WO2014208710A1 - 積層体およびその製造方法 - Google Patents
積層体およびその製造方法 Download PDFInfo
- Publication number
- WO2014208710A1 WO2014208710A1 PCT/JP2014/067100 JP2014067100W WO2014208710A1 WO 2014208710 A1 WO2014208710 A1 WO 2014208710A1 JP 2014067100 W JP2014067100 W JP 2014067100W WO 2014208710 A1 WO2014208710 A1 WO 2014208710A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyamide film
- laminate
- film
- metal foil
- polyamide
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Definitions
- the present invention relates to a laminate and a manufacturing method thereof, and more particularly, to a laminate having moldability and a manufacturing method thereof.
- Metal foils such as aluminum foil are used in a wide range of fields from food packaging applications to industrial applications because of their excellent gas barrier properties and water vapor permeability.
- examples of applications that require metal foils to be processed include press-through packs for food packaging applications, and laminates for laminated lithium ion batteries for industrial applications.
- a laminate obtained by laminating a resin layer such as a barrier coat layer and a barrier resin layer has insufficient gas barrier properties and water vapor barrier properties. For this reason, it is necessary to use an aluminum foil.
- the moldability is improved by adopting a laminate structure in which polyamide film / aluminum foil / sealant film are laminated in this order. .
- a similar laminate is also disclosed in Patent Documents 2-5.
- the moldability of the known laminate described above depends on the performance of the polyamide film.
- the polyamide film has excellent performance such as heat resistance, dimensional stability, thickness accuracy, and the like, and has a stretching balance in length and width. Anisotropy generated from the difference is likely to occur. For this reason, it is difficult for the laminated body of the said structure which laminated
- the present invention improves the moldability of a laminate in which a polyamide film / metal foil / sealant film is laminated in this order even when a polyamide film produced by a tenter type biaxial stretching machine is used.
- the purpose is to be able to.
- the present inventors manufactured a polyamide film in a laminate in which a polyamide film / metal foil / sealant film are laminated in this order under a specific condition by a tenter type biaxial stretching method. Extensiveness not available with polyamide films manufactured by the axial stretching method can be imparted to the metal foil, and cracks and pinholes do not occur during molding using laminates, that is, deep drawing molding and stretch molding processing It was found that a laminate excellent in moldability suitable for the above can be obtained. As a result, the present inventors have solved the problem of moldability of a laminate using a polyamide film such as a known tenter-type biaxially stretched polyamide film, and have completed the present invention.
- the gist of the present invention is as follows. (1) A laminate comprising a polyamide film produced by a tenter biaxial stretching method and having a crystallinity of 20 to 35%, a metal foil, and a sealant film laminated in this order.
- a packaging material having a concave portion for storing contents which is a product obtained by deep drawing or overmolding one of the above laminates (1) to (4).
- a polyamide film, a metal foil, and a sealant film which are manufactured by a tenter type biaxial stretching method and have a crystallinity of 20 to 35%, are laminated in this order. It is possible to provide a laminate excellent in moldability suitable for a stretch molding process. According to the present invention, this laminate can be suitably used as a press-through pack or a lithium ion battery package.
- the polyamide film it is necessary for the polyamide film to be produced by a tenter biaxial stretching method and have a crystallinity of 20 to 35% in order to impart extensibility to the metal foil.
- a polyamide film having a crystallinity of less than 20% or more than 35% cannot sufficiently bring out the spreadability of the metal foil, and delamination, cracks and pinholes are likely to occur during deep drawing.
- the Eriksen value is less than 10 mm.
- the crystallinity of the polyamide film is calculated using the following formula.
- X (crystallinity) (ds-da) / (dc-da)
- ds is the amorphous density in the sample
- dc is the crystalline density in the sample
- da is the density of the sample.
- the density of the sample is measured based on JISK6810 (polyamide resin molding material test method).
- the crystallinity of the polyamide film can be controlled by, for example, the conditions of the heat treatment temperature during production.
- the maximum temperature of the heat treatment is preferably 200 ° C. to 225 ° C., more preferably 205 ° C. to 215 ° C.
- the heat treatment time is preferably 3.5 to 8.0 seconds.
- the maximum heat treatment temperature is less than 200 ° C. or the heat treatment time is less than 3.5 seconds, the crystallinity is low, and the moldability of the laminate is improved.
- the heat shrinkage rate is increased, and there is a problem such as delamination. In addition to being easily generated, the basic performance as a film is reduced.
- the maximum temperature of the heat treatment exceeds 225 ° C. or when the heat treatment time exceeds 8.0 seconds, the degree of crystallinity increases, so that the heat shrinkage reduction and dimensional stability are improved, but the polyamide film is stretched Tends to be difficult, and the moldability of the laminate tends to decrease.
- the thermal shrinkage rate of the polyamide film of the present invention during heat treatment at 160 ° C. for 5 minutes is preferably 2.5% or less for both MD and TD.
- the thermal shrinkage rate satisfies both 2.5% or less for both MD and TD.
- the polyamide film constituting the laminate of the present invention is a film produced by a tenter type biaxial stretching method. More specifically, the film is produced by a tenter simultaneous biaxial stretching method or a tenter sequential biaxial stretching method.
- Polyamide films can be produced by other methods, for example, the tubular biaxial stretching method, but the polyamide film obtained by the same method has low thickness accuracy, so delamination, cracks and pinholes occur during molding. It's easy to do.
- the draw ratio is preferably 2.5 to 5.0 times in the longitudinal and transverse directions. When the draw ratio is less than 2.5 times, sufficient physical properties may not be obtained even if drawn. On the contrary, when the stretching ratio exceeds 5 times, the stretching may be difficult.
- the polyamide film is controlled to be from 20% to 35%, whereby the polyamide film is converted into a tenter type biaxial stretching method.
- a polyamide film / metal foil / sealant film is laminated in this order, and the laminate is excellent in moldability. Can be provided.
- the polyamide resin used for the polyamide film is preferably nylon 6.
- the total thickness of the polyamide film is not particularly limited, but is preferably 6 to 25 ⁇ m, more preferably 12 to 25 ⁇ m. If the thickness is less than 6 ⁇ m, imparting of spreadability to the metal foil is insufficient. When thickness exceeds 25 micrometers, the moldability of polyamide film itself falls.
- one or more kinds of various inorganic lubricants and organic lubricants may be blended as a lubricant for imparting slip properties.
- the method of adding a lubricant include a method of incorporating lubricant particles in a polyamide resin as a raw material, a method of adding directly to an extruder, and the like. Any one of these methods may be adopted, or two methods may be used in combination.
- bending pinhole resistance improvers such as polyolefins, polyamide elastomers and polyester elastomers, pigments, antioxidants, ultraviolet absorbers,
- additives such as preservatives, antistatic agents and inorganic fine particles may be added.
- the metal foil constituting the laminate of the present invention is preferably an aluminum foil, and there is no particular limitation as to whether it is a pure aluminum foil or an aluminum alloy foil.
- the aluminum alloy foil it is preferable to contain iron, and the other components can be used as long as they are within the range of known contents stipulated in ISO as long as the moldability of the laminate is not impaired. May be included.
- the thickness of the aluminum foil is preferably about 20 to 80 ⁇ m, more preferably 25 to 60 ⁇ m.
- the sealant film constituting the laminate of the present invention is not particularly limited, but a thermoplastic resin such as an olefin copolymer represented by polyethylene or polypropylene can be applied.
- the polyamide film / metal foil is laminated using an adhesive.
- the adhesive at that time include urethane adhesives and acrylic adhesives.
- a two-component reactive adhesive is preferred from the viewpoint of adhesive strength.
- An anchor coat layer may be provided on the metal foil for the purpose of improving adhesiveness.
- dry lamination or extrusion lamination can be applied.
- one or more other layers may be laminated on the polyamide film according to the purpose.
- a polyester film is suitable as the other layer. This is because heat resistance and chemical resistance are increased and the peel strength is improved for unknown reasons.
- the polyester include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2, 6-naphthalate and the like. PET is preferable from the viewpoint of cost effectiveness.
- the laminate of the present invention preferably has an Erichsen value of 10 mm or more by an Ericksen test based on ISO20482.
- Erichsen value means using an Erichsen tester, placing a sheet-like laminate on an annular base and pressing the center with a spherical projection, and then delamination, cracks, pinholes on the laminate The depth at which the spherical protrusion has invaded until the occurrence of the is shown. If the Erichsen value is 10 mm or more, good moldability can be obtained.
- the peel strength at the interface when the polyamide film and the metal foil are peeled from each other is preferably 2.9 N / cm or more.
- the peel strength is high, the polyamide film may break, but such a state is likely to occur when the peel strength exceeds 4.0 N / cm. In that case, the peel strength is 2. It can be considered that it is 9 N / cm or more.
- the peel strength between the polyamide film and the metal foil is less than 2.9 N / cm, delamination is likely to occur during deep drawing, resulting in the metal foil in the gap formed between the polyamide film and the metal foil. Loss of spreadability tends to cause cracks and pinholes.
- the polyamide film and the metal foil are bonded together by an adhesive as described above, but the peeling interface when peeling is preferably not between the adhesive layer and the metal foil. That is, it is preferable that the peeling interface is between the polyamide film and the adhesive, or the peeling is performed by cohesive failure of the adhesive.
- the peeling interface is between the adhesive and the metal foil, the adhesive strength between the metal foil and the adhesive layer is weak, and this causes the spreadability of the metal foil to be lost, resulting in cracks and pinholes. Will do.
- peeling strength indicates a force required to peel off a polyamide film and a metal foil that have been dry-laminated using an adhesive for dry lamination (for example, urethane adhesive or acrylic adhesive). Further, the “cohesive failure of the adhesive” means that when the peeling is performed, the adhesive layer is broken.
- the peel strength is affected by the crystallinity of the polyamide film.
- the crystallized part and the amorphous part are compared, the crystallized part tends to be relatively inferior in adhesiveness. Therefore, in order to increase the peel strength, it is preferable that the crystallinity is low.
- the polyamide film was allowed to stand for 2 hours or more in an environment of 23 ° C. ⁇ 50% RH, and then cut into strips having a length of 150 mm and a width of 10 mm.
- a dry heat shrinkage test piece was created by marking a pair of marks at intervals of 110 mm in the length direction. After measuring the distance between the gauge points, heat treatment was performed at 160 ° C. for 5 minutes using a hot air dryer, and the mixture was allowed to stand at 23 ° C. ⁇ 50% RH for 2 hours or more, and then the distance between gauge points was measured.
- the thermal contraction rate of MD was measured using a test piece cut so that the MD of the film was in the length direction and the TD of the film was in the width direction.
- the thermal shrinkage rate of TD was measured using a test piece cut so that the TD of the film was in the length direction and the MD of the film was in the width direction.
- an Erichsen test machine (No. 5755 manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used, and a steel ball punch was pressed against the laminated body at a predetermined indentation depth to obtain an Erichsen value.
- the laminate was cut into a strip of MD 100 mm ⁇ TD 15 mm at 23 ° C. ⁇ 50% RH, and the polyamide film and aluminum foil were peeled 30 mm from each other using tweezers to prepare a laminate strength test piece.
- an adhesive layer was interposed between the polyamide film and the aluminum foil, but the adhesive layer was thinner than the polyamide film and the aluminum foil. It was not possible to selectively separate the foil. For this reason, the polyamide film and the aluminum foil were peeled off as described above with the adhesive layer appropriately attached to the polyamide film and / or the aluminum foil.
- a two-component polyurethane adhesive (manufactured by Toyo Morton Co., Ltd., product name: TM-K55 / CAT-10L) was applied to a polyamide film (thickness 25 ⁇ m) so that the coating amount was 5 g / m 2 , at 80 ° C. Dried for 10 seconds. And the aluminum foil (50 micrometers in thickness) was bonded together to the surface at the side of the adhesive agent of a polyamide film. Next, the same adhesive was apply
- an unstretched polypropylene film manufactured by Mitsui Chemical Tosero Co., Ltd., product name: GHC, thickness 50 ⁇ m
- an aging treatment is performed in an atmosphere at 40 ° C. for 72 hours to create a laminate A. did.
- Polyester film polyamide film, aluminum foil, sealant film laminate (laminate B)
- the same two-component polyurethane adhesive as described above is applied to a PET film (thickness 12 ⁇ m) as a polyester film under the same conditions as described above, dried, and on the adhesive layer side, a polyamide film (thickness 25 ⁇ m) is applied. Pasted together.
- the aluminum foil and the sealant film are bonded to the polyamide film side of the laminate of the polyester film and the polyamide film in the same manner as the polyamide film, the aluminum foil, and the sealant film laminate A, and the laminate A
- the laminated body B was created by performing an aging treatment under the same conditions as in.
- the obtained unstretched sheet was subjected to water treatment at 60 ° C. for 1 minute. Thereafter, the end in the width direction of the sheet was held with a clip of a tenter type simultaneous biaxial stretching apparatus, and simultaneous biaxial stretching was performed at a stretching temperature of 185 ° C. at a stretching ratio of 3 times in MD and 3.3 times in TD. . Then, heat treatment is performed for 6.5 seconds under a temperature condition where the maximum temperature in the heat treatment zone is 200 ° C., and further relaxation treatment of 5.0% is performed to obtain a polyamide film having a thickness of 25 ⁇ m and a crystallinity of 20%. It was.
- the laminate of Example 1 was obtained by manufacturing the laminate A using the polyamide film.
- the other heat treatment temperature was changed as shown in Table 1 to obtain another polyamide film having a crystallinity different from that of the polyamide film of Example 1.
- the laminated body A and the laminated body B were obtained as shown in Table 1 using these polyamide films.
- Example 6 A laminate B was obtained using the same polyamide film as in Example 1.
- the stretching method in the production method of the polyamide film of Example 1 was changed to biaxial stretching sequentially. And the point which does not perform a water-containing process compared with Example 1 was made to differ. And the polyamide film was manufactured on the conditions similar to Example 1 except these points and the following heat processing temperature in Example 8. FIG. That is, by setting the heat treatment temperature to the temperature described in Table 1, films having the crystallinity described in Table 1 were obtained. And the laminated body A was obtained as shown in Table 1 with the above-mentioned lamination method.
- Table 1 shows the evaluation results for the above-described examples and comparative examples.
- Comparative Examples 1 and 3 since the crystallinity of the polyamide film was too low, a high peel strength was obtained, but the peel interface was an adhesive / aluminum foil interface. That is, the formability of the aluminum foil was lost due to the loss of the spreadability of the aluminum foil, so that cracks and pinholes were likely to occur.
- Comparative Examples 2 and 4 since the crystallinity of the polyamide film was too high, the peel strength value was less than 2.9 N / cm, and thus sufficient moldability was not obtained.
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- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Wrappers (AREA)
Abstract
Description
(1)テンター式二軸延伸法で製造されかつ結晶化度が20~35%であるポリアミドフィルムと、金属箔と、シーラントフィルムとがこの順に積層されていることを特徴とする積層体。
X(結晶化度)=(ds-da)/(dc-da)
ポリアミドフィルムの結晶化度は、例えば、製造時の熱処理温度の条件によって制御することができる。
下記の実施例、比較例において、ポリアミドフィルムおよび積層体の物性評価は、以下のようにして行った。
熱収縮率(%)={(熱処理前の標点間距離 -熱処理後の標点間距離)
/(熱処理前の標点間距離)}×100
(1)ポリアミドフィルム、アルミニウム箔、シーラントフィルム積層体(積層体A)
ユニチカ社製ナイロン6樹脂(品名:A1030BRF)と、滑剤としてのシリカを6質量%含有するナイロン6樹脂(ユニチカ社製、品名A1030QW)とを、(A1030BRF)/(A1030QW)=99.7/1.3(質量比)の組成比率にて押出機内で溶融混錬し、Tダイへ供給してシート状に吐出し、20℃に温調した金属ドラムに巻き付けて冷却し、そのうえで金属ドラムから繰り出してロール状に巻き取った。これにより、約150μmの厚みの未延伸シートを製造した。次いで、得られた未延伸シートに60℃で1分間の含水処理を施した。その後、シートの幅方向の端部をテンター式同時二軸延伸装置のクリップで保持し、延伸温度185℃でMDに3倍、TDに3.3倍の延伸倍率で同時二軸延伸を行った。そして熱処理ゾーンでの最高温度が200℃の温度条件で6.5秒間熱処理を施し、さらに5.0%の弛緩処理することで、厚さが25μm、結晶化度が20%のポリアミドフィルムを得た。
実施例1と同じポリアミドフィルムを用いて、積層体Bを得た。
比較例2、4は、ポリアミドフィルムの結晶化度が高すぎたため、剥離強力値が2.9N/cm未満となり、したがって十分な成形性が得られなかった。
Claims (5)
- テンター式二軸延伸法で製造されかつ結晶化度が20~35%であるポリアミドフィルムと、金属箔と、シーラントフィルムとがこの順に積層されていることを特徴とする積層体。
- ISO20482に基づくエリクセン試験によるエリクセン値が10mm以上であることを特徴とする請求項1記載の積層体。
- ポリアミドフィルムと金属箔とを互いに剥離したときの剥離強力が2.9N/cm以上であることを特徴とする請求項1または2記載の積層体。
- 剥離の際の剥離界面が、接着剤層と金属箔との層間ではないことを特徴とする請求項3記載の積層体。
- 請求項1から4までのいずれか1項に記載の積層体を深絞り成型または張り出し成型したものであることを特徴とする内容物を収納する凹部を有する包装材。
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Cited By (4)
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JP2017178398A (ja) * | 2016-03-31 | 2017-10-05 | 三菱ケミカル株式会社 | オーブン調理用フィルム、および包装体 |
EP3266606A1 (en) * | 2016-07-04 | 2018-01-10 | Amcor Flexibles Rorschach AG | Deep-drawable film |
JP2018176670A (ja) * | 2017-04-20 | 2018-11-15 | 共同印刷株式会社 | 積層フィルム |
WO2023022086A1 (ja) * | 2021-08-18 | 2023-02-23 | 大日本印刷株式会社 | 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス |
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CN108886115B (zh) * | 2016-04-06 | 2022-02-18 | 大日本印刷株式会社 | 电池用包装材料、其制造方法和电池 |
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- 2014-06-27 TW TW103122229A patent/TWI621532B/zh active
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2017178398A (ja) * | 2016-03-31 | 2017-10-05 | 三菱ケミカル株式会社 | オーブン調理用フィルム、および包装体 |
EP3266606A1 (en) * | 2016-07-04 | 2018-01-10 | Amcor Flexibles Rorschach AG | Deep-drawable film |
WO2018007025A1 (en) * | 2016-07-04 | 2018-01-11 | Amcor Flexibles Rorschach Ag | Deep-drawable film |
RU2750606C2 (ru) * | 2016-07-04 | 2021-06-29 | Амкор Флексиблес Роршах Аг | Способная к глубокой вытяжке пленка (deep-drawable film) |
US11951711B2 (en) | 2016-07-04 | 2024-04-09 | Amcor Flexibles Rorschach Ag | Deep-drawable film |
JP2018176670A (ja) * | 2017-04-20 | 2018-11-15 | 共同印刷株式会社 | 積層フィルム |
WO2023022086A1 (ja) * | 2021-08-18 | 2023-02-23 | 大日本印刷株式会社 | 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス |
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