JP2009079762A - Vacuum heat insulating structure and its manufacturing method - Google Patents
Vacuum heat insulating structure and its manufacturing method Download PDFInfo
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- JP2009079762A JP2009079762A JP2008227679A JP2008227679A JP2009079762A JP 2009079762 A JP2009079762 A JP 2009079762A JP 2008227679 A JP2008227679 A JP 2008227679A JP 2008227679 A JP2008227679 A JP 2008227679A JP 2009079762 A JP2009079762 A JP 2009079762A
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- film
- heat insulating
- metal
- deposited
- metal oxide
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Images
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
- E04B1/78—Heat insulating elements
- E04B1/80—Heat insulating elements slab-shaped
- E04B1/803—Heat insulating elements slab-shaped with vacuum spaces included in the slab
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2201/00—Insulation
- F25D2201/10—Insulation with respect to heat
- F25D2201/14—Insulation with respect to heat using subatmospheric pressure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/24—Structural elements or technologies for improving thermal insulation
- Y02A30/242—Slab shaped vacuum insulation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
- Y02B80/10—Insulation, e.g. vacuum or aerogel insulation
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Acoustics & Sound (AREA)
- Electromagnetism (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Thermal Insulation (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、真空断熱構造体及びその製造方法に関するものであり、更に詳しくは、優れた断熱性能を示し、更に、伸縮や屈曲に対する耐性に優れ、長期間使用した際にもクラックやピンホールが生じにくく断熱性能の低下しない真空断熱構造体及びその製造方法に関するものである。 The present invention relates to a vacuum heat insulating structure and a method for producing the same, and more specifically, exhibits excellent heat insulating performance, and further exhibits excellent resistance to expansion and contraction and bending, and has cracks and pinholes even when used for a long time. The present invention relates to a vacuum heat insulating structure that hardly occurs and does not deteriorate heat insulating performance, and a manufacturing method thereof.
従来、冷蔵庫や電気ポットの断熱材、あるいは住宅用断熱壁用の断熱パネルとしては、ポリウレタンフォームを用いた断熱体が利用されてきたが、近年これに代わる、優れた材料として、グラスウール、酸化珪素、発泡樹脂などの断熱性材料を芯材とし、これをガスバリア性ラミネートフィルムで密封し且つ内部を真空とした真空断熱構造体が用いられ始めている。 Conventionally, heat insulating materials using polyurethane foam have been used as heat insulating materials for refrigerators and electric pots or heat insulating walls for houses, but in recent years, glass wool, silicon oxide have been used as excellent alternative materials. A vacuum heat insulating structure in which a heat insulating material such as foamed resin is used as a core material, which is sealed with a gas barrier laminate film and the inside is vacuumed, has begun to be used.
かかるガスバリア性ラミネートフィルムとして、アルミ箔を含有した多層フィルムや、ポリビニルアルコール樹脂フィルムを含有した多層フィルムなどが挙げられる。 Examples of the gas barrier laminate film include a multilayer film containing an aluminum foil and a multilayer film containing a polyvinyl alcohol resin film.
例えば、エチレン−ビニルアルコール共重合体樹脂フィルムを含有した多層フィルムを含む真空断熱構造体としては、芯材と、前記芯材を外包する外装袋外被材とを備え、前記外装袋が、蒸着層を有するラミネートフィルム同士、もしくは蒸着層を有するラミネートフィルムと、金属箔を有するラミネートフィルムとを、熱溶着によって袋状にしたものであり、前記蒸着層を有するラミネートフィルムが、熱溶着層と、ガスバリア層と、最外層とを含み、前記ガスバリア層がエチレン−ビニルアルコール共重合体樹脂を含むプラスチックフィルムの片側にアルミ蒸着を施したものであり、かつ、アルミ蒸着を施した面が熱溶着層側に設けられている真空断熱体（例えば、特許文献１参照。）や、また、断熱性材料を二軸延伸ポリビニルアルコールフィルムを含む多層フィルムにより密封包装して得られる真空断熱構造体であり、かかる多層フィルムとしては、二軸延伸ポリビニルアルコールと、金属が蒸着されていてもよいポリエステルフィルム、ポリアミドフィルム、ポリオレフィンフィルム等が積層した多層フィルムを用いた真空断熱構造体（例えば、特許文献２参照）が提案されている。 For example, the vacuum heat insulating structure including a multilayer film containing an ethylene-vinyl alcohol copolymer resin film includes a core material and an outer bag envelope material that encloses the core material, and the outer bag is a vapor deposition Laminate films having layers, or a laminate film having a vapor deposition layer, and a laminate film having a metal foil are formed into a bag shape by heat welding, and the laminate film having the vapor deposition layer is a heat weld layer, A gas barrier layer and an outermost layer, wherein the gas barrier layer is formed by vapor-depositing aluminum on one side of a plastic film containing an ethylene-vinyl alcohol copolymer resin, and the aluminum-deposited surface is a heat-welded layer A vacuum insulator (see, for example, Patent Document 1) provided on the side, or a biaxially stretched polyvinyl alcohol as a heat insulating material This is a vacuum heat insulating structure obtained by hermetically packaging with a multilayer film including a film, such as a biaxially stretched polyvinyl alcohol and a polyester film, a polyamide film, a polyolefin film, etc. on which metal may be deposited. A vacuum heat insulating structure (for example, see Patent Document 2) using a laminated multilayer film has been proposed.
しかしながら、金属箔を有するラミネートフィルムは、金属を使用するため伸縮あるいは屈曲に対する耐性に乏しく、かかるフィルムを含む真空断熱構造体の外装袋に伸縮あるいは屈曲が加わると、その部分においてフィルムにクラックやピンホールが生じフィルムのガスバリア性が著しく低下し、真空断熱構造体としての断熱性能が低下してしまうという欠点がある。
また、二軸延伸ポリビニルアルコールと、金属が蒸着されていてもよいポリエステルフィルム、ポリアミドフィルム、ポリオレフィンフィルム等が積層した多層フィルムについても、外装袋として加工した際に優れたガスバリア性能を持たせることを優先するあまり、ポリエステルフィルムを主として３層、４層と多種の層を重ね合わせた構成となっており、この場合多層フィルムの伸縮あるいは屈曲に対する耐性は著しく損なわれているのが現状であり、かかる多層フィルムを含む外装袋に伸縮あるいは屈曲が加わると、やはりガスバリア性は著しく低下し、真空断熱構造体としての断熱性能が低下してしまう可能性があった。
However, a laminate film having a metal foil is poor in resistance to expansion and contraction or bending because of the use of metal, and when expansion or bending is applied to an exterior bag of a vacuum heat insulating structure including such a film, cracks or pins are added to the film at that portion. There is a drawback that holes are generated and the gas barrier property of the film is remarkably lowered, and the heat insulation performance as a vacuum heat insulation structure is lowered.
In addition, a multilayer film in which a biaxially stretched polyvinyl alcohol and a polyester film, a polyamide film, a polyolefin film or the like on which metal may be deposited is laminated also has excellent gas barrier performance when processed as an exterior bag. Too much priority, the polyester film is mainly composed of 3 layers, 4 layers and various layers. In this case, the resistance to expansion and contraction or bending of the multilayer film is significantly impaired. If expansion or contraction or bending is applied to the outer bag containing the multilayer film, the gas barrier property is remarkably lowered, and the heat insulation performance as a vacuum heat insulation structure may be lowered.
そこで、本発明ではこのような背景下において、優れた断熱性能を示し、更に、伸縮や屈曲に対する耐性に優れ、長期間使用した際にもクラックやピンホールが生じにくく断熱性能の低下しない真空断熱構造体及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。 Therefore, in the present invention, in such a background, vacuum insulation that exhibits excellent heat insulation performance, is excellent in resistance to expansion and contraction, and does not easily generate cracks or pinholes even when used for a long period of time. An object of the present invention is to provide a structure and a manufacturing method thereof.
しかるに、本発明者はかかる事情に鑑み鋭意研究を重ねた結果、断熱性材料を密封包装するにあたり、外装袋として、金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）と、金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）とが、蒸着面同士が向き合うように積層されてなる多層フィルムを用いることにより、長期間の使用においてもクラックやピンホールを生じることなく断熱性能に非常に高い信頼性を示す真空断熱構造体が得られることを見出し、本発明を完成した。 However, as a result of intensive research in view of such circumstances, the present inventor, as a result of sealing and packaging the heat insulating material, as an exterior bag, a polyolefin film (A) on which metal or metal oxide is deposited, and metal or metal By using a multilayer film formed by laminating the gas barrier film (B) on which the oxide is deposited so that the vapor deposition surfaces face each other, even in long-term use, it does not cause cracks or pinholes, resulting in heat insulation performance. The inventors have found that a vacuum heat insulating structure having very high reliability can be obtained, and have completed the present invention.
即ち、本発明の要旨は、金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）と、金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）を含む多層フィルムと断熱性材料を含む真空断熱構造体であって、該ポリオレフィン系フィルム（Ａ）の金属或いは金属酸化物が蒸着された面と該ガスバリア性フィルム（Ｂ）の金属或いは金属酸化物が蒸着された面が向き合うように積層され、且つ、該多層フィルムが断熱性材料を密封包装していることを特徴とする真空断熱構造体に関するものである。
また、本発明では、前記多層フィルムを袋状に加工する工程、３０℃以上、０．９Ｔｏｏｒ以下の条件下で乾燥する工程、断熱性材料を減圧下にて密封する工程を含むことを特徴とする真空断熱構造体の製造方法をも提供するものである。
That is, the gist of the present invention includes a polyolefin film (A) on which a metal or metal oxide is deposited, a multilayer film including a gas barrier film (B) on which a metal or metal oxide is deposited, and a heat insulating material. A vacuum heat insulating structure, laminated so that the surface of the polyolefin film (A) on which the metal or metal oxide is deposited faces the surface of the gas barrier film (B) on which the metal or metal oxide is deposited. In addition, the present invention relates to a vacuum heat insulating structure characterized in that the multilayer film hermetically wraps a heat insulating material.
Further, the present invention includes a step of processing the multilayer film into a bag shape, a step of drying under a condition of 30 ° C. or more and 0.9 Toor or less, and a step of sealing the heat insulating material under reduced pressure. The manufacturing method of the vacuum heat insulation structure which performs is also provided.
なお、従来本願発明と同程度のガスバリア性を達成するためには、金属蒸着されたポリビニルアルコール系フィルム等のガスバリア性フィルムの外層（袋状にしたときの外気に面する側）に、ガスバリア性に優れる金属蒸着されたポリエステル系フィルムを貼り合せ、更にその外層にもポリオレフィン系フィルムやポリアミド系フィルムを用いる必要があった。
しかし、かかる構成の多層フィルムでは高いガスバリア性は達成されるものの、多層フィルム全体の厚みが厚くなっており、特に金属蒸着されたポリエステル系フィルムを用いているため、長時間使用する場合の伸縮あるいは屈曲に対する耐性は劣るものであった。そこで、本願発明においては、最外層に用いたポリオレフィン系フィルムに金属蒸着を施し、更にかかる蒸着面を金属蒸着されたガスバリア性フィルムの金属蒸着面と向き合うように貼り合せることによって、ガスバリア性に優れる金属蒸着されたポリエステル系フィルムを用いることなくても、優れたガスバリア性を示すことができ、更には長期間の使用においてもクラックやピンホールを生じることなく断熱性能に非常に高い信頼性を示す多層フィルムを見出すことができたのである。
In order to achieve the same level of gas barrier property as that of the present invention of the present application, the gas barrier property is provided on the outer layer of the gas barrier film such as a metal-deposited polyvinyl alcohol film (side facing the outside air when the bag is formed). It was necessary to use a metal film-deposited polyester film excellent in the above-mentioned properties and to use a polyolefin film or a polyamide film for the outer layer.
However, although the multilayer film having such a structure achieves a high gas barrier property, the thickness of the entire multilayer film is thick, and in particular, since a polyester film deposited by metal deposition is used, it is possible to expand or contract when used for a long time. Resistance to bending was inferior. Therefore, in the present invention, the metal film is vapor-deposited on the polyolefin film used for the outermost layer, and the vapor-deposited surface is bonded so that the vapor-deposited surface faces the metal vapor-deposited surface of the gas-deposited gas barrier film. Even without using a metal-deposited polyester film, it can show excellent gas barrier properties, and even in long-term use, it shows very high reliability in heat insulation performance without causing cracks and pinholes I was able to find a multilayer film.
本発明の真空断熱構造体は、柔軟性の高い多層フィルムを用いているため、該多層フィルムで断熱性材料を減圧下にて密封する際に、多層フィルムに発生するシワ部分における応力の低減が図れ、さらに、これらシワ部分に加わる局所的な応力によるクラックあるいはピンホールの発生に対して耐性が高くなり、その結果、長期間にわたり使用した際にも高い信頼度で真空を維持することができ、断熱性能が低下しないといった効果を有するものである。更に、多層フィルムを構成するフィルムとして低熱伝導性の樹脂素材を含むフィルムを用いているため、断熱性能にも優れるものである。 Since the vacuum heat insulating structure of the present invention uses a highly flexible multilayer film, when the heat insulating material is sealed with the multilayer film under reduced pressure, the stress in the wrinkles generated in the multilayer film can be reduced. In addition, it is highly resistant to cracks or pinholes due to local stress applied to these wrinkles, and as a result, a vacuum can be maintained with high reliability even when used for a long period of time. The heat insulation performance is not lowered. Furthermore, since a film containing a resin material having low thermal conductivity is used as a film constituting the multilayer film, the heat insulation performance is also excellent.
以下に、本発明を詳細に説明する。
まず、断熱性材料を密封包装するための多層フィルムに関して説明する。
The present invention is described in detail below.
First, a multilayer film for hermetically packaging a heat insulating material will be described.
本発明で用いられる金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）に関して、まず、蒸着処理を施す前のポリオレフィン系フィルム（ポリオレフィン系フィルム（Ａ’）とする）について説明する。 Regarding the polyolefin film (A) on which the metal or metal oxide used in the present invention is deposited, first, a polyolefin film (hereinafter referred to as polyolefin film (A ′)) before being subjected to the vapor deposition treatment will be described.
ポリオレフィン系フィルム（Ａ’）の原料であるポリオレフィン系樹脂組成物としては、特に限定されることなく、例えば、ポリプロピレン、ポリブテン−１、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレンなどのホモポリマーが挙げられる他、プロピレンを主成分とするエチレン、ブテン−１、ペンテン−１、４−メチルペンテン−１、ヘキセン−１、オクテン−１、５−エチリデン−２−ノルボルネン、５−メチレン−２−ノルボルネン、１，４−ヘキサジエン、スチレンなどとの共重合体、さらには無水マレイン酸などのカルボン酸でグラフト変性されたもの、ブテン−１を主成分とするエチレン、プロピレン、ブテン−２、イソブチレン、ブタジエン、ペンテン−１、４−メチルペンテン−１、ヘキセン−１、オクテン−１などとの共重合体、さらには無水マレイン酸などのカルボン酸でグラフト変性されたもの、エチレンを主成分とするプロピレン、ブテン−１、４−メチルペンテン−１、１−ヘキセン、１−オクテン、５−エチリデン−２−ノルボルネン、５−メチレン−２−ノルボルネン、スチレン、酢酸ビニル、アクリル酸メチル、アクリル酸エチル、アクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸、メタクリル酸グリシディルなどとの共重合体、さらには無水マレイン酸などのカルボン酸でグラフト変性されたもの等を挙げられる。これらの中でも、特にはポリプロピレンを用いることが防湿性および工業的な生産性の点で好ましい。 The polyolefin resin composition that is the raw material of the polyolefin film (A ′) is not particularly limited, and examples thereof include homopolymers such as polypropylene, polybutene-1, high density polyethylene, medium density polyethylene, and low density polyethylene. In addition to the above, ethylene mainly composed of propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene , Copolymers with 1,4-hexadiene, styrene, and the like, and further graft-modified with carboxylic acids such as maleic anhydride, ethylene, propylene, butene-2, isobutylene, butadiene mainly containing butene-1 , Pentene-1,4-methylpentene-1, hexene-1, octene A copolymer with a carboxylic acid such as maleic anhydride, propylene having a main component of ethylene, butene-1,4-methylpentene-1, 1-hexene, -Octene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, styrene, vinyl acetate, methyl acrylate, ethyl acrylate, acrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid, glycidyl methacrylate, etc. And those obtained by graft modification with a carboxylic acid such as maleic anhydride. Among these, it is particularly preferable to use polypropylene from the viewpoint of moisture resistance and industrial productivity.
前記共重合体のうちアクリル酸やメタクリル酸との共重合体は、ナトリウム、亜鉛、アルミニウムなどで架橋されていても良いし、また酢酸ビニルとの共重合体は、酢酸ビニル成分の一部または全てがケン化されていても良い。またポリエチレンは、無水マレイン酸などのカルボン酸でグラフト変性されていても良い。 Among the copolymers, a copolymer with acrylic acid or methacrylic acid may be crosslinked with sodium, zinc, aluminum or the like, and a copolymer with vinyl acetate is a part of vinyl acetate component or All may be saponified. Polyethylene may be graft-modified with a carboxylic acid such as maleic anhydride.
また、必要に応じて、本発明の目的を損なわない範囲で、酸化防止剤、耐熱安定剤、耐候安定剤、帯電防止剤、スリップ剤、アンチブロッキング剤、防曇剤、滑剤、染料、顔料、天然油、合成油、ワックス、充填剤などを配合することができる。 Further, if necessary, as long as the purpose of the present invention is not impaired, an antioxidant, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, Natural oils, synthetic oils, waxes, fillers and the like can be blended.
ポリオレフィン系フィルム（Ａ’）の厚みに関しては、特に限定されないが、通常５〜２００μｍ、特には１０〜１００μｍであることが好ましい。フィルム厚みが薄すぎると、得られる真空断熱構造体の芯材となる断熱性材料の充填性が低下し、厚すぎると、加工性が悪くなるばかりでなく経済的にも不利となる。 The thickness of the polyolefin film (A ′) is not particularly limited, but is usually 5 to 200 μm, particularly preferably 10 to 100 μm. If the film thickness is too thin, the fillability of the heat insulating material that will be the core material of the resulting vacuum heat insulating structure will be reduced, and if it is too thick, not only will the workability deteriorate, but it will also be economically disadvantageous.
更に、かかるポリオレフィン系フィルム（Ａ’）は、初期弾性率が０．５〜１００ＧＰａ、更には１〜５０ＧＰａであることが好ましく、また、水蒸気透過度が１０ｇ／ｍ2／ｄａｙ以下、更には８ｇ／ｍ2／ｄａｙ以下であることが好ましい。
ポリオレフィン系フィルム（Ａ‘）の弾性率が低すぎると積層した後に得られる外装袋が柔軟になりすぎて後の断熱材充填作業および真空脱気封入の工程で形状保持性が低くなり生産性が低下する。弾性率が高すぎると外装袋の柔軟性が失われすぎて真空脱気に不適当である。また、水蒸気透過度が高すぎると過剰な水蒸気が積層体内に取り込まれ、ひいてはポリビニルアルコール系フィルムの水蒸気透過度まで低下させてしまうことで積層体全体の水蒸気透過度の低下をまねき、真空断熱構造体を構成した後に水蒸気が内部に侵入し性能を著しく低下させる。
Further, the polyolefin film (A ′) preferably has an initial elastic modulus of 0.5 to 100 GPa, more preferably 1 to 50 GPa, and a water vapor transmission rate of 10 g / m 2 / day or less, further 8 g. / M 2 / day or less is preferable.
If the elastic modulus of the polyolefin film (A ′) is too low, the outer bag obtained after lamination becomes too flexible, and the shape retention is reduced in the subsequent heat insulating material filling operation and vacuum degassing and sealing process, resulting in increased productivity. descend. If the elastic modulus is too high, the flexibility of the outer bag is lost too much, which is inappropriate for vacuum degassing. In addition, if the water vapor permeability is too high, excess water vapor is taken into the laminate, which in turn lowers the water vapor permeability of the polyvinyl alcohol film, leading to a reduction in the water vapor permeability of the entire laminate, and a vacuum heat insulating structure After constructing the body, water vapor enters the interior and significantly reduces performance.
なお、上記初期弾性率は、ＪＩＳ Ｋ ７１２７に則して測定された２３℃×６０％ｒ．ｈ．での値であり、水蒸気透過度は、ＪＩＳ Ｚ ０２０８に則して測定された２３℃×Δ９０％ｒ．ｈ．での値である。 The initial elastic modulus is 23 ° C. × 60% r.D. measured in accordance with JIS K 7127. h. The water vapor permeability is 23 ° C. × Δ90% r.s measured according to JIS Z 0208. h. The value at.
ポリオレフィン系フィルム（Ａ’）の厚みと初期弾性率に関しては、厚みを換えることで初期弾性率を調整できる関係にあり、最適な弾性率に調整されたポリオレフィン系フィルム（Ａ’）を含む積層体は、外装袋とした際に、芯材である断熱性材料に対する優れた充填性と、本発明の目的である耐屈曲性とを両立させることができるのである。 Regarding the thickness of the polyolefin film (A ′) and the initial elastic modulus, the initial elastic modulus can be adjusted by changing the thickness, and the laminate includes the polyolefin film (A ′) adjusted to the optimum elastic modulus. When it is used as an exterior bag, it is possible to achieve both excellent filling properties with respect to a heat insulating material as a core material and bending resistance, which is an object of the present invention.
本発明で用いるポリオレフィン系フィルム（Ａ’）の製造方法に関しては、特に限定されず、例えば、ポリオレフィン系樹脂組成物を押出機で溶融した後、Ｔダイよりシート状に押出し、冷却ロールで冷却固化し、未延伸シートを製造する方法などが挙げられる。 The method for producing the polyolefin film (A ′) used in the present invention is not particularly limited. For example, after the polyolefin resin composition is melted with an extruder, it is extruded into a sheet form from a T-die and cooled and solidified with a cooling roll. And a method for producing an unstretched sheet.
かくして得られるポリオレフィン系フィルム（Ａ’）に関しては、このまま用いても良いが、延伸処理を施し、一軸延伸或いは二軸延伸ポリオレフィン系フィルムとして用いることが好ましく、特には、より薄膜でより高いガスバリア性を得るという点から、二軸延伸ポリオレフィン系フィルムが好ましく用いられる。 The polyolefin film (A ′) thus obtained may be used as it is, but it is preferably subjected to stretching treatment and used as a uniaxially stretched or biaxially stretched polyolefin film. From the viewpoint of obtaining a biaxially stretched polyolefin-based film is preferably used.
かかる二軸延伸ポリオレフィン系フィルムの製造方法に関しては、公知の方法を用いることができる。延伸倍率に関しては、縦方向に１．５〜６倍延伸することが好ましく、横方向に１．５〜１０倍延伸することが好ましい。また、縦方向と横方向の延伸は同時に行なってもよいし、別々に行なってもよく、別々に行なう場合には、縦延伸は温度１１０〜１３０℃で行なうことが好ましく、横延伸は温度１５０〜１６５℃で行なうことが好ましい。 A known method can be used as a method for producing such a biaxially stretched polyolefin film. Regarding the stretching ratio, it is preferable to stretch 1.5 to 6 times in the longitudinal direction, and preferably 1.5 to 10 times in the transverse direction. In addition, the stretching in the machine direction and the transverse direction may be performed simultaneously or separately, and when performed separately, the longitudinal stretching is preferably performed at a temperature of 110 to 130 ° C., and the transverse stretching is performed at a temperature of 150. It is preferable to carry out at ˜165 ° C.
なお、二軸延伸方法としては、テンター同時二軸延伸法、ロールとテンターによる逐次二軸延伸法のいずれでもよい。また、チューブラー法で二軸延伸フィルムを製造してもよい。 The biaxial stretching method may be either a tenter simultaneous biaxial stretching method or a sequential biaxial stretching method using a roll and a tenter. Moreover, you may manufacture a biaxially stretched film with a tubular method.
また、上記ポリオレフィン系フィルム（Ａ’）には、必要に応じて、コロナ放電処理、表面硬化処理、メッキ処理、着色処理、あるいは各種のコーティング処理による表面処理を付与することができる。 Further, the polyolefin film (A ′) can be subjected to surface treatment by corona discharge treatment, surface hardening treatment, plating treatment, coloring treatment, or various coating treatments, if necessary.
かくして得られるポリオレフィン系フィルム（Ａ’）に、金属或いは金属酸化物を蒸着することにより、金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）を得ることができる。 By depositing a metal or metal oxide on the polyolefin film (A ′) thus obtained, a polyolefin film (A) on which the metal or metal oxide is deposited can be obtained.
かかる金属或いは金属酸化物としては、特に限定されることなく、例えば、アルミニウム、金、銀、銅、ニッケル、コバルト、クロム、スズなどの金属、或いはかかる金属の酸化物を用いることができる。それらのなかでも、アルミニウム、金、銀、スズが好ましく用いられ、特にアルミニウムが、コストの面から好ましく用いられる。 Such a metal or metal oxide is not particularly limited, and for example, a metal such as aluminum, gold, silver, copper, nickel, cobalt, chromium, tin, or an oxide of such a metal can be used. Among these, aluminum, gold, silver, and tin are preferably used, and aluminum is particularly preferably used from the viewpoint of cost.
かかる金属或いは金属酸化物が蒸着されて形成される蒸着層の厚みは、特に限定されるものではなく、好ましくは２００〜１０００Å、特に好ましくは３００〜８００Åである。蒸着層の厚みが薄すぎると、熱放射特性が得られにくい傾向があり、厚すぎるとその厚みを得るための蒸着時間が長すぎて、蒸着時の熱的な影響が大きくなりすぎる傾向があり、工業的に好ましくない。
また、上記蒸着層は、一度の蒸着処理で得られたものであってもよいし、複数回にわたり蒸着処理を繰り返して得られたものであってもよい。
The thickness of the vapor deposition layer formed by vapor deposition of such a metal or metal oxide is not particularly limited, and is preferably 200 to 1000 mm, particularly preferably 300 to 800 mm. If the thickness of the deposited layer is too thin, thermal radiation characteristics tend to be difficult to obtain, and if too thick, the deposition time for obtaining the thickness is too long, and the thermal influence during deposition tends to be too great. Industrially unfavorable.
Moreover, the said vapor deposition layer may be obtained by one vapor deposition process, and may be obtained by repeating vapor deposition process in multiple times.
かかる金属或いは金属酸化物の蒸着方法としては、例えば、スパッタリング法、イオンプレーティング法、抵抗加熱蒸着法、高周波誘導加熱蒸着法、電子ビーム加熱蒸着法などの一般的な真空蒸着法を用いることができる。 As a deposition method of such metal or metal oxide, for example, a general vacuum deposition method such as a sputtering method, an ion plating method, a resistance heating deposition method, a high-frequency induction heating deposition method, or an electron beam heating deposition method is used. it can.
また、ポリオレフィン系フィルム（Ａ’）に蒸着処理を施す前に、基材フィルムの表面に前処理をすることも可能であり、かかる前処理としては、例えば、コロナ処理等の基材そのものの活性化を促す方法と、ポリエチレンやポリエーテルを主剤としウレタン系硬化剤を用いるようなコーティング剤で薄膜層を形成する方法等を挙げることができる。 Moreover, it is also possible to pre-treat the surface of the base film before subjecting the polyolefin-based film (A ′) to the vapor deposition treatment. As such pre-treatment, for example, the activity of the base material itself such as corona treatment can be used. And a method of forming a thin film layer with a coating agent such as polyethylene or polyether as a main ingredient and a urethane-based curing agent.
次に、本発明で用いられる金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）に関して、まず、蒸着処理を施す前のガスバリア性フィルム（ガスバリア性フィルム（Ｂ’）とする）について説明する。 Next, regarding the gas barrier film (B) on which the metal or metal oxide used in the present invention is deposited, first, a gas barrier film (denoted as a gas barrier film (B ′)) before being subjected to the vapor deposition treatment will be described. .
本発明で用いられるガスバリア性フィルム（Ｂ’）は、ガスバリア性を有するフィルムであればよく、通常、かかるガスバリア性フィルムの中でも、２３℃−５０％ＲＨの条件でＪＩＳ Ｋ ７１２６（等圧法）に記載の方法に準じて測定した際の酸素透過量が、１ｍｌ／（ｍ2・ｄａｙ・ａｔｍ）以下（好ましくは、０．１ｍｌ／（ｍ2・ｄａｙ・ａｔｍ）以下）のフィルムを用いることが好ましい。具体的には、ビニルアルコール系フィルムであることが高いガスバリア性を得るという点で特に好ましい。 The gas barrier film (B ′) used in the present invention may be a film having a gas barrier property, and usually, among such gas barrier films, it is JIS K 7126 (isobaric method) under the condition of 23 ° C.-50% RH. It is preferable to use a film having an oxygen transmission amount of 1 ml / (m 2 · day · atm) or less (preferably 0.1 ml / (m 2 · day · atm) or less) when measured according to the described method. preferable. Specifically, a vinyl alcohol film is particularly preferable in terms of obtaining high gas barrier properties.
かかるビニルアルコール系フィルムは、ビニルアルコール系樹脂より製膜されてなるものであり、ビニルアルコール系樹脂とは、ビニルエステル単位がケン化されてなるビニルアルコール単位を有するものであればよく、ビニルアルコール系樹脂としては、例えば、ポリビニルアルコール系樹脂（以下、ＰＶＡ系樹脂と略記することがある）や、エチレン−ビニルアルコール系共重合体（以下、ＥＶＯＨと略記することがある）を挙げることができる。更に、ＰＶＡ系樹脂としては、酢酸ビニルを単独重合し、それをケン化したＰＶＡと、変性ＰＶＡを挙げることができ、かかる変性ＰＶＡとしては、共重合変性品と後変性品とを挙げることができる。 Such a vinyl alcohol film is formed from a vinyl alcohol resin, and the vinyl alcohol resin may have any vinyl alcohol unit obtained by saponifying a vinyl ester unit. Examples of the resin include a polyvinyl alcohol resin (hereinafter sometimes abbreviated as PVA resin) and an ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH). . Furthermore, examples of the PVA resin include PVA obtained by homopolymerizing vinyl acetate and saponification thereof, and modified PVA. Examples of such modified PVA include copolymer modified products and post-modified products. it can.
ビニルアルコール系フィルムとしては、公知のＰＶＡ系樹脂又はＥＶＯＨ樹脂を含むフィルムを用いることができるが、これら樹脂について簡単に説明する。 As the vinyl alcohol film, a film containing a known PVA resin or EVOH resin can be used. These resins will be briefly described.
ＰＶＡ系樹脂としては、上記の通りＰＶＡや変性ＰＶＡが挙げられ、ＰＶＡは、酢酸ビニルを単独重合し、更にそれをケン化して製造される。また変性ＰＶＡは、酢酸ビニルと酢酸ビニルと共重合可能な不飽和単量体を共重合させた後ケン化して製造されるものであり、その変性量としては通常１０モル％未満である。 Examples of the PVA resin include PVA and modified PVA as described above, and PVA is produced by homopolymerizing vinyl acetate and further saponifying it. The modified PVA is produced by copolymerizing an unsaturated monomer copolymerizable with vinyl acetate and vinyl acetate and then saponifying, and the amount of modification is usually less than 10 mol%.
上記酢酸ビニルと共重合可能な不飽和単量体としては、例えばエチレンやプロピレン、イソブチレン、α−オクテン、α−ドデセン、α−オクタデセン等のオレフィン類、３−ブテン−１−オール、４−ペンテン−１−オール、５−ヘキセン−１−オール等のヒドロキシ基含有α−オレフィン類およびそのアシル化物などの誘導体、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸、ウンデシレン酸等の不飽和酸類、その塩、モノエステル、あるいはジアルキルエステル、アクリロニトリル、メタアクリロニトリル等のニトリル類、ジアセトンアクリルアミド、アクリルアミド、メタクリルアミド等のアミド類、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸類あるいはその塩、アルキルビニルエーテル類、ジメチルアリルビニルケトン、Ｎ−ビニルピロリドン、塩化ビニル、ビニルエチレンカーボネート、２，２−ジアルキル−４−ビニル−１，３−ジオキソラン、グリセリンモノアリルエーテル、３，４−ジアセトキシ−１−ブテン、等のビニル化合物、酢酸イソプロペニル、１−メトキシビニルアセテート等の置換酢酸ビニル類、塩化ビニリデン、１，４−ジアセトキシ−２−ブテン、ビニレンカーボネート、等が挙げられる。 Examples of the unsaturated monomer copolymerizable with vinyl acetate include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, 3-buten-1-ol, and 4-pentene. Derivatives such as hydroxy group-containing α-olefins such as -1-ol and 5-hexen-1-ol and acylated products thereof, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, undecylenic acid Unsaturated acids such as salts, monoesters or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as diacetone acrylamide, acrylamide and methacrylamide, ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid Olefin sulfonic acids such as Or salts thereof, alkyl vinyl ethers, dimethylallyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2,2-dialkyl-4-vinyl-1,3-dioxolane, glycerol monoallyl ether, 3,4 -Vinyl compounds such as diacetoxy-1-butene, substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinyl acetate, vinylidene chloride, 1,4-diacetoxy-2-butene, and vinylene carbonate.
また、変性ＰＶＡとしては、ＰＶＡを後変性することにより製造することもできる。かかる後変性の方法としては、ＰＶＡをアセト酢酸エステル化、アセタール化、ウレタン化、エーテル化、グラフト化、リン酸エステル化、オキシアルキレン化する方法等が挙げられる。 Moreover, as modified PVA, it can also manufacture by post-modifying PVA. Examples of such post-modification methods include a method of converting PVA into acetoacetate ester, acetalization, urethanization, etherification, grafting, phosphoric esterification, and oxyalkylene.
本発明においては、上記ＰＶＡ系樹脂の重合度が１１００以上、平均ケン化度９０モル％以上であることが好ましく、重合度の更に好ましい範囲は１１００〜４０００、特に好ましい範囲は１２００〜２６００である。かかる重合度が低すぎると得られるフィルムとしたときの機械強度が低下する傾向にある。なお、重合度が高すぎると製膜および延伸時の加工性が低下する傾向にある。平均ケン化度の更に好ましい範囲は９５〜１００モル％、特に好ましい範囲は９９〜１００モル％である。かかる平均ケン化度が低すぎると耐水性が低下し、ガスバリア性の湿度による変化が著しくなる傾向にあるので、比較的高いものを選ぶことが好ましい。 In the present invention, the polymerization degree of the PVA resin is preferably 1100 or more and the average saponification degree is 90 mol% or more, and the more preferable range of the polymerization degree is 1100 to 4000, and the particularly preferable range is 1200 to 2600. . If the degree of polymerization is too low, the mechanical strength of the resulting film tends to decrease. If the degree of polymerization is too high, the processability during film formation and stretching tends to decrease. A more preferable range of the average saponification degree is 95 to 100 mol%, and a particularly preferable range is 99 to 100 mol%. If the average degree of saponification is too low, the water resistance is lowered, and the change of the gas barrier property due to humidity tends to be remarkable. Therefore, it is preferable to select a relatively high saponification degree.
また、上記ＰＶＡ系樹脂の２０℃における４重量％水溶液の粘度としては、２．５〜１００ｍＰａ・ｓが好ましく、更には２．５〜７０ｍＰａ・ｓ、特には２．５〜６０ｍＰａ・ｓが好ましい。該粘度が低すぎるとフィルム強度等の機械的物性が劣る傾向があり、高すぎるとフィルムへの製膜性が悪くなる傾向がある。
尚、上記粘度はＪＩＳ Ｋ６７２６に準じて測定されるものである。
Further, the viscosity of the 4 wt% aqueous solution of the PVA resin at 20 ° C. is preferably 2.5 to 100 mPa · s, more preferably 2.5 to 70 mPa · s, and particularly preferably 2.5 to 60 mPa · s. . If the viscosity is too low, mechanical properties such as film strength tend to be inferior, and if it is too high, film-forming properties on the film tend to be poor.
The viscosity is measured according to JIS K6726.
次に、ＥＶＯＨ樹脂としては、通常１０〜６０モル％のエチレンとビニルエステルとの共重合体をケン化して得られるものであり、かかるビニルエステルとしては酢酸ビニルが代表的なものとして挙げられるが、その他の脂肪酸ビニルエステル（プロピオン酸ビニル、ピバリン酸ビニルなど）も使用できる。また、ＥＶＯＨ樹脂には、加熱溶融時の安定性向上のために共重合成分としてビニルシラン化合物を０．０００２〜０．２モル％含有させることもできる。ここで、ビニルシラン系化合物としては、たとえば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリ（β−メトキシ−エトキシ）シラン、γ−メタクリルオキシプロピルメトキシシランが挙げられる。なかでも、ビニルトリメトキシシラン、ビニルトリエトキシシランが好適に用いられる。さらに、本発明の目的が阻害されない範囲で、他の共重合性単量体、例えば、プロピレン、ブチレン；（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチルなどの不飽和カルボン酸またはそのエステル；Ｎ−ビニルピロリドンなどのビニルピロリドン等を共重合することもできる。 Next, the EVOH resin is usually obtained by saponifying a copolymer of 10 to 60 mol% ethylene and vinyl ester, and vinyl acetate is a typical example of such vinyl ester. Other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used. In addition, the EVOH resin may contain 0.0002 to 0.2 mol% of a vinylsilane compound as a copolymerization component in order to improve the stability at the time of heating and melting. Here, examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloxypropylmethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used. Further, other copolymerizable monomers such as propylene, butylene; unsaturated (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, etc., as long as the object of the present invention is not inhibited. Carboxylic acid or an ester thereof; vinyl pyrrolidone such as N-vinyl pyrrolidone can be copolymerized.
ＥＶＯＨ樹脂のエチレン含有量は１０〜６０モル％であるが、良好な延伸性を得る観点からは、エチレン含有量は１５モル％以上、さらには２５モル％以上であるものが特に好ましい。また、ガスバリア性の観点からは、エチレン含有量は５５モル％以下、さらには５０モル％以下であるものが特に好ましい。エチレン含有量が少なすぎると溶融成形性が悪化する傾向があり、多すぎるとガスバリア性が不足する傾向がある。
なお、かかるＥＶＯＨ樹脂のエチレン含有量は、核磁気共鳴（ＮＭＲ）法により求めることができる。
The ethylene content of the EVOH resin is 10 to 60 mol%, but from the viewpoint of obtaining good stretchability, the ethylene content is particularly preferably 15 mol% or more, and more preferably 25 mol% or more. From the viewpoint of gas barrier properties, those having an ethylene content of 55 mol% or less, more preferably 50 mol% or less are particularly preferred. If the ethylene content is too low, the melt moldability tends to deteriorate, and if it is too high, the gas barrier property tends to be insufficient.
In addition, the ethylene content of the EVOH resin can be obtained by a nuclear magnetic resonance (NMR) method.
また、かかるＥＶＯＨ樹脂のケン化度は、好適には９０％以上であり、より好適には９５％以上であり、更に好適には９９％以上である。ケン化度が低すぎると、高湿度下でのガスバリア性が低下する傾向がある。
なお、ここで、ＥＶＯＨ樹脂が、ケン化度の異なる２種類以上のＥＶＯＨ樹脂の配合物を含む場合には、配合重量比から算出される平均値をケン化度とする。
Further, the saponification degree of such EVOH resin is preferably 90% or more, more preferably 95% or more, and further preferably 99% or more. If the degree of saponification is too low, the gas barrier property under high humidity tends to decrease.
Here, when the EVOH resin contains a blend of two or more types of EVOH resins having different saponification degrees, the average value calculated from the blending weight ratio is defined as the saponification degree.
さらに、本発明の目的を阻外しない範囲内で加熱溶融時の安定性を向上させるためにＥＶＯＨ樹脂にホウ素化合物をブレンドすることもできる。ここでホウ素化合物としては、ホウ酸類、ホウ酸エステル、ホウ酸塩、水素化ホウ素類等が挙げられる。具体的には、ホウ酸類としては、オルトホウ酸、メタホウ酸、四ホウ酸などが挙げられ、ホウ酸エステルとしてはホウ酸トリエチル、ホウ酸トリメチルなどが挙げられ、ホウ酸塩としては上記の各種ホウ酸類のアルカリ金属塩、アルカリ土類金属塩、ホウ砂などが挙げられる。これらの化合物のうちでもオルトホウ酸（以下、単にホウ酸と表示する場合がある）であることが好ましい。 Furthermore, a boron compound can be blended with the EVOH resin in order to improve the stability at the time of heating and melting within a range that does not obstruct the object of the present invention. Examples of the boron compound include boric acids, boric acid esters, borates, borohydrides, and the like. Specific examples of boric acids include orthoboric acid, metaboric acid, and tetraboric acid. Examples of boric acid esters include triethyl borate and trimethyl borate. Examples include alkali metal salts of acids, alkaline earth metal salts, and borax. Among these compounds, orthoboric acid (hereinafter sometimes simply referred to as boric acid) is preferable.
ＥＶＯＨ樹脂にホウ素化合物をブレンドする場合、ホウ素化合物の含有量は、好ましくはホウ素元素換算で２０〜２０００ｐｐｍ、より好ましくは５０〜１０００ｐｐｍである。この範囲内でホウ素化合物をブレンドすることで加熱溶融時のトルク変動が抑制されたＥＶＯＨ樹脂を得ることができる。ホウ素化合物の含有量が少なすぎると添加効果が小さく、多すぎるとゲル化しやすく、成形性不良となる場合がある。 When a boron compound is blended with the EVOH resin, the content of the boron compound is preferably 20 to 2000 ppm, more preferably 50 to 1000 ppm in terms of boron element. By blending the boron compound within this range, it is possible to obtain an EVOH resin in which torque fluctuation during heating and melting is suppressed. If the content of the boron compound is too small, the effect of addition is small, and if it is too large, gelation tends to occur and the moldability may be poor.
かかるＥＶＯＨ樹脂の２３０℃、２１６０ｇ荷重下における好適なメルトフローレート（ＭＦＲ）は、通常１〜５０ｇ／１０分であり、より好適には３〜４０ｇ／１０分、更に好適には５〜３０ｇ／１０分である。これらのＥＶＯＨは、それぞれ単独で用いることもできるし、２種以上を混合して用いることもできる。 The suitable melt flow rate (MFR) of the EVOH resin at 230 ° C. under a load of 2160 g is usually 1 to 50 g / 10 min, more preferably 3 to 40 g / 10 min, and further preferably 5 to 30 g / min. 10 minutes. These EVOHs can be used alone or in combination of two or more.
本発明では、上記ビニルアルコール系樹脂を用いてフィルム製膜するのであるが、かかる製膜方法も公知のものでよく、特に限定されず、例えば、ドラム、エンドレスベルト等の金属面上にビニルアルコール系樹脂溶液を流延してフィルム形成する流延式成形法、あるいは押出機により溶融押出する溶融成形法によって製膜される。 In the present invention, a film is formed using the above vinyl alcohol resin, but such a film forming method may be a known one, and is not particularly limited. For example, vinyl alcohol is formed on a metal surface such as a drum or an endless belt. The film is formed by a cast molding method in which a film is formed by casting a resin resin solution, or by a melt molding method in which the resin solution is melt extruded by an extruder.
かかるビニルアルコール系フィルムは、無延伸フィルムとして用いてもよいが、通常一軸延伸或いは二軸延伸フィルムとして用いることが好ましく、特にガスバリア性の点から、二軸延伸フィルムとして用いるのが好ましい。かかる一軸および二軸延伸フィルムの流れ方向（ＭＤ方向）の延伸倍率としては２．５〜５倍であることが好ましい。 Such a vinyl alcohol film may be used as a non-stretched film, but is usually preferably used as a uniaxially stretched film or a biaxially stretched film, and is particularly preferably used as a biaxially stretched film from the viewpoint of gas barrier properties. The stretching ratio in the flow direction (MD direction) of the uniaxially or biaxially stretched film is preferably 2.5 to 5 times.
かかる延伸処理方法は、通常行われる一軸延伸方法や、同時二軸延伸、逐次二軸延伸など、公知方法に従い行うことが可能である。 Such a stretching treatment method can be performed according to a known method such as a uniaxial stretching method that is usually performed, simultaneous biaxial stretching, and sequential biaxial stretching.
本発明においては、かかる二軸延伸ビニルアルコール系フィルムの中でも、二軸延伸ＰＶＡ系フィルム、二軸延伸ＥＶＯＨ系フィルムが、特に好ましく用いられるが、これら二軸延伸フィルムの具体的な製法について説明する。 In the present invention, among these biaxially stretched vinyl alcohol-based films, biaxially stretched PVA-based films and biaxially stretched EVOH-based films are particularly preferably used. A specific method for producing these biaxially stretched films will be described. .
まず、二軸延伸ＰＶＡ系フィルムについて説明する。 First, the biaxially stretched PVA film will be described.
上記ＰＶＡ系樹脂を用いて、ＰＶＡ系フィルム（延伸前ＰＶＡ系フィルム）を製膜するわけであるが、通常は、製膜用の原液として、ＰＶＡ系樹脂濃度が５〜７０重量％、好ましくは１０〜６０重量％のＰＶＡ系樹脂−水の組成物を調製する。 A PVA-based film (PVA-based film before stretching) is formed using the PVA-based resin. Usually, a PVA-based resin concentration is 5 to 70% by weight, preferably as a stock solution for film formation. A composition of 10 to 60% by weight of PVA resin-water is prepared.
かかるＰＶＡ系樹脂−水の組成物には、本発明の効果を損なわない範囲でエチレングリコール、グリセリン、ポリエチレングリコール、ジエチレングリコール、トリエチレングリコール等の多価アルコール類の可塑剤やフェノール系、アミン系等の抗酸化剤、リン酸エステル類等の安定剤、着色料、香料、増量剤、消包剤、剥離剤、紫外線吸収剤、無機粉体、界面活性剤等の通常の添加剤を適宜配合しても差し支えない。また、澱粉、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース等のＰＶＡ系樹脂以外の他の水溶性樹脂を混合してもよい。 In such a PVA resin-water composition, a plasticizer of polyhydric alcohols such as ethylene glycol, glycerin, polyethylene glycol, diethylene glycol, and triethylene glycol, phenolic, amine-based, etc., as long as the effects of the present invention are not impaired. Regular additives such as antioxidants, stabilizers such as phosphate esters, colorants, fragrances, extenders, defoamers, release agents, UV absorbers, inorganic powders, surfactants, etc. There is no problem. Moreover, you may mix other water-soluble resins other than PVA-type resin, such as starch, carboxymethylcellulose, methylcellulose, and hydroxymethylcellulose.
ＰＶＡ系フィルムの製膜法については、特に限定されないが、上記ＰＶＡ系樹脂−水の組成物を押出機に供給して溶融混練した後、Ｔダイ法、インフレーション法により押出し製膜し、乾燥する方法が好ましい。 The method for forming the PVA film is not particularly limited, but the PVA resin-water composition is supplied to an extruder and melt-kneaded, and then extruded and formed by the T-die method and the inflation method, followed by drying. The method is preferred.
かかる方法における押出機内での溶融混練温度は、５５〜１６０℃が好ましい。かかる温度が低すぎるとフィルム肌の不良を招き、高すぎると発泡現象を招く傾向にある。また、製膜後のフィルムの乾燥については、７０〜１２０℃で行なうことが好ましく、更には８０〜１００℃で行なうことが好ましい。 The melt kneading temperature in the extruder in such a method is preferably 55 to 160 ° C. If the temperature is too low, the film skin will be defective, and if it is too high, the foaming phenomenon tends to occur. Moreover, about the drying of the film after film forming, it is preferable to carry out at 70-120 degreeC, and also it is preferable to carry out at 80-100 degreeC.
上記で得られたＰＶＡ系フィルムに対して、更に二軸延伸を施すことにより、本発明で好ましく用いられる二軸延伸ＰＶＡ系フィルムとなる。
かかる二軸延伸については、機械の流れ方向（ＭＤ方向）の延伸倍率が２．５〜５倍、幅方向（ＴＤ方向）の延伸倍率が２〜４．５倍であることが好ましく、特に好ましくはＭＤ方向の延伸倍率が３〜５倍、ＴＤ方向の延伸倍率が２．５〜４．５倍である。該ＭＤ方向の延伸倍率が低すぎると延伸による物性向上が得難くかつ耐熱性が損なわれる傾向があり、高すぎるとフィルムがＭＤ方向へ裂けやすくなる傾向がある。また、ＴＤ方向の延伸倍率が低すぎると延伸による物性向上が得難く、かつ耐熱性が損なわれる傾向があり、高すぎると工業的にフィルムを製造する際に延伸時の破断が多発する傾向がある。
The biaxially stretched PVA film preferably used in the present invention is obtained by further biaxially stretching the PVA film obtained above.
For such biaxial stretching, the stretching ratio in the machine flow direction (MD direction) is preferably 2.5 to 5 times, and the stretching ratio in the width direction (TD direction) is preferably 2 to 4.5 times, particularly preferably. The MD has a stretching ratio of 3 to 5 times, and the TD direction has a stretching ratio of 2.5 to 4.5 times. If the draw ratio in the MD direction is too low, it is difficult to improve physical properties due to stretching and the heat resistance tends to be impaired. If it is too high, the film tends to tear in the MD direction. Further, if the stretching ratio in the TD direction is too low, it is difficult to obtain physical properties by stretching, and the heat resistance tends to be impaired. If it is too high, breakage during stretching tends to occur frequently when the film is industrially produced. is there.
二軸延伸としては、逐次二軸延伸、同時二軸延伸などが挙げられ、かかる逐次二軸延伸あるいは同時二軸延伸を行なうにあたっては、ＰＶＡ系フィルムの含水率を５〜３０重量％、特には２０〜３０重量％に調整しておくことが好ましい。含水率の調整は、乾燥前のＰＶＡ系フィルムを引き続き乾燥する方法、含水率５重量％未満のＰＶＡ系フィルムを水に浸漬あるいは調湿等を施す方法等により行なうことができる。かかる含水率が低すぎても、高すぎても延伸工程でＭＤ方向、ＴＤ方向の延伸倍率を高めることができない傾向がある。 Examples of the biaxial stretching include sequential biaxial stretching and simultaneous biaxial stretching. In performing the sequential biaxial stretching or simultaneous biaxial stretching, the water content of the PVA film is 5 to 30% by weight, particularly It is preferable to adjust to 20 to 30% by weight. The moisture content can be adjusted by a method in which the PVA film before drying is subsequently dried, a method in which a PVA film having a moisture content of less than 5% by weight is immersed in water or is conditioned. Even if the moisture content is too low or too high, there is a tendency that the stretching ratio in the MD direction and the TD direction cannot be increased in the stretching process.
更に、二軸延伸を施した後は、熱固定を行うことが好ましく、かかる熱固定の温度は、ＰＶＡ系樹脂の融点より低い温度を選択することが好ましく、特には１４０〜２５０℃であることが好ましい。熱固定温度が、融点より８０℃以上低い温度の場合は、寸法安定性が悪く収縮率が大きくなる傾向があり、一方、融点より高い場合は、フィルムの厚み変動が大きくなる傾向がある。また、熱固定時間は１〜３０秒間であることが好ましく、より好ましくは５〜１０秒間である。 Furthermore, after performing biaxial stretching, it is preferable to perform heat setting, and the temperature of such heat setting is preferably selected to be lower than the melting point of the PVA-based resin, particularly 140 to 250 ° C. Is preferred. When the heat setting temperature is lower than the melting point by 80 ° C. or more, the dimensional stability tends to be poor and the shrinkage rate tends to be large. On the other hand, when the temperature is higher than the melting point, the thickness variation of the film tends to be large. The heat setting time is preferably 1 to 30 seconds, and more preferably 5 to 10 seconds.
また、必要に応じて、熱変形性をさらに減少させる目的で、かかる二軸延伸ＰＶＡ系フィルムに、水溶液への接触および乾燥の加工を施すことも可能である。水溶液との接触においては、通常５〜６０℃、好ましくは１０〜５０℃の水溶液が用いられ、水溶液との接触時間は、水溶液の温度に応じて適宜選択されるが、工業的には１０〜６０秒であることが好ましい。 In addition, for the purpose of further reducing the heat deformability, it is possible to subject the biaxially stretched PVA-based film to contact with an aqueous solution and to drying as necessary. In the contact with the aqueous solution, an aqueous solution of usually 5 to 60 ° C., preferably 10 to 50 ° C. is used, and the contact time with the aqueous solution is appropriately selected according to the temperature of the aqueous solution, but industrially 10 to 10 ° C. Preferably it is 60 seconds.
かかる水溶液との接触方法については、特に限定されないが、例えば、水溶液への浸漬や水溶液の噴霧、水溶液の塗布、スチーム処理などが挙げられ、これらを併用することもできる。
なお、水溶液とは、水溶性の物質が常識の範囲で溶解した水を主成分とする溶液のことであり、水も含む意味である。
The contact method with such an aqueous solution is not particularly limited, and examples thereof include immersion in an aqueous solution, spraying of an aqueous solution, application of an aqueous solution, steam treatment, and the like, and these can be used in combination.
The aqueous solution is a solution containing water as a main component in which a water-soluble substance is dissolved within a range of common sense, and includes water.
水溶液との接触の後、工業的には、エアーシャワー等で非接触的に表面の付着水を取り除き、次いでニップロール等で接触的な水分除去を行うことが好ましい。また、乾燥機の種類としては、特に限定されないが、例えば、金属ロールやセラミックロール等に直接接触して乾燥する方法、あるいは非接触型の乾燥機を用いる方法などが挙げられる。 After contact with the aqueous solution, industrially, it is preferable to remove the adhering water on the surface in a non-contact manner using an air shower or the like, and then to remove the contact water using a nip roll or the like. Further, the type of the dryer is not particularly limited, and examples thereof include a method of directly contacting a metal roll, a ceramic roll or the like for drying, or a method using a non-contact type dryer.
かかる水溶液との接触と乾燥の後に、得られた二軸延伸ＰＶＡ系フィルムを再度巻き取ってロール状とする場合は、フィルムの水分量を通常３重量％以下、好ましくは０．１〜２重量％にすることが望まれる。かかる水分量が多すぎるとフィルムロールの中でフィルム同士が密着してしまう傾向があり、再度加工のための巻き出しを行う際にフィルムが破損するなどの問題を発生するおそれがある。
かくして本発明で好適に用いられる二軸延伸ＰＶＡ系フィルムが得られる。
When the obtained biaxially stretched PVA-based film is wound up again after the contact with the aqueous solution and drying, the water content of the film is usually 3% by weight or less, preferably 0.1 to 2% by weight. % Is desired. If the amount of moisture is too large, the films tend to adhere to each other in the film roll, and there is a risk of problems such as damage to the film when unwinding for processing again.
Thus, a biaxially stretched PVA film suitably used in the present invention is obtained.
次に、二軸延伸ＥＶＯＨ系フィルムについて説明する。
上記ＥＶＯＨ樹脂を用いて、ＥＶＯＨ系フィルム（延伸前ＥＶＯＨ系フィルム）を製膜するわけである。
Next, the biaxially stretched EVOH film will be described.
An EVOH film (an EVOH film before stretching) is formed using the EVOH resin.
かかるＥＶＯＨ樹脂には、本発明の目的を阻外しない範囲内で、酸化防止剤、色剤、紫外線吸収剤、スリップ剤、帯電防止剤、可塑剤、硼酸等の架橋剤、無機充填剤、無機乾燥剤等の各種添加剤、ポリアミド、ポリオレフィン、高吸水性樹脂等の各種樹脂を配合してもよい。 Such EVOH resins include antioxidants, colorants, ultraviolet absorbers, slip agents, antistatic agents, plasticizers, cross-linking agents such as boric acid, inorganic fillers, inorganic fillers, and the like within the scope of the present invention. You may mix | blend various resins, such as various additives, such as a desiccant, polyamide, polyolefin, and a super absorbent polymer.
上記ＥＶＯＨ樹脂を用いて、ＥＶＯＨ系フィルムを製膜する際には、主に溶融成形が用いられる。以下に溶融成形方法について説明する。
かかる溶融成形時の条件としては、特に限定されないが、通常はノンベント、スクリュータイプ押出機を用い、溶融温度１９０〜２５０℃で押出製膜される。通常、圧縮比２．０〜４．５のスクリューを用い、Ｔダイス、または丸ダイスを用いて製膜される。
When forming an EVOH film using the EVOH resin, melt molding is mainly used. The melt molding method will be described below.
The conditions at the time of melt molding are not particularly limited, but are usually formed by extrusion using a non-vented, screw-type extruder at a melting temperature of 190 to 250 ° C. Usually, a screw having a compression ratio of 2.0 to 4.5 is used to form a film using a T die or a round die.
かくしてＥＶＯＨ系フィルムが得られるわけであるが、該ＥＶＯＨ系フィルムに対しては、更に、二軸延伸、好ましくは逐次二軸延伸を施すことにより、二軸延伸ＥＶＯＨ系フィルムとすることができる。 Thus, an EVOH film can be obtained. The EVOH film can be further biaxially stretched, preferably sequentially biaxially stretched to obtain a biaxially stretched EVOH film.
かかる二軸延伸の面積倍率については、好ましくは３倍以上、より好ましくは６倍以上、特に好ましくは９倍以上であることが、ガスバリア性および機械強度の観点から重要である。延伸する方法としては、ダブルバブル法、テンター法、ロール法等の一軸または二軸延伸する方法等公知の延伸方法を採用することができ、二軸延伸の場合は、同時延伸、逐次延伸のいずれの方式も採用できる。 The area ratio of such biaxial stretching is preferably 3 times or more, more preferably 6 times or more, and particularly preferably 9 times or more from the viewpoint of gas barrier properties and mechanical strength. As a stretching method, a known stretching method such as a uniaxial or biaxial stretching method such as a double bubble method, a tenter method, a roll method, etc. can be adopted. In the case of biaxial stretching, either simultaneous stretching or sequential stretching can be used. This method can also be adopted.
また、延伸前の原反フィルムに予め含水させておくことで容易な連続延伸が可能となり、延伸前の原反フィルムの水分率としては、２〜３０重量％が好ましく、特には５〜３０重量％が好ましく、更には１０〜３０重量％が好ましい。水分率が少なすぎると、延伸斑が残りやすく、また特にテンターで延伸する場合、グリップに近い部分の延伸倍率が高くなるために、グリップ近辺での破れが生じやすくなることがある。一方、水分率が高すぎると、延伸された部分の弾性率が低く、未延伸部分との差が十分でなく、延伸斑が残りやすくなることがある。 Moreover, easy continuous stretching is possible by pre-hydrating the original film before stretching, and the moisture content of the original film before stretching is preferably 2 to 30% by weight, particularly 5 to 30% by weight. % Is preferable, and further 10 to 30% by weight is preferable. If the moisture content is too low, stretch spots are likely to remain, and particularly when stretched with a tenter, the stretch ratio in the portion close to the grip becomes high, so that tearing near the grip may easily occur. On the other hand, if the moisture content is too high, the elastic modulus of the stretched portion is low, the difference from the unstretched portion is not sufficient, and stretched spots may remain easily.
かかる延伸温度に関しては、延伸前の原反フィルムの水分率によって多少異なるが、一般に５０〜１３０℃の範囲が適応可能である。特に同時二軸延伸においては、７０〜１００℃の範囲において、厚み斑の少ない二軸延伸ＥＶＯＨ系フィルムが得られやすく、逐次二軸延伸においては、ロールでの長手方向の延伸において７０〜１００℃、テンターでの幅方向の延伸において８０〜１２０℃の温度範囲で行うことにより、厚み斑の少ない二軸延伸ＥＶＯＨ系フィルムが得られやすい。 The stretching temperature varies somewhat depending on the moisture content of the original film before stretching, but a range of 50 to 130 ° C. is generally applicable. Particularly in simultaneous biaxial stretching, a biaxially stretched EVOH-based film with little thickness unevenness is easily obtained in the range of 70 to 100 ° C., and in sequential biaxial stretching, 70 to 100 ° C. in longitudinal stretching with a roll. By performing the stretching in the width direction with a tenter in the temperature range of 80 to 120 ° C., a biaxially stretched EVOH-based film with few thickness spots is easily obtained.
そして、二軸延伸ＥＶＯＨ系フィルムの製造に関するさらに重要な因子としては、延伸後の熱処理と、その熱処理の結果として得られる二軸延伸ＥＶＯＨ系フィルムの密度および水分率がある。熱処理は、ＥＶＯＨ樹脂の融点より５〜４０℃低い温度で、５〜２０秒間行われることが好ましい。熱処理温度が低すぎると、熱処理が不十分なため、蒸着工程に耐えるだけの耐熱性および充分なガスバリア性が得られないことがある。一方、熱処理温度が高すぎると、部分的に延伸効果が低減されることがある。
かくして本発明で好適に用いられる二軸延伸ＥＶＯＨ系フィルムが得られる。
Further, further important factors relating to the production of the biaxially stretched EVOH film include the heat treatment after stretching, and the density and moisture content of the biaxially stretched EVOH film obtained as a result of the heat treatment. The heat treatment is preferably performed at a
Thus, a biaxially stretched EVOH film suitably used in the present invention is obtained.
本発明で用いられるガスバリア性フィルム（Ｂ’）の厚みとしては、通常５〜１００μｍ、好ましくは８〜５０μｍであることが、工業的な生産性の面で有利である。また、二軸延伸ＰＶＡ系フィルムを用いる際のフィルムの厚みは、好ましくは５〜５０μｍ、特に好ましくは８〜３０μｍであり、二軸延伸ＥＶＯＨを用いる際のフィルムの厚みは、好ましくは５〜５０μｍ、特に好ましくは１０〜４０μｍである。 The thickness of the gas barrier film (B ′) used in the present invention is usually 5 to 100 μm, preferably 8 to 50 μm, in terms of industrial productivity. The thickness of the film when using the biaxially stretched PVA film is preferably 5 to 50 μm, particularly preferably 8 to 30 μm, and the thickness of the film when using biaxially stretched EVOH is preferably 5 to 50 μm. Especially preferably, it is 10-40 micrometers.
かくして本発明におけるガスバリア性フィルム（Ｂ’）が得られのであり、かかるガスバリア性フィルム（Ｂ’）に、金属或いは金属酸化物を蒸着することにより、金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）を得ることができる。
ガスバリア性フィルム（Ｂ’）への金属或いは金属酸化物の蒸着処理に関しては、上述したポリオレフィン系フィルム（Ａ’）への蒸着処理に関する記載を参考に、同様の方法により蒸着を行なえばよい。
Thus, the gas barrier film (B ′) in the present invention is obtained, and the gas barrier film in which the metal or metal oxide is deposited by depositing the metal or metal oxide on the gas barrier film (B ′). (B) can be obtained.
With respect to the vapor deposition treatment of the metal or metal oxide on the gas barrier film (B ′), vapor deposition may be carried out by the same method with reference to the description relating to the vapor deposition treatment on the polyolefin film (A ′) described above.
本発明で用いる多層フィルムは、金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）と、金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）とが、蒸着面同士が向き合うように積層されてなる多層フィルムであるが、蒸着面同士を貼り合わせるに際しては、通常、接着剤等が用いられ、かかる接着剤としては、例えば、有機チタン化合物、イソシアネート化合物、ポリエステル系化合物等が挙げられる。 In the multilayer film used in the present invention, the deposition surface of the polyolefin film (A) on which a metal or metal oxide is deposited and the gas barrier film (B) on which a metal or metal oxide is deposited face each other. Although it is a multilayer film formed by laminating, an adhesive agent or the like is usually used when the vapor deposition surfaces are bonded together, and examples of the adhesive agent include an organic titanium compound, an isocyanate compound, and a polyester compound. .
また、必要に応じて、金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）や金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）には塗料層を設けることも、より薄い層構成に於いて高いバリア性を得るという点で好ましい。塗料層は金属或いは金属酸化物が蒸着された蒸着層側の面及び該蒸着層とは反対側の面のどちらに設けてもよい。塗料層を付与する場合においては、任意の塗料を選ぶことができるが、熱放射特性の点から、その塗料層の反射率が６０％以上、特には８０％以上であることが好ましく、色として白色、白銀色、銀色等が好適に用いられる。塗料層の形成方法としては特に制限されないが、市販の塗料をグラビア印刷、オフセット印刷あるいはフレキソ印刷等の印刷法によって付与する方法が実用的である。金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）や金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）と塗料層とのバインダーについても、特に限定されないが、バインダーにウレタン系硬化剤を配合しておく方が密着性の点から好ましい。
なお、かかる金属或いは金属酸化物が蒸着されて形成される蒸着層の厚みは、特に限定されるものではなく、好ましくは２００〜１０００Å、特に好ましくは３００〜８００Åである。蒸着層の厚みが薄すぎると、熱放射特性が得られにくい傾向があり、厚すぎるとその厚みを得るための蒸着時間が長すぎて、蒸着時の熱的な影響が大きくなりすぎる傾向があり、工業的に好ましくない。
Further, if necessary, a coating layer may be provided on the polyolefin film (A) on which a metal or metal oxide is deposited or the gas barrier film (B) on which a metal or metal oxide is deposited. It is preferable in terms of obtaining a high barrier property in the configuration. The coating layer may be provided either on the surface on the side of the vapor deposition layer where the metal or metal oxide is vapor deposited or on the surface opposite to the vapor deposition layer. In the case of applying a paint layer, any paint can be selected, but from the viewpoint of thermal radiation characteristics, the reflectance of the paint layer is preferably 60% or more, particularly 80% or more, White, white silver, silver and the like are preferably used. The method for forming the paint layer is not particularly limited, but a method of applying a commercially available paint by a printing method such as gravure printing, offset printing or flexographic printing is practical. The binder between the polyolefin film (A) on which the metal or metal oxide is deposited or the gas barrier film (B) on which the metal or metal oxide is deposited and the paint layer is not particularly limited. From the viewpoint of adhesion, it is preferable to add an agent.
In addition, the thickness of the vapor deposition layer formed by vapor-depositing such metal or metal oxide is not particularly limited, and is preferably 200 to 1000 mm, particularly preferably 300 to 800 mm. If the thickness of the deposited layer is too thin, thermal radiation characteristics tend to be difficult to obtain, and if too thick, the deposition time for obtaining the thickness is too long, and the thermal influence during deposition tends to be too great. Industrially unfavorable.
また、金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）や金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）の表面に塗料層を施すにあたり、より塗料層との密着性を向上する目的で、金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）や金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）の表面に前処理を行うこともできる。前処理としてはコロナ処理等の基材そのものの活性化を促す方法と、ポリエチレンやポリエーテルを主剤としウレタン系硬化剤を用いるようなコーティング剤で薄膜層を形成する方法が例示できる。
なお、ここで言う表面とは、金属或いは金属酸化物が蒸着された蒸着層側の面及び該蒸着層とは反対側の面のどちらも含む。
In addition, when a paint layer is applied to the surface of a polyolefin film (A) on which a metal or metal oxide is vapor-deposited or a gas barrier film (B) on which a metal or metal oxide is vapor-deposited, the adhesion to the paint layer is further improved. For the purpose of improving, the surface of the polyolefin film (A) on which a metal or metal oxide is deposited or the gas barrier film (B) on which a metal or metal oxide is deposited can be pretreated. Examples of the pretreatment include a method of promoting activation of the substrate itself such as corona treatment, and a method of forming a thin film layer with a coating agent using polyethylene or polyether as a main ingredient and a urethane-based curing agent.
In addition, the surface said here includes both the surface by the side of the vapor deposition layer in which the metal or metal oxide was vapor-deposited, and the surface on the opposite side to this vapor deposition layer.
また、本発明で用いられる多層フィルムは、金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）と、金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）とが、蒸着面同士が向き合うように積層されてなるものであるが、各層の外側に、粘着剤層、シール層等、他の層を有していてもよい。 In addition, the multilayer film used in the present invention includes a polyolefin film (A) on which a metal or metal oxide is vapor-deposited and a gas barrier film (B) on which a metal or metal oxide is vapor-deposited. The layers are laminated so as to face each other, but other layers such as an adhesive layer and a seal layer may be provided outside each layer.
本発明で用いられる多層フィルムの水蒸気透過度は、前述のポリオレフィン系フィルム（Ａ'）での記載と同様で、通常１０ｇ／ｍ2／ｄａｙ以下であり、更には８ｇ／ｍ2／ｄａｙ以下であることが好ましい。多層フィルムの水蒸気透過度が高すぎると過剰な水蒸気が積層体内に取り込まれ、ひいてはポリビニルアルコール系フィルムの水蒸気透過度まで低下させてしまうことで積層体全体の水蒸気透過度の低下をまねき、真空断熱構造体を構成した後に水蒸気が内部に侵入し性能を著しく低下させる。なお、水蒸気透過度は、ＪＩＳ Ｚ ０２０８に則して測定された２３℃×Δ９０％ｒ．ｈ．での値である。 The water vapor permeability of the multilayer film used in the present invention is the same as that described for the polyolefin film (A ′), usually 10 g / m 2 / day or less, and further 8 g / m 2 / day or less. Preferably there is. If the water vapor permeability of the multilayer film is too high, excess water vapor is taken into the laminate, which in turn reduces the water vapor permeability of the polyvinyl alcohol film, leading to a reduction in the water vapor permeability of the entire laminate, and vacuum insulation. After the structure is constructed, water vapor enters the inside and the performance is significantly reduced. The water vapor permeability was 23 ° C. × Δ90% r.s measured according to JIS Z 0208. h. The value at.
また、多層フィルムの酸素透過量は、前述のガスバリア性フィルム（Ｂ'）での記載と同様で、２３℃−５０％ＲＨの条件でＪＩＳ Ｋ ７１２６（等圧法）に記載の方法に準じて測定した際の値が、通常１ｍｌ／（ｍ2・ｄａｙ・ａｔｍ）以下、好ましくは、０．１ｍｌ／（ｍ2・ｄａｙ・ａｔｍ）以下である。 Moreover, the oxygen permeation amount of the multilayer film is the same as described in the gas barrier film (B ′), and is measured according to the method described in JIS K 7126 (isobaric method) under the condition of 23 ° C.-50% RH. The value at this time is usually 1 ml / (m 2 · day · atm) or less, preferably 0.1 ml / (m 2 · day · atm) or less.
次に、上記多層フィルムを用いて、断熱性材料を密封包装して得られる真空断熱構造体について説明する。 Next, a vacuum heat insulating structure obtained by sealing and packaging a heat insulating material using the multilayer film will be described.
かかる断熱性材料を包装するに当たって、その包装方法は特に限定されないが、例えば、多層フィルムを袋状に加工した外装袋を形成し、その中に断熱性材料を入れる方法を用いることができる。 In packaging such a heat insulating material, the packaging method is not particularly limited. For example, a method of forming an outer bag obtained by processing a multilayer film into a bag shape and placing the heat insulating material therein can be used.
多層フィルムから外装袋を形成する際には、外装袋の内側となる面に、シール層を設けることが好ましい。シール層として特に限定されないが、シール強度の観点からポリオレフィン系樹脂層が好ましく、中でもポリプロピレンや高密度ポリエチレンや低密度ポリエチレンあるいはエチレン−酢酸ビニル共重合体などが好適に用いられる。シール層については、上記樹脂より別途フィルムを作製しておき、かかるフィルムを外装袋の内側となる面に接着剤等を用いて貼り付け積層してもよいし、また、外装袋の内側となる面に直接押し出して積層してもよい。シール層をフィルムとして積層する場合は、無延伸フィルムとして積層する方がシール性を得る点で有利である。シール層の厚みは特に限定されないが、通常は１０〜１００μｍ、特には２０〜８０μｍが好ましい。 When forming an exterior bag from a multilayer film, it is preferable to provide a seal layer on the inner surface of the exterior bag. Although it does not specifically limit as a sealing layer, A polyolefin-type resin layer is preferable from a viewpoint of sealing strength, and a polypropylene, a high density polyethylene, a low density polyethylene, an ethylene-vinyl acetate copolymer etc. are used suitably especially. For the sealing layer, a film may be prepared separately from the above resin, and the film may be laminated using an adhesive or the like on the inner surface of the outer bag, or the inner side of the outer bag. You may laminate by extruding directly to the surface. When laminating the sealing layer as a film, laminating it as an unstretched film is advantageous in terms of obtaining sealing properties. Although the thickness of a sealing layer is not specifically limited, Usually, 10-100 micrometers is preferable, and 20-80 micrometers is especially preferable.
本発明の多層フィルムを用いて断熱性材料を密封包装する際の好ましい層構成としては、より屈曲に対する高い耐性を得るという点から、外層側（断熱性材料とは逆側）から、
（１）：［（Ａ）：ポリオレフィン系フィルム（Ａ’）／／金属或いは金属酸化物の蒸着層］／［接着剤層］／［金属或いは金属酸化物の蒸着層／／ガスバリア性フィルム（Ｂ’）：（Ｂ）］／［接着剤層］／［シール層］、
（２）：［（Ａ）：ポリオレフィン系フィルム（Ａ’）／／金属或いは金属酸化物の蒸着層］／［接着剤層］／［金属或いは金属酸化物の蒸着層／／ガスバリア性フィルム（Ｂ’）：（Ｂ）］／［シール層］、
を挙げることができるが、かかる層構成に限定されるものではない。
As a preferable layer configuration when sealing and packaging the heat insulating material using the multilayer film of the present invention, from the viewpoint of obtaining higher resistance to bending, from the outer layer side (the side opposite to the heat insulating material),
(1): [(A): Polyolefin film (A ′) // deposition layer of metal or metal oxide] / [adhesive layer] / [deposition layer of metal or metal oxide // gas barrier film (B '): (B)] / [adhesive layer] / [seal layer]
(2): [(A): Polyolefin film (A ′) // deposition layer of metal or metal oxide] / [adhesive layer] / [deposition layer of metal or metal oxide // gas barrier film (B '): (B)] / [seal layer],
However, the present invention is not limited to such a layer structure.
多層フィルムを用いて真空断熱構造体を製造する際には、かかる多層フィルムを袋状に加工した後に、３０℃以上、０．９Ｔｏｒｒ以下の条件下で乾燥させることが好ましく、特に好ましい温度は、３０〜１５０℃、更には４０〜１２０℃であり、また、特に好ましい圧力は０.００１〜０.９Ｔｏｒｒ、更には０.０１〜０.５Ｔｏｒｒである。かかる温度が低すぎると多層フィルムの内部まで乾燥が届かない傾向があり、高すぎると多層フィルムを構成するフィルムが収縮等の変形をおこす傾向がある。また、かかる圧力が低すぎるとその圧力を達成するためのコストが工業的に見合わなくなる傾向があり、高すぎると多層フィルムの内部まで乾燥が届かない傾向がある。 When producing a vacuum heat insulating structure using a multilayer film, it is preferable to dry the multilayer film under the conditions of 30 ° C. or more and 0.9 Torr or less after processing the multilayer film into a bag shape. The pressure is 30 to 150 ° C., further 40 to 120 ° C., and particularly preferable pressure is 0.001 to 0.9 Torr, and further 0.01 to 0.5 Torr. If the temperature is too low, drying tends not to reach the inside of the multilayer film, and if it is too high, the film constituting the multilayer film tends to undergo deformation such as shrinkage. Moreover, when the pressure is too low, the cost for achieving the pressure tends to be industrially unsuitable, and when it is too high, the drying does not reach the inside of the multilayer film.
多層フィルムを含む外装袋に入れる断熱性材料としては特に限定されず、例えば、アルミナ、シリカ、パーライトなどの微粉末、グラスウール、ロックウール、ケイソウ土、ケイ酸カルシウム成形体、連続気泡を有するウレタンフォーム、カーボンフォーム、フェノールフォーム、フェノールーウレタンフォームなどを用いることができる。 The heat insulating material to be put in the outer bag containing the multilayer film is not particularly limited. For example, fine powder such as alumina, silica, pearlite, glass wool, rock wool, diatomaceous earth, calcium silicate molded body, urethane foam having open cells. Carbon foam, phenol foam, phenol-urethane foam and the like can be used.
これらの中でも、グラスウールなどの繊維状断熱性材料、粒状酸化ケイ素、発泡樹脂体などの粒状断熱性材料が、多層フィルムを含む外装袋内部を真空引きしても形状を保持できる点や、気泡を有しているため真空断熱構造体の断熱効果を保持することができる点で好ましい。 Among these, fibrous heat-insulating materials such as glass wool, granular heat-insulating materials such as granular silicon oxide and foamed resin bodies can retain the shape even when the inside of the outer bag containing the multilayer film is evacuated, Since it has, it is preferable at the point which can hold | maintain the heat insulation effect of a vacuum heat insulation structure.
また、かかる断熱性材料には、使用しているガスバリア性フィルム（Ｂ）が含有する水分により真空度の低下をまねく場合があるため、シリカゲルや塩化カルシウム等の乾燥剤を混合して使用することも好ましい。 In addition, the heat insulating material may be mixed with a desiccant such as silica gel or calcium chloride because the moisture content of the gas barrier film (B) used may reduce the degree of vacuum. Is also preferable.
かかる断熱性材料を多層フィルムを含む外装袋に入れ、減圧し、最後に袋の開口部をシールして閉じることで真空断熱構造体を得ることができる。該真空断熱構造体の真空度としては、特に制限されるわけではないが、１Ｔｏｒｒ以下が好ましく、さらには０．８Ｔｏｒｒ以下が好ましく、特には０．６Ｔｏｒｒ以下が好ましい。 A vacuum heat insulating structure can be obtained by putting such a heat insulating material in an outer bag containing a multilayer film, depressurizing, and finally sealing and closing the opening of the bag. The degree of vacuum of the vacuum heat insulating structure is not particularly limited, but is preferably 1 Torr or less, more preferably 0.8 Torr or less, and particularly preferably 0.6 Torr or less.
本発明においては、真空断熱構造体の形状、大きさは特に限定されるものではなく、目的に応じて決めればよい。例えば、かかる真空断熱構造体形状については、一つの真空断熱構造体に対し、多層フィルムを含む外装袋が一つ含まれる形状でもよいし、一つの真空断熱構造体に対し、外装袋が複数個含まれる形状のものでもよい。 In the present invention, the shape and size of the vacuum heat insulating structure are not particularly limited, and may be determined according to the purpose. For example, the shape of the vacuum heat insulating structure may be a shape including one outer bag containing a multilayer film for one vacuum heat insulating structure, or a plurality of outer bags for one vacuum heat insulating structure. The thing of the shape contained may be sufficient.
かかる外装袋が複数個含まれる形状である場合においては、外装袋部同士のつなぎ目になるシール部分が真空断熱構造体の中で厚みの薄い部分となり、真空断熱構造体を変形させた場合の変形の中心部となるため、真空断熱構造体が容易に変形することが可能となり好ましい。
更には、外的要因によって穴等が発生し、真空断熱構造体の真空性が失われてしまう場合にも、外装袋が複数個含まれる形状であると、断熱性の減少を最小限に留めることができ好ましい。
In the case of a shape including a plurality of such exterior bags, the seal part that becomes a joint between the exterior bag parts becomes a thin part in the vacuum heat insulation structure, and deformation when the vacuum heat insulation structure is deformed Therefore, the vacuum heat insulating structure can be easily deformed, which is preferable.
Furthermore, even when a hole or the like is generated due to an external factor, and the vacuum property of the vacuum heat insulating structure is lost, the decrease in the heat insulating property is kept to a minimum if the shape includes a plurality of exterior bags. Can be preferable.
かかる真空断熱構造体の大きさに関しては、一般的に厚み５〜１００ｍｍで、縦と横が１００〜１０００ｍｍの範囲の直方体状に加工される場合が多い。真空断熱構造体の体積が不必要に大きいと、多層フィルムの袋に穴等の欠陥が発生した場合に性能を失う面積が大きくなり、真空断熱構造体を利用した最終商品の性能を低下させるおそれがあるため、適当な大きさとすることが好ましい。 As for the size of such a vacuum heat insulating structure, it is often processed into a rectangular parallelepiped shape having a thickness of 5 to 100 mm and a length and width of 100 to 1000 mm. If the volume of the vacuum insulation structure is unnecessarily large, the area that loses performance increases when defects such as holes occur in the bag of the multilayer film, which may reduce the performance of the final product using the vacuum insulation structure. Therefore, it is preferable to set the size appropriately.
かくして本発明では、優れた断熱性能を示し、更に伸縮や屈曲に対する耐性にも優れるため、長期間使用した際にもクラックやピンホールが生じにくく、断熱性能が低下しない真空断熱構造体が得られる。かかる真空断熱構造体は、クーラーボックス、ボトルケース等の生活用品、冷蔵庫、ジャーポット、炊飯器等の生活家電、温水器、浴槽、ユニットバス、便座等の住宅設備、床暖房、太陽光屋根、低温輻射板等の住宅システム、外壁用断熱パネル等の住宅建材、等の断熱材として有効に用いることができるが、これらの中でも、冷蔵庫用の断熱材として特に好適に用いることができる。 Thus, in the present invention, excellent heat insulation performance is exhibited and resistance to expansion and contraction and bending is also excellent, so that a vacuum heat insulation structure that does not easily cause cracks and pinholes even when used for a long time and does not deteriorate heat insulation performance is obtained. . Such vacuum heat insulating structures include household appliances such as cooler boxes and bottle cases, household appliances such as refrigerators, jar pots, rice cookers, housing equipment such as water heaters, bathtubs, unit baths, toilet seats, floor heating, solar roofs, Although it can be effectively used as a heat insulating material such as a housing system such as a low-temperature radiation plate and a housing building material such as a heat insulating panel for an outer wall, among them, it can be particularly suitably used as a heat insulating material for a refrigerator.
以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。
尚、例中「部」、「％」とあるのは、断りのない限り重量基準を意味する。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the examples, “parts” and “%” mean weight basis unless otherwise specified.
＜実施例１＞
ジャケット温度を６０〜１５０℃に設定した二軸押出機型混練機（スクリューＬ／Ｄ＝４０）のホッパーからＰＶＡ（重合度１７００、４重量％水溶液の粘度４０ｍＰａ・ｓ、ケン化度９９．７モル％、酢酸ナトリウム含有量０．３％、日本合成化学工業社製「ゴーセノールＮＨ−１７Ｑ」）と水をＰＶＡ／水の重量比４０／６０にて、定量ポンプにより供給し、混練し、吐出量５００ｋｇ／ｈｒの条件で吐出した。
この吐出物を直ちに一軸押出機（スクリューＬ／Ｄ＝３０）に圧送し、温度８５〜１４０℃にて混練した後、Ｔダイより５℃のキャストロールに押出し、９０℃の熱風乾燥機で３０秒間乾燥し、含水率２５％のＰＶＡフィルム（厚み１５０μｍ）を作製した。引き続き、かかるＰＶＡフィルムをＭＤ方向に３．８倍延伸した後、テンターでＴＤ方向に３．８倍延伸し、次いで１８０℃で８秒間熱固定し、二軸延伸ＰＶＡフィルム（厚み１２μｍ）を得た。
<Example 1>
From a hopper of a twin-screw extruder type kneader (screw L / D = 40) whose jacket temperature is set to 60 to 150 ° C., a PVA (polymerization degree 1700, viscosity of 4 wt% aqueous solution 40 mPa · s, saponification degree 99.7) Mol%, sodium acetate content 0.3%, “GOHSENOL NH-17Q” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and water are supplied by a metering pump at a PVA / water weight ratio of 40/60, kneaded and discharged. The discharge was performed under the condition of an amount of 500 kg / hr.
This discharged material was immediately pumped to a single screw extruder (screw L / D = 30), kneaded at a temperature of 85-140 ° C., extruded from a T-die onto a 5 ° C. cast roll, and then heated at 90 ° C. with a hot air dryer. The film was dried for 2 seconds to prepare a PVA film (thickness 150 μm) having a water content of 25%. Subsequently, the PVA film was stretched 3.8 times in the MD direction, then stretched 3.8 times in the TD direction with a tenter, and then heat-fixed at 180 ° C. for 8 seconds to obtain a biaxially stretched PVA film (thickness 12 μm). It was.
得られた二軸延伸ＰＶＡフィルムの片面に、電子線加熱方式による真空蒸着装置により金属アルミニウムを蒸発させ、厚さ４００Åのアルミニウムを蒸着してアルミ蒸着二軸延伸ＰＶＡフィルムを得た。 On one side of the obtained biaxially stretched PVA film, metal aluminum was evaporated by a vacuum deposition apparatus using an electron beam heating method, and aluminum having a thickness of 400 mm was deposited to obtain an aluminum deposited biaxially stretched PVA film.
二軸延伸ポリプロピレンフィルム（東セロ社製「ＯＰ Ｕ−１ ＃２０」 水蒸気透過度＝５．３８ｇ／ｍ2／ｄａｙ）に、電子線加熱方式による真空蒸着装置により金属アルミニウムを蒸発させ、厚さ４００Åのアルミニウムを蒸着して、アルミ蒸着二軸延伸ポリプロピレンフィルムを得た。 Metal aluminum is evaporated on a biaxially stretched polypropylene film (“OP U-1 # 20” manufactured by Tosero Co., Ltd., water vapor permeability = 5.38 g / m 2 / day) by a vacuum vapor deposition apparatus using an electron beam heating method, and the thickness is 400 mm. Aluminum was vapor-deposited to obtain an aluminum-deposited biaxially stretched polypropylene film.
得られたアルミ蒸着二軸延伸ＰＶＡフィルムの蒸着面側に、得られたアルミ蒸着二軸延伸ポリプロピレンフィルムの蒸着面を蒸着面同士が合わさるようにして、ポリエステル系／イソシアネート二液型ポリウレタン系接着剤（武田薬品社製「タケラックＡ−３２１０」／武田薬品社製「タケネートＡ−３０７２」＝３／１（重量比））により７０℃で貼合した後、４０℃の環境で２日間エージングした。
さらに、アルミ蒸着二軸延伸ＰＶＡフィルムの非蒸着面に、熱溶融した高密度ポリエチレン（日本ポリエチレン社製「ノバテックＨＤ ＬＹ２０」）をＴダイコーターから３１５℃の設定で押出しながらコート厚４０μｍとなるように積層し、多層フィルムを得た（層構成＝［二軸延伸ポリプロピレンフィルム／／アルミ蒸着面］／［接着剤層］／［アルミ蒸着面／／二軸延伸ＰＶＡフィルム］／［ポリエチレン層（シール層）］）（図１参照）。
Polyester / isocyanate two-component polyurethane adhesive so that the vapor-deposited surfaces of the obtained aluminum-deposited biaxially-stretched polypropylene film are aligned with the vapor-deposited side of the obtained aluminum-deposited biaxially-stretched PVA film. After pasting at 70 ° C. using (Takelac A-3210 manufactured by Takeda Pharmaceutical Co., Ltd./“Takenate A-3072 ”manufactured by Takeda Pharmaceutical Co., Ltd. = 3/1 (weight ratio)), it was aged in an environment of 40 ° C. for 2 days.
Furthermore, hot-melted high-density polyethylene (“Novatech HD LY20” manufactured by Nippon Polyethylene Co., Ltd.) is extruded from a T-die coater at a setting of 315 ° C. on the non-deposition surface of the aluminum-deposited biaxially stretched PVA film so that the coating thickness becomes 40 μm To obtain a multilayer film (layer structure = [biaxially stretched polypropylene film // aluminum deposited surface] / [adhesive layer] / [aluminum deposited surface // biaxially stretched PVA film] / [polyethylene layer (seal Layer)]) (see FIG. 1).
＜実施例２＞
実施例１において、アルミ蒸着二軸延伸ＰＶＡフィルムの変わりに、市販のアルミ蒸着二軸延伸ＥＶＯＨフィルム（東洋メタライジング社製「ＶＭ−ＥＶＯＨ」）を使用した以外は、実施例１と同様に行い、多層フィルムを得た。（層構成＝［二軸延伸ポリプロピレンフィルム／／アルミ蒸着面］／［接着剤層］／［アルミ蒸着面／／二軸延伸ＥＶＯＨフィルム］／［ポリエチレン層（シール層）］）
<Example 2>
In Example 1, it replaced with the aluminum vapor deposition biaxial stretching PVA film, and performed similarly to Example 1 except having used a commercially available aluminum vapor deposition biaxial stretching EVOH film ("VM-EVOH" by Toyo Metallizing Co., Ltd.). A multilayer film was obtained. (Layer structure = [biaxially stretched polypropylene film // aluminum vapor deposition surface] / [adhesive layer] / [aluminum vapor deposition surface // biaxially stretched EVOH film] / [polyethylene layer (seal layer)])
＜比較例１＞
実施例１のアルミ蒸着二軸延伸ＰＶＡフィルムとアルミ蒸着二軸延伸ポリプロピレンに加えて、更にアルミ蒸着ＰＥＴフィルム（東洋メタライジング社製「ＶＭ−ＰＥＴ１５１０」）を使用し、積層した以外は、実施例１と同様に行い、多層フィルムを得た。（層構成＝[二軸延伸ポリプロピレンフィルム／／アルミ蒸着層]／[接着剤層]／[アルミ蒸着層／／ＰＥＴフィルム]／[接着剤層]／[アルミ蒸着層／／二軸延伸ＰＶＡフィルム]／[ポリエチレン（シール層）]）
<Comparative Example 1>
In addition to the aluminum vapor-deposited biaxially stretched PVA film and the aluminum vapor-deposited biaxially-stretched polypropylene of Example 1, an aluminum vapor-deposited PET film (“VM-PET1510” manufactured by Toyo Metallizing Co., Ltd.) was used and laminated. 1 was performed to obtain a multilayer film. (Layer constitution = [Biaxially stretched polypropylene film // Aluminum deposited layer] / [Adhesive layer] / [Aluminum deposited layer // PET film] / [Adhesive layer] / [Aluminum deposited layer // Biaxially stretched PVA film ] / [Polyethylene (seal layer)])
＜比較例２＞
実施例１のアルミ蒸着二軸延伸ＰＶＡフィルムの代わりに、アルミニウムホイル（東陽アルミ社製アルミ箔（６μｍ）を用いた以外は、実施例１と同様に行い、多層フィルムを得た。（層構成＝[二軸延伸ポリプロピレンフィルム／／アルミ蒸着層]／[接着剤層]／[アルミニウムホイル]／[ポリエチレン層（シール層）]）
<Comparative example 2>
A multilayer film was obtained in the same manner as in Example 1 except that an aluminum foil (aluminum foil (6 μm) manufactured by Toyo Aluminum Co., Ltd.) was used instead of the aluminum vapor-deposited biaxially stretched PVA film of Example 1. = [Biaxially stretched polypropylene film // Aluminum deposition layer] / [Adhesive layer] / [Aluminum foil] / [Polyethylene layer (seal layer)])
＜酸素透過度＞
上記多層フィルムを、ＭＯＤＥＲＮ ＣＯＮＴＲＯＬＳ．ＩＮＫ製 酸素透過度測定装置 「ＭＯＣＯＮ ＯＸ−ＴＲＡＮ ２／２０型」（検出限界値０．０１ｍｌ／（ｍ2・ｄａｙ・ａｔｍ））を用い、２３℃−５０％ＲＨの条件でＪＩＳ Ｋ ７１２６（等圧法）に記載の方法に準じて測定した。なお、本発明でいう酸素透過度は、任意の膜厚で測定した透過度（ｍｌ／（ｍ2・ｄａｙ・ａｔｍ））である。また、該酸素透過度が上記した装置の検出限界値以下であった場合は≦０．０１と記載する。
<Oxygen permeability>
The multilayer film is made into MODERN CONTROLS. By using an oxygen permeability measuring device “MOCON OX-
＜水蒸気透過度＞
上記多層フィルムを、Ｌ８０−５０００型水蒸気透過度計（検出限界値０．０１ｇ／ｍ2／ｄａｙ）（Ｌｙｓｓｙ社製）を用い、４０℃−Δ９０％ＲＨの条件でＪＩＳ Ｋ ７１２９（Ａ法）に記載の方法に準じて測定した。なお、本発明でいう透過度は、任意の膜厚で測定した値（ｇ／ｍ2／ｄａｙ）である。また、該水蒸気透過度が上記した装置の検出限界値以下であった場合は≦０．０１と記載する。
<Water vapor permeability>
JIS K 7129 (Method A) using the L80-5000 type water vapor permeability meter (detection limit value 0.01 g / m 2 / day) (manufactured by Lyssy) using the above multilayer film under conditions of 40 ° C. and Δ90% RH. It measured according to the method of description. In addition, the transmittance | permeability said by this invention is the value (g / m < 2 > / day) measured by arbitrary film thicknesses. In addition, when the water vapor transmission rate is not more than the detection limit value of the above-described apparatus, it is described as ≦ 0.01.
＜屈曲疲労試験＞
屈曲疲労試験（以下、ゲルボ試験）は、理学工業社製のゲルボフレックステスターを用いて評価した。条件としては、（ＭＩＬ−Ｂ１３１Ｈ）ＤＥ１１２インチ×８インチの試験片を直径３（１／２）インチの円筒状とし、両端を保持し、初期把握間隔７インチとし、ストロークの３（１／２）インチで、４００度のひねりを加える。この動作の繰り返し往復運動を４０回／ｍｉｎの速さで、５０回行う。測定雰囲気は、２０℃、相対湿度は６５％である。
<Bending fatigue test>
The bending fatigue test (hereinafter referred to as a gelbo test) was evaluated using a gelbo flex tester manufactured by Rigaku Corporation. As a condition, a (MIL-B131H) DE 112 inch × 8 inch test piece was formed into a cylindrical shape having a diameter of 3 (1/2) inch, both ends were held, an initial grasping interval was 7 inches, and a stroke 3 (1/2 ) Add a 400 degree twist in inches. The reciprocating motion of this operation is performed 50 times at a speed of 40 times / min. The measurement atmosphere is 20 ° C. and the relative humidity is 65%.
上記で得られた実施例１、２および比較例１、２の多層フィルムに上記の屈曲疲労試験を行って、屈曲疲労試験後多層フィルムを得た。 The above-described bending fatigue test was performed on the multilayer films of Examples 1 and 2 and Comparative Examples 1 and 2 obtained above to obtain a multilayer film after the bending fatigue test.
得られた実施例１、２及び比較例１、２の多層フィルムを縦２０ｃｍ、横２０ｃｍの正方形に成形し、これを積層した高密度ポリエチレン層同士が合わせられるように重ね合わせ、その周囲３方の周辺部を幅１ｃｍでヒートシールして貼り合わせ（シール温度１４０℃）、得られた袋状多層構造体を６０℃で０．１Ｔｏｒｒの条件の乾燥機内で３時間乾燥した後、その袋状多層構造体の内部に縦１７ｃｍ、横１７ｃｍに裁断した厚さ２５ｍｍのグラスウール片（マグ社製「マグロールＲＲ２４２５」）を入れて、これを真空包装装置内（ＮＰＣ社製：「特殊真空包装機」）で０．０１Ｔｏｒｒの真空度にした状態で、残る１方の開口部を先と同じ条件で熱融着し、真空断熱構造体を得た。 The obtained multilayer films of Examples 1 and 2 and Comparative Examples 1 and 2 were formed into a square of 20 cm in length and 20 cm in width, and superposed so that the high-density polyethylene layers laminated together could be combined, and the surrounding three sides The peripheral part of the film was heat-sealed with a width of 1 cm and bonded together (sealing temperature 140 ° C.), and the obtained bag-shaped multilayer structure was dried at 60 ° C. in a dryer under the condition of 0.1 Torr for 3 hours. A glass wool piece of 25 mm thickness ("Magroll RR2425" manufactured by Mag Co., Ltd.) cut into a length of 17 cm and a width of 17 cm is placed inside the multilayer structure, and this is placed in a vacuum packaging apparatus (NPC Corporation: "Special Vacuum Packaging Machine") ), The remaining one opening was heat-sealed under the same conditions as above to obtain a vacuum heat insulating structure.
上記の実施例１、２および比較例１、２の屈曲疲労試験後多層フィルムを用いて上記と同じ方法で真空断熱構造体を得た。 Using the multilayer film after the bending fatigue test of Examples 1 and 2 and Comparative Examples 1 and 2, a vacuum heat insulating structure was obtained in the same manner as described above.
＜断熱性能＞
上記で得られた実施例１、２および比較例１、２の多層フィルムを含む真空断熱構造体と実施例１、２および比較例１、２の屈曲疲労試験後多層フィルムを含む真空断熱構造体を、４０℃×９０％ｒ．ｈ．の恒温槽内に１ヶ月間放置したものを、厚さ３ｍｍのアルミニウム板で、一辺２０ｃｍの一面だけ開閉可能とした立方体（アルミニウム箱）の中に、各面（６面）の内側を覆うようにして敷き詰め、内部に温度記録計を入れた。開閉可能にした面を開放した状態で、５℃に保持した恒温装置の中に２４時間放置した後、開閉可能にした面を閉じて真空断熱構造体とともに密閉して、このアルミニウム箱を４０℃の恒温装置の中に入れ、３０分後の内部温度を測定し、断熱性能を評価した。
<Insulation performance>
Vacuum heat insulating structure including the multilayer films of Examples 1 and 2 and Comparative Examples 1 and 2 obtained above and a vacuum heat insulating structure including the multilayer film after bending fatigue test of Examples 1 and 2 and Comparative Examples 1 and 2 Of 40 ° C. × 90% r. h. Covering the inside of each surface (six sides) in a cube (aluminum box) that can be opened and closed only on one side of 20 cm with an aluminum plate with a thickness of 3 mm. The temperature recorder was placed inside. After leaving the surface that can be opened and closed in a thermostat kept at 5 ° C. for 24 hours, the surface that can be opened and closed is closed and sealed together with the vacuum heat insulating structure. The thermostat was evaluated by measuring the internal temperature after 30 minutes.
上記試験を、屈曲疲労試験前の多層フィルムを用いて行なった場合の結果を表１に、屈曲疲労試験後の多層フィルムを用いて行なった場合の結果を表２に示す。 Table 1 shows the results when the above test was performed using the multilayer film before the bending fatigue test, and Table 2 shows the results when the multilayer film was subjected to the bending fatigue test.
［表１］屈曲疲労試験前
［表２］屈曲疲労試験後
上記表１で示されるように、屈曲疲労試験前の多層フィルムを用いた場合、耐酸素・耐水蒸気透過度、断熱性能の全てにおいて実施例と比較例で効果の差はあまり見られないものであったが、屈曲疲労試験後の多層フィルムを用いた場合、表２で示されるように、実施例１及び２のデータは、比較例１及び２よりも耐酸素・耐水蒸気透過度と断熱性能の両方が優れるものである。
このことは、本発明の多層フィルムは、比較例のＰＥＴフィルムやアルミ箔のように硬い素材を用いていないため、伸縮や屈曲に対する耐性に優れるものであり、長期間使用した際にもクラックやピンホールが生じにくく、断熱性能の低下しない真空断熱構造体を形成することが可能であることを示している。
As shown in Table 1 above, when the multilayer film before the bending fatigue test is used, there is not much difference in the effect between Example and Comparative Example in all of oxygen resistance / water vapor resistance and heat insulation performance. However, when the multilayer film after the bending fatigue test was used, as shown in Table 2, the data of Examples 1 and 2 are more resistant to oxygen and water vapor and the heat insulation performance than Comparative Examples 1 and 2. Both are excellent.
This is because the multilayer film of the present invention does not use a hard material like the PET film or aluminum foil of the comparative example, and therefore has excellent resistance to expansion and contraction and bending. This indicates that it is possible to form a vacuum heat insulating structure that does not easily generate pinholes and does not deteriorate the heat insulating performance.
本発明の真空断熱構造体は、金属或いは金属酸化物が蒸着されたポリオレフィン系フィルム（Ａ）と、金属或いは金属酸化物が蒸着されたガスバリア性フィルム（Ｂ）を含む多層フィルムと断熱性材料を含む真空断熱構造体であって、該ポリオレフィン系フィルム（Ａ）の金属或いは金属酸化物が蒸着された面と該ガスバリア性フィルム（Ｂ）の金属或いは金属酸化物が蒸着された面が向き合うように積層されて、且つ、該多層フィルムが断熱性材料を密封包装してなるため、耐酸素・水蒸気透過度、断熱性能に優れるのは勿論のこと、長期間使用した際にもクラックやピンホールが生じにくいため、クーラーボックス、ボトルケース等の生活用品、冷蔵庫、ジャーポット、炊飯器等の生活家電、温水器、浴槽、ユニットバス、便座等の住宅設備、床暖房、太陽光屋根、低温輻射板等の住宅システム、外壁用断熱パネル等の住宅建材、等の断熱材として有効に用いることができるが、これらの中でも、冷蔵庫用の断熱材として特に好適に用いることができる。 The vacuum heat insulating structure of the present invention comprises a polyolefin film (A) on which a metal or metal oxide is deposited, a multilayer film including a gas barrier film (B) on which a metal or metal oxide is deposited, and a heat insulating material. A vacuum heat insulating structure including a surface of the polyolefin-based film (A) on which the metal or metal oxide is deposited and a surface of the gas barrier film (B) on which the metal or metal oxide is deposited. Since it is laminated and the multilayer film is hermetically packaged with a heat-insulating material, it has excellent resistance to oxygen and water vapor and heat insulation, as well as cracks and pinholes even when used for a long time. Living items such as cooler boxes and bottle cases, household appliances such as refrigerators, jar pots, rice cookers, water heaters, bathtubs, unit baths, toilet seats, etc. It can be used effectively as a heat insulating material for housing systems such as equipment, floor heating, solar roofs, low-temperature radiation plates, etc., heat insulating panels for outer walls, etc., among these, especially as heat insulating materials for refrigerators It can be used suitably.
１ 二軸延伸ポリプロピレンフィルム
２ アルミ蒸着層
３ 接着剤層
４ アルミ蒸着層
５ 二軸延伸ＰＶＡフィルム
６ ポリエチレン層（シール層）
DESCRIPTION OF
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Cited By (4)
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| WO2014095536A1 (en) * | 2012-12-18 | 2014-06-26 | BSH Bosch und Siemens Hausgeräte GmbH | Wall for a household refrigeration appliance with a top layer comprising high-gloss polystyrene and/or silver particles and household appliance comprising said type of wall |
| JP2014126098A (en) * | 2012-12-26 | 2014-07-07 | Nippon Synthetic Chem Ind Co Ltd:The | Vacuum insulation structure and outer package bag for vacuum insulation structure |
| JP2016223545A (en) * | 2015-06-01 | 2016-12-28 | 凸版印刷株式会社 | Laminate for vacuum heat insulation material and vacuum heat insulation material using the same |
| WO2020184523A1 (en) * | 2019-03-11 | 2020-09-17 | 株式会社クラレ | Multilayer structure, and packaging material for retort using same |
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| KR101263577B1 (en) * | 2010-12-24 | 2013-05-13 | (주)엘지하우시스 | Phenolic foam as core material for vacuum insulation panel and method for fabricating vacuum insulation panel using the same |
| CN102128474A (en) * | 2011-05-05 | 2011-07-20 | 杨军 | Energy-saving type radiation refrigerating and heating module |
| EP2889526A4 (en) * | 2012-08-23 | 2016-04-13 | Asahi Glass Co Ltd | Vacuum heat-insulating material and method for manufacturing vacuum heat-insulating material |
| JP2020008084A (en) * | 2018-07-06 | 2020-01-16 | 大日本印刷株式会社 | Outer packaging material for vacuum insulation material, vacuum heat insulation material, and articles with vacuum insulation material |
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| WO2014095536A1 (en) * | 2012-12-18 | 2014-06-26 | BSH Bosch und Siemens Hausgeräte GmbH | Wall for a household refrigeration appliance with a top layer comprising high-gloss polystyrene and/or silver particles and household appliance comprising said type of wall |
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| JP2014126098A (en) * | 2012-12-26 | 2014-07-07 | Nippon Synthetic Chem Ind Co Ltd:The | Vacuum insulation structure and outer package bag for vacuum insulation structure |
| JP2016223545A (en) * | 2015-06-01 | 2016-12-28 | 凸版印刷株式会社 | Laminate for vacuum heat insulation material and vacuum heat insulation material using the same |
| WO2020184523A1 (en) * | 2019-03-11 | 2020-09-17 | 株式会社クラレ | Multilayer structure, and packaging material for retort using same |
| JPWO2020184523A1 (en) * | 2019-03-11 | 2020-09-17 | ||
| US11813823B2 (en) | 2019-03-11 | 2023-11-14 | Kuraray Co., Ltd. | Multilayer structure, and packaging material for retort using same |
| JP7437381B2 (en) | 2019-03-11 | 2024-02-22 | 株式会社クラレ | Multilayer structure and retort packaging material using the same |
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