリア性、水蒸気バリア性ともに優れたものであった。 In Examples 1 to 18, since the specific production conditions were satisfied, the obtained polyamide film having a multilayer structure satisfies all of the characteristic values (1) to (6) defined in the present invention. It had a matte surface with a matte surface and was excellent in impact strength, dimensional stability, oxygen barrier property, and water vapor barrier property.
一方、比較例１ではシリカを含有しないポリアミド樹脂を用いたため、得られた複層構成のポリアミドフィルムは光沢度が高く、マット調を有するものではなかった。
比較例２は、バリア層（Ｙ）を形成していないため、必要とする酸素透過度及び水蒸気透過度が得られなかった。比較例３〜５では、未延伸フィルムの水分率が低すぎたため、延伸応力が高くなり、得られた複層構成のポリアミドフィルムは、熱水収縮率斜め差が大きくなり、空隙率が高く、衝撃強度が低いものとなった。さらには延伸性も悪かった。比較例６〜１１では、予熱温度、延伸温度、熱固定温度のいずれかが好適な範囲ではなかったため、本発明で規定する特性値（２）〜（４）を満足するものではなかった。また、比較例１２では、シリカの含有量が多いポリアミド樹脂を用いたため、空隙率が大きくなり、衝撃強度の低いものとなった。さらには、引張強度や引張伸度の低いものとなり、延伸性も悪かった。比較例１３〜１４では、未延伸フィルムの水分率が低く、かつ予熱温度、延伸温度ともに低いものであったため、熱水収縮率斜め差が大きくなり、空隙率が高いものであった。比較例１５では、バリア層（Ｙ）の厚みが、薄すぎたため、得られた複層構成のポリアミドフィルムは、本発明で規定する特性値（５）〜（６）を満足するものではなかった。
On the other hand, in Comparative Example 1, since a polyamide resin not containing silica was used, the obtained polyamide film having a multilayer structure had high glossiness and did not have a matte tone.
In Comparative Example 2, since the barrier layer (Y) was not formed, the required oxygen permeability and water vapor permeability could not be obtained. In Comparative Examples 3 to 5, since the moisture content of the unstretched film was too low, the stretching stress was increased, and the resulting polyamide film having a multilayer structure had a large difference in the hot water shrinkage rate and the porosity was high. The impact strength was low. Furthermore, the stretchability was also poor. In Comparative Examples 6 to 11, any one of the preheating temperature, the stretching temperature, and the heat setting temperature was not in a suitable range, and thus the characteristic values (2) to (4) defined in the present invention were not satisfied. Moreover, in the comparative example 12, since the polyamide resin with much silica content was used, the porosity became large and the impact strength was low. Furthermore, the tensile strength and tensile elongation were low, and the stretchability was also poor. In Comparative Examples 13 to 14, since the moisture content of the unstretched film was low and the preheating temperature and the stretching temperature were both low, the oblique difference in hot water shrinkage ratio was large and the porosity was high. In Comparative Example 15, since the thickness of the barrier layer (Y) was too thin, the obtained polyamide film having a multilayer structure did not satisfy the characteristic values (5) to (6) defined in the present invention. .
Claims (3)
下記（１）〜（６）の条件を同時に満たすことを特徴とするマット調バリアポリアミドフィルム。
（１）光沢度が５０％以下
（２）フィルムの空隙率が０．１〜５％
（３）２０℃条件下で測定される衝撃強度が０．３５Ｊ以上
（４）フィルムの幅方向（ＴＤ方向）に対して４５度の方向と１３５度の方向における熱水収縮率の差が２．０％以下
（５）酸素透過度が、２０℃、６５％ＲＨ下で、１００ｍｌ／ｍ２・ｄａｙ・ＭＰａ以下
（６）水蒸気透過度が、４０℃、９０％ＲＨ下で、２０ｇ／ｍ２・ｄａｙ以下 A polyamide film having a multilayer structure including a polyamide film (X) made of a polyamide resin containing silica and a barrier layer (Y),
A mat-like barrier polyamide film characterized by simultaneously satisfying the following conditions (1) to (6):
(1) Glossiness is 50% or less (2) Porosity of film is 0.1 to 5%
(3) Impact strength measured at 20 ° C. is 0.35 J or more. (4) The difference in hot water shrinkage between the direction of 45 degrees and the direction of 135 degrees with respect to the film width direction (TD direction) is 2. 0.05% or less (5) Oxygen permeability at 20 ° C. under 65% RH, 100 ml / m 2 · day · MPa or less (6) Water vapor permeability at 40 ° C. under 90% RH, 20 g / m 2 · day or less
（１）未延伸フィルムの水分率が３〜９％になるように温水槽で吸水させた後、未延伸フィルムの少なくとも一方の面にポリ塩化ビニリデン系共重合体を含有するバリア層形成用塗料を塗布する。
（２）予熱温度１８０〜２５０℃で予熱を行い、温度１７０〜２３０℃で延伸を行い、さらに温度１８０〜２３０℃で熱固定を行う。 A method for producing a matte-like barrier polyamide film according to claim 1 or 2, wherein the steps (1) and (2) are sequentially performed.
(1) A barrier layer-forming coating material comprising a polyvinylidene chloride copolymer on at least one surface of an unstretched film after water absorption in a hot water tank so that the moisture content of the unstretched film is 3 to 9%. Apply.
(2) Preheating is performed at a preheating temperature of 180 to 250 ° C., stretching is performed at a temperature of 170 to 230 ° C., and heat setting is further performed at a temperature of 180 to 230 ° C.
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| WO2021149815A1 (en) * | 2020-01-24 | 2021-07-29 | ユニチカ株式会社 | Method for producing polyamide resin film |
| WO2022059472A1 (en) * | 2020-09-18 | 2022-03-24 | 旭化成株式会社 | Gas and water vapor barrier laminated body |
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| EP4094923A4 (en) * | 2020-01-24 | 2024-04-17 | Unitika Ltd. | Method for producing polyamide resin film |
| US12012491B2 (en) | 2020-01-24 | 2024-06-18 | Unitika Ltd. | Method for producing polyamide resin film |
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| JP7441323B2 (en) | 2020-09-18 | 2024-02-29 | 旭化成株式会社 | Gas and water vapor barrier laminate |
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