JP2016223545A - Laminate for vacuum heat insulation material and vacuum heat insulation material using the same - Google Patents

Laminate for vacuum heat insulation material and vacuum heat insulation material using the same Download PDF

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JP2016223545A
JP2016223545A JP2015111193A JP2015111193A JP2016223545A JP 2016223545 A JP2016223545 A JP 2016223545A JP 2015111193 A JP2015111193 A JP 2015111193A JP 2015111193 A JP2015111193 A JP 2015111193A JP 2016223545 A JP2016223545 A JP 2016223545A
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vacuum heat
heat insulating
laminate
insulating material
vacuum
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JP6623563B2 (en
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朋子 松本
Tomoko Matsumoto
朋子 松本
小河原 賢次
Kenji Ogawara
賢次 小河原
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Toppan Inc
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Toppan Printing Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a vacuum heat insulation material which has high gas barrier properties and which can maintain heat insulation performance even in a place which is exposed to high humidity, and a laminate for vacuum heat insulation material used for the same.SOLUTION: A laminate for vacuum heat insulation material is used for a vacuum heat insulation material in which a heat insulation core material is coated by the laminate for vacuum heat insulation material, and in which the inside is brought into a vacuum state by degassing. In the laminate for vacuum heat insulation material, steam permeability of the laminate for vacuum heat insulation material is equal to or less than 0.1 g/mday, and the steam permeability after bending is equal to or less than 0.5 g/mday.SELECTED DRAWING: Figure 1

Description

本発明は、真空断熱材用積層体およびそれを用いた真空断熱材に関するものである。   The present invention relates to a laminate for a vacuum heat insulating material and a vacuum heat insulating material using the same.

真空断熱材は、芯材を真空断熱材用積層体で被覆し、芯材の周囲を真空状態にし、気体による熱伝導率を限りなくゼロに近づけることにより、断熱性能を高めた断熱材である。   The vacuum heat insulating material is a heat insulating material whose heat insulating performance is improved by covering the core material with a laminate for vacuum heat insulating material, making the periphery of the core material in a vacuum state, and bringing the thermal conductivity by gas as close to zero as possible. .

真空断熱材用積層体には内部の真空度を保つため、ガスバリア性が要求される。しかしながら、従来の真空断熱材には、ガスバリア層としてアルミニウム箔を使用しているため、真空断熱材の真空断熱材用積層体を伝わる熱伝導、いわゆるヒートブリッジ現象によって真空断熱材の断熱効果が小さくなる現象が見られた。   The laminated body for vacuum heat insulating material is required to have gas barrier properties in order to maintain the internal vacuum. However, since the conventional vacuum heat insulating material uses aluminum foil as a gas barrier layer, the heat insulation effect of the vacuum heat insulating material is small due to the heat conduction that travels through the laminate for the vacuum heat insulating material of the vacuum heat insulating material, so-called heat bridge phenomenon. A phenomenon was seen.

特許文献1には、アルミ蒸着エチレン−ビニルアルコール共重合体フィルムを用い、所定の酸素透過度及び水蒸気透過度を有する外装材を用いることによって、断熱性能を向上して、信頼性を確保した真空断熱材が提案されている。   Patent Document 1 uses an aluminum-deposited ethylene-vinyl alcohol copolymer film and uses an exterior material having a predetermined oxygen permeability and water vapor permeability to improve heat insulation performance and ensure reliability. Insulation has been proposed.

アルミ蒸着エチレン−ビニルアルコール共重合体フィルムを用いた構成では、真空断熱材成型時にアルミ蒸着が損傷を受けても、エチレン−ビニルアルコール共重合体がガスバリア性を補う。しかしながら、エチレン−ビニルアルコール共重合体は水蒸気バリア性がないため、高湿に曝される場所では適さない。また防湿のためのガスバリアフィルムが屈曲によってガスバリア性能が低下することも問題とされてきた。   In the configuration using the aluminum-deposited ethylene-vinyl alcohol copolymer film, the ethylene-vinyl alcohol copolymer supplements the gas barrier property even if the aluminum deposition is damaged during the vacuum heat insulating material molding. However, ethylene-vinyl alcohol copolymer is not suitable for places exposed to high humidity because it has no water vapor barrier property. In addition, it has been a problem that the gas barrier performance for the moisture barrier film deteriorates due to bending.

特許第5608472号Japanese Patent No. 5608472

本発明は、このような従来技術の問題点を解決しようとするものであり、ガスバリア性が高く、高湿に曝される場所でも断熱性能を維持でき、屈曲によるガスバリア性能の劣化を起こしにくい、真空断熱材用積層体およびそれを用いた真空断熱材を提供することを課題とする。   The present invention is intended to solve such problems of the prior art, has a high gas barrier property, can maintain heat insulation performance even in places exposed to high humidity, and hardly causes deterioration of gas barrier performance due to bending, It aims at providing the laminated body for vacuum heat insulating materials, and the vacuum heat insulating material using the same.

本発明に於いて上記課題を達成するために、まず請求項1の発明は、断熱芯材を真空断熱材用積層体で被覆し、内部を脱気し真空状態とした真空断熱材に用いられる真空断熱材用積層体において、該真空断熱材用積層体の、水蒸気透過度が0.1g/m・day以下、屈曲後の水蒸気透過度が0.5g/m・day以下であることを特徴とする真空断熱材用積層体である。 In order to achieve the above object in the present invention, first, the invention of claim 1 is used for a vacuum heat insulating material in which a heat insulating core material is covered with a laminate for a vacuum heat insulating material and the inside is deaerated to be in a vacuum state. In the laminate for vacuum heat insulating material, the water vapor permeability of the laminate for vacuum heat insulating material is 0.1 g / m 2 · day or less, and the water vapor permeability after bending is 0.5 g / m 2 · day or less. It is the laminated body for vacuum heat insulating materials characterized by these.

また、請求項2の発明は、前記真空断熱材用積層体が、プラスチック基材の少なくとも片面に、金属又は無機酸化物或いはそれらの混合物である蒸着薄膜層を積層したバリアフィルム、アルミ蒸着フィルム、塩化ビニリデンフィルム、熱融着層の順に積層されたことを特徴とする請求項1に記載の真空断熱材用積層体である。   Further, the invention of claim 2 is a barrier film in which the laminate for a vacuum heat insulating material is formed by laminating a vapor deposition thin film layer which is a metal or an inorganic oxide or a mixture thereof on at least one surface of a plastic substrate, an aluminum vapor deposition film, 2. The laminate for a vacuum heat insulating material according to claim 1, wherein a vinylidene chloride film and a heat sealing layer are laminated in this order.

また、請求項3の発明は、前記真空断熱材用積層体が、プラスチック基材の少なくとも片面に、金属又は無機酸化物或いはそれらの混合物である蒸着薄膜層、水溶性高分子と(
a)1種以上のアルコキシドまたはその加水分解物、または両者、あるいは(b)塩化錫の少なくともいずれか1つを含む水溶液、あるいは水/アルコール混合溶液を主剤とするコーティング剤からなる被膜層とを積層したバリアフィルム、アルミ蒸着フィルム、塩化ビニリデンフィルム、熱融着層の順に積層されたことを特徴とする請求項1に記載の真空断熱材用積層体である。
Moreover, the invention of claim 3 is characterized in that the laminate for a vacuum heat insulating material is formed on at least one surface of a plastic substrate with a vapor-deposited thin film layer, a water-soluble polymer, or a metal or an inorganic oxide or a mixture thereof.
a) one or more alkoxides or hydrolysates thereof, or both, or (b) an aqueous solution containing at least one of tin chloride, or a coating layer comprising a coating agent mainly composed of a water / alcohol mixed solution. The laminated body for a vacuum heat insulating material according to claim 1, wherein the laminated barrier film, the aluminum vapor deposition film, the vinylidene chloride film, and the heat fusion layer are laminated in this order.

また、請求項4の発明は、前記熱融着層が、直鎖状低密度ポリエチレンフィルムであることを特徴とする請求項1〜請求項3のいずれかに記載の真空断熱材用積層体である。   The invention according to claim 4 is the laminate for a vacuum heat insulating material according to any one of claims 1 to 3, wherein the heat-sealing layer is a linear low-density polyethylene film. is there.

また、請求項5の発明は、前記熱融着層の密度が、0.934g/cm以下であることを特徴とする請求項4に記載の真空断熱材用積層体である。 The invention according to claim 5 is the laminate for a vacuum heat insulating material according to claim 4, wherein the density of the heat-fusible layer is 0.934 g / cm 3 or less.

また、請求項6の発明は、真空断熱材において、前記請求項1〜請求項5のいずれかに記載の真空断熱材用積層体を用いてなることを特徴とする真空断熱材である。   Moreover, invention of Claim 6 is a vacuum heat insulating material characterized by using the laminated body for vacuum heat insulating materials in any one of the said Claims 1-5 in a vacuum heat insulating material.

本発明は、ガスバリア性が高く、高湿に曝される場所でも断熱性能を維持でき、屈曲によるガスバリア性能の劣化を起こしにくい、真空断熱材用積層体およびそれを用いた真空断熱材を提供することができる。   The present invention provides a laminate for a vacuum heat insulating material and a vacuum heat insulating material using the same, which have high gas barrier properties, can maintain heat insulating performance even in a place exposed to high humidity, and are less likely to deteriorate gas barrier performance due to bending. be able to.

本発明の真空断熱材の一実施形態の断面模式図である。It is a cross-sectional schematic diagram of one Embodiment of the vacuum heat insulating material of this invention. 本発明に用いることができるバリアフィルムの一実施例を図解的に示す図である。It is a figure which shows typically one Example of the barrier film which can be used for this invention. 本発明に用いることができるバリアフィルムの他の実施例を図解的に示す図である。It is a figure showing other examples of a barrier film which can be used for the present invention diagrammatically. 本発明による真空断熱材用積層体の一実施例の層構成を図解的に示す図である。It is a figure which shows the layer structure of one Example of the laminated body for vacuum heat insulating materials by this invention schematically.

以下発明を実施するための形態について、図1〜図4を参照しながら詳細な説明を加える。ただし、本発明はこれらの例にのみ限定されるものではない。   A detailed description will be given below with reference to FIGS. However, the present invention is not limited only to these examples.

図1は本発明の真空断熱材の一実施形態の断面模式図である。芯材3は真空断熱材用積層体2で被覆され封入され真空断熱材1を構成する。このとき内部は脱気され真空状態となっている。   FIG. 1 is a schematic cross-sectional view of an embodiment of the vacuum heat insulating material of the present invention. The core material 3 is covered and enclosed with the laminate 2 for vacuum heat insulating material to constitute the vacuum heat insulating material 1. At this time, the inside is deaerated and is in a vacuum state.

図4は本発明の真空断熱材用積層体の一実施例の層構成を図解的に示す図である。本発明による真空断熱材用積層体において、ここに示す例は真空断熱材用積層体2がプラスチック基材5の少なくとも片面に、金属又は無機酸化物或いはそれらの混合物である蒸着薄膜層、水溶性高分子と(a)1種以上のアルコキシドまたは/及びその加水分解物または(b)塩化錫の少なくともいずれか1つを含む水溶液、あるいは水/アルコール混合溶液を主剤とするコーティング剤からなる被膜層とを積層したバリアフィルム4、アルミ蒸着フィルム10、ポリ塩化ビニリデンフィルム11、熱融着層12の順に積層されたことを特徴とする真空断熱材用積層体2である。この状態において、本発明による真空断熱材用積層体の水蒸気透過度は、0.1g/m・day以下、屈曲試験であるゲルボ試験後の水蒸気透過度は0.5g/m・day以下である。 FIG. 4 is a diagram schematically showing a layer configuration of one embodiment of the laminate for a vacuum heat insulating material of the present invention. In the laminated body for a vacuum heat insulating material according to the present invention, the example shown here is a vapor-deposited thin film layer in which the laminated body 2 for a vacuum heat insulating material is a metal or an inorganic oxide or a mixture thereof on at least one surface of a plastic substrate 5, water-soluble A coating layer comprising a polymer and an aqueous solution containing at least one of (a) one or more alkoxides and / or hydrolysates thereof and (b) tin chloride, or a coating agent mainly composed of a water / alcohol mixed solution. The laminate 2 for vacuum heat insulating material is characterized in that the barrier film 4, the aluminum vapor-deposited film 10, the polyvinylidene chloride film 11, and the heat fusion layer 12 are laminated in this order. In this state, the water vapor permeability of the laminate for a vacuum heat insulating material according to the present invention is 0.1 g / m 2 · day or less, and the water vapor permeability after the gelbo test which is a bending test is 0.5 g / m 2 · day or less. It is.

ここでは各層の積層は接着層13を介して積層されている。また真空断熱材用積層体2同士の接着は、積層体の熱融着層12同士を対向させて重ね、加熱、加圧して行なうこと
ができる。
Here, the layers are stacked via the adhesive layer 13. Adhesion between the laminates 2 for vacuum heat insulating materials can be performed by stacking the heat fusion layers 12 of the laminate facing each other, heating and pressurizing them.

まず、図2 に示す本発明に用いることができるバリアフィルムの一実施例において、バリアフィルム4 は、基材5がプラスチック材料からなるフィルム基材であり、その片面に蒸着薄膜層6、被膜層7が順次積層されている。
基材5のプラスチック材料は、例えば、ポリエチレンテレフタレート(PET)やポリエチレンナフタレート(PEN)などのポリエステルフィルム、ポリエチレンやポリプロピレンなどのポリオレフィンフィルム、ポリスチレンフィルム、ポリアミドフィルム、ポリカーボネートフィルム、ポリアクリルニトリルフィルム、ポリイミドフィルム等を用いることができる。これらは、機械的強度や寸法安定性を有するものであれば、延伸されたものでも未延伸のものでも構わない。通常これらのものを、フィルム状に加工して用いられる。特に耐熱性等の観点から二軸方向に任意に延伸されたポリエチレンテレフタレートフィルムやポリアミドフィルムが好ましく用いられる。
また、この基材5の蒸着薄膜層6が設けられる面と反対側の表面に、周知の種々の添加剤や安定剤、例えば帯電防止剤、紫外線防止剤、可塑剤、滑剤などが使用されていても良い。また、蒸着薄膜層6との密着性を良くするために、基材5の積層面側を前処理としてコロナ処理、低温プラズマ処理、イオンボンバード処理、薬品処理、溶剤処理などのいずれかの処理を施しても良い。
First, in one embodiment of the barrier film that can be used in the present invention shown in FIG. 2, the barrier film 4 is a film base material in which the base material 5 is made of a plastic material. 7 are sequentially laminated.
Examples of the plastic material of the base material 5 include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films, polycarbonate films, polyacrylonitrile films, and polyimides. A film or the like can be used. These may be stretched or unstretched as long as they have mechanical strength and dimensional stability. Usually, these are processed into a film and used. In particular, a polyethylene terephthalate film or a polyamide film arbitrarily stretched in the biaxial direction from the viewpoint of heat resistance or the like is preferably used.
In addition, various well-known additives and stabilizers such as antistatic agents, anti-ultraviolet agents, plasticizers, lubricants, and the like are used on the surface of the substrate 5 opposite to the surface on which the deposited thin film layer 6 is provided. May be. Further, in order to improve the adhesion with the deposited thin film layer 6, any one of corona treatment, low temperature plasma treatment, ion bombardment treatment, chemical treatment, solvent treatment, etc. is performed with the laminated surface side of the substrate 5 as a pretreatment. You may give it.

基材5の厚さは、とくに限定されるものではなく、また基材としての適性を考慮して、単体フィルム以外の異なる性質のフィルムを積層したフィルムを使用することもできる。加工性を考慮すれば、3〜200μmの範囲が好ましく、特に6〜30μmが好ましい。   The thickness of the substrate 5 is not particularly limited, and a film obtained by laminating films having different properties other than the single film can be used in consideration of suitability as a substrate. In consideration of workability, the range of 3 to 200 μm is preferable, and 6 to 30 μm is particularly preferable.

また、量産性を考慮すれば、連続的に各層を形成できる長尺の連続フィルムとすることが望ましい。   In consideration of mass productivity, it is desirable to use a long continuous film capable of continuously forming each layer.

次に蒸着薄膜層6は、金属、例えばアルミニウム、銅、銀など、もしくは無機酸化物、例えばイットリウムタンタルオキサイド、酸化アルミニウム、酸化珪素、酸化マグネシウム或いはそれらの混合物の蒸着膜からなり、酸素、水蒸気等のガスバリア性を有する。これらの中では、特にアルミニウム、酸化アルミニウム及び酸化珪素、酸化マグネシウムが好ましい。なお、上述の金属および無機酸化物に限定されず、酸素、水蒸気等のガスバリア性を有する材料であれば用いることができる。   Next, the deposited thin film layer 6 is made of a deposited film of a metal, such as aluminum, copper, silver, or an inorganic oxide, such as yttrium tantalum oxide, aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof. It has a gas barrier property. Among these, aluminum, aluminum oxide, silicon oxide, and magnesium oxide are particularly preferable. Note that the material is not limited to the above-described metals and inorganic oxides, and any material having gas barrier properties such as oxygen and water vapor can be used.

蒸着薄膜層6の厚さは、用いられる化合物の種類・構成により最適条件が異なるが、5〜300nmの範囲内が望ましく、その厚さ適宜選択することができる。ただし、膜厚が5nm未満の場合は、均一な膜が得られず、膜厚が十分とはいえない。また、無機酸化物の場合、膜厚が300nmを越える場合は薄膜にフレキシビリティを発揮することができず、成膜後に折り曲げ、引っ張りなどの外的要因により、薄膜に亀裂を生じるおそれがある。好ましくは、10〜150nmの範囲内である。   The optimum thickness of the vapor-deposited thin film layer 6 varies depending on the type and configuration of the compound used, but is preferably in the range of 5 to 300 nm, and the thickness can be appropriately selected. However, when the film thickness is less than 5 nm, a uniform film cannot be obtained and the film thickness is not sufficient. In the case of an inorganic oxide, when the film thickness exceeds 300 nm, the thin film cannot exhibit flexibility, and the thin film may be cracked due to external factors such as bending and pulling after the film formation. Preferably, it exists in the range of 10-150 nm.

蒸着薄膜層6をプラスチック基材上に形成する方法としては、通常の真空蒸着法により形成することができる。また、その他の薄膜形成方法としてスパッタリング法やイオンプレーティング法、プラズマ気相成長法(PCVD) などを用いることも可能である。生産性を考慮すれば、現時点では真空蒸着法が最も優れる。
真空蒸着法の加熱手段としては電子線加熱方式や抵抗加熱方式、誘導加熱方式のいずれかが好ましい。
また、蒸着薄膜層6と基材5の密着性及び蒸着薄膜層6の緻密性を向上させるために、プラズマアシスト法やイオンビームアシスト法を用いて蒸着することも可能である。また、蒸着膜の透明性を上げるために蒸着の際、酸素ガスなど吹き込む反応蒸着を行ってよい。
As a method of forming the deposited thin film layer 6 on the plastic substrate, it can be formed by a normal vacuum deposition method. Further, as other thin film forming methods, a sputtering method, an ion plating method, a plasma vapor deposition method (PCVD), or the like can be used. Considering productivity, the vacuum deposition method is the best at present.
As a heating means of the vacuum deposition method, any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable.
Moreover, in order to improve the adhesiveness of the vapor deposition thin film layer 6 and the base material 5, and the denseness of the vapor deposition thin film layer 6, it is also possible to vapor-deposit using a plasma assist method or an ion beam assist method. Further, in order to increase the transparency of the deposited film, reactive deposition by blowing oxygen gas or the like may be performed during the deposition.

さらに、ガスバリア層を形成する第2の層である被膜層7を説明する。被膜層7は、水溶性高分子と、(a)1種以上のアルコキシドまたはその加水分解物、または両者、あるいは(b)塩化錫の少なくともいずれか1つを含む水溶液、あるいは水/ アルコール混合溶液を主剤とするコーティング剤を用いて形成される。例えば、水溶性高分子と塩化錫を水系(水或いは水/アルコール混合)溶媒で溶解させた溶液、或いはこれに金属アルコキシドを直接、或いは予め加水分解させるなど処理を行ったものを混合した溶液を調整し溶液とする。この溶液を無機化酸化物からなる蒸着薄膜層6にコーティング後、加熱乾燥し形成される。   Further, the coating layer 7 as the second layer for forming the gas barrier layer will be described. The coating layer 7 is an aqueous solution containing at least one of a water-soluble polymer and (a) one or more alkoxides or hydrolysates thereof, or (b) tin chloride, or a water / alcohol mixed solution. It is formed using the coating agent which uses as a main ingredient. For example, a solution in which a water-soluble polymer and tin chloride are dissolved in an aqueous (water or water / alcohol mixed) solvent, or a solution in which a metal alkoxide is directly or previously hydrolyzed is mixed. Adjust to make a solution. After coating this solution on the vapor-deposited thin film layer 6 made of inorganic oxide, it is formed by heating and drying.

コーティング剤に用いられる水溶性高分子は、ポリビニルアルコール、ポリビニ
ルピロリドン、デンプン、メチルセルロース、カルボキシメチルセルロース、アルギン酸ナトリウム等が挙げられる。特にポリビニルアルコール(PVA)を用いるとガスバリア性が最も優れる。このPVA は、一般にポリ酢酸ビニルをけん化して得られるものであり、酢酸基が数十%残存している、いわゆる部分けん化PVAから酢酸基が数%しか残存していない完全PVA等までを含み、特に限定されない。
Examples of the water-soluble polymer used in the coating agent include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. In particular, when polyvinyl alcohol (PVA) is used, the gas barrier property is most excellent. This PVA is generally obtained by saponifying polyvinyl acetate and includes from so-called partially saponified PVA in which several tens percent of acetic acid groups remain to complete PVA in which only several percent of acetic acid groups remain. There is no particular limitation.

またコーティング剤に用いられる塩化錫は、塩化第一錫(SnCl)、塩化第二錫(SnCl)、或いはそれらの混合物であってもよい。またこれらの塩化錫は、無水物でも水和物でもあってもよい。 The tin chloride used for the coating agent may be stannous chloride (SnCl 2 ), stannic chloride (SnCl 4 ), or a mixture thereof. These tin chlorides may be anhydrous or hydrated.

更にコーティング剤に用いられる金属アルコキシドは、一般式、M(OR)n(M:Si,Ti,Al,Zr等の金属、R:CH,C等のアルキル基)で表せる化合物である。具体的にはテトラエトキシシラン〔Si(OC〕、トリイソプロポキシアルミニウム〔Al(O−2'−C〕などがあげられ、中でもテトラエトキシシラン、トリイソプロポキシアルミニウムが加水分解後、水系の溶媒中において比較的安定であるので好ましい。 Furthermore, the metal alkoxide used for the coating agent is a compound represented by the general formula, M (OR) n (M: metal such as Si, Ti, Al, Zr, R: alkyl group such as CH 3 , C 2 H 5 ). is there. Specific examples include tetraethoxysilane [Si (OC 2 H 5 ) 4 ] and triisopropoxyaluminum [Al (O-2′-C 3 H 7 ) 3 ], among which tetraethoxysilane and triisopropoxy. Aluminum is preferable because it is relatively stable in an aqueous solvent after hydrolysis.

コーティング剤のガスバリア性を損なわない範囲で、イソシアネート化合物、シランカップリング剤、或いは分散剤、安定化剤、粘度調整剤、着色剤などの公知の添加剤を必要に応じて加えることができる。   As long as the gas barrier properties of the coating agent are not impaired, known additives such as isocyanate compounds, silane coupling agents, or dispersants, stabilizers, viscosity modifiers, and colorants can be added as necessary.

例えばコーティング剤に加えられるイソシアネート化合物としては、その分子中に2 個以上のイソシアネート基を有するものが好ましい。例えばトリレンジイソシアネート、トリフェニルメタントリイソシアネート、テトラメチルキシレンジイソシアネートなどのモノマー類と、これらの重合体、誘導体が挙げられる。   For example, the isocyanate compound added to the coating agent is preferably one having two or more isocyanate groups in the molecule. For example, monomers such as tolylene diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, and polymers and derivatives thereof can be mentioned.

コーティング剤の塗布方法には、通常用いられるディッピング法、ロールコーティング法、スクリーン印刷法、スプレー法、グラビア印刷法などの従来公知の手段を用いることができる。被膜の厚さは、コーティング剤の種類や加工機や加工条件によって異なる。乾燥後の厚さが、0.01μm以下の場合は、均一な塗膜が得られず十分なガスバリア性を得られない場合があるので好ましくない。また厚さが50μmを超える場合は膜にクラックが生じ易くなるため問題がある。好ましくは0.01〜50μmの範囲にあることが好ましく、より好ましくは0.1〜10μmの範囲にあることである。   For the coating method of the coating agent, conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method, a gravure printing method and the like that are usually used can be used. The thickness of the coating varies depending on the type of coating agent, processing machine, and processing conditions. When the thickness after drying is 0.01 μm or less, a uniform coating film may not be obtained and sufficient gas barrier properties may not be obtained. Further, when the thickness exceeds 50 μm, there is a problem because cracks are likely to be generated in the film. It is preferably in the range of 0.01 to 50 μm, more preferably in the range of 0.1 to 10 μm.

なお、図3に示すように蒸着薄膜層6、被膜層7上にさらに蒸着薄膜層8、被膜層9を同様に設けることも可能であり、必要に応じて複数層を積層して設けることができる。   In addition, as shown in FIG. 3, it is also possible to provide the vapor deposition thin film layer 8 and the coating layer 9 similarly on the vapor deposition thin film layer 6 and the coating layer 7, and a plurality of layers may be laminated as necessary. it can.

ポリ塩化ビニリデンフィルムの厚みは特に規定されるものではないが、より好ましくは12〜15μm位が望ましい。   The thickness of the polyvinylidene chloride film is not particularly defined, but more preferably about 12 to 15 μm.

熱融着層としては、ポリエチレン、無延伸ポリプロピレン、ポリアクリロニトリル、無延伸ポリエチレンテレフタレート、無延伸ナイロンなどが使用可能である。   As the heat sealing layer, polyethylene, unstretched polypropylene, polyacrylonitrile, unstretched polyethylene terephthalate, unstretched nylon, or the like can be used.

熱融着層として直鎖状低密度ポリエチレンフィルムを用いると、耐突き刺し性、耐屈曲性が高く、シール性も優れているため特に適している。また熱融着層は密度が、0.934g/cm以下の直鎖状低密度ポリエチレンフィルムであることがより好ましい。 When a linear low density polyethylene film is used as the heat-sealing layer, it is particularly suitable because it has high puncture resistance and bending resistance and excellent sealing properties. Further, the heat fusion layer is more preferably a linear low density polyethylene film having a density of 0.934 g / cm 3 or less.

本発明の真空断熱材用積層体を構成する各層の積層方法は、2液硬化型ウレタン系接着剤を用いたドライ・ラミネーションによる方法や、エクストルージョンラミネーションによる方法などが採用できるが、特に指定するものではない。   The method of laminating each layer constituting the laminate for a vacuum heat insulating material of the present invention may be a dry lamination method using a two-component curable urethane adhesive, an extrusion lamination method, or the like. It is not a thing.

このようにして得られる真空断熱材用積層体を用いて真空断熱材を作成することができる。したがって本発明によれば、ガスバリア性が高く、高湿に曝される場所でも断熱性能を維持でき、屈曲によるガスバリア性能の劣化を起こしにくい、真空断熱材用積層体およびそれを用いた真空断熱材を提供することが可能である。   A vacuum heat insulating material can be prepared using the laminate for a vacuum heat insulating material thus obtained. Therefore, according to the present invention, a laminated body for a vacuum heat insulating material that has high gas barrier properties, can maintain heat insulating performance even in a place exposed to high humidity, and is unlikely to cause deterioration of gas barrier performance due to bending, and a vacuum heat insulating material using the same. Can be provided.

以下、本発明の実施例について具体的に説明するが、本発明はこれに限定されるものではない。   Examples of the present invention will be specifically described below, but the present invention is not limited thereto.

(実施例1)
<真空断熱材の外装材の製造>
基材5として、厚さ12μmの2軸延伸ポリエチレンテレフタレート(PET)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、そこに酸素ガスを導入し、厚さ15nmの酸化アルミニウムを蒸着して無機酸化物からなる蒸着薄膜層6を形成した。次いで下記組成からなるコーティング剤をグラビアコート法により塗布し、その後120℃ 1分間乾燥させ厚さ0.5μmの被膜層7を形成しバリアフィルム4とした。コーティング剤の組成は、「1液」と「2液」を配合比(wt%)で60/40に混合したもの。
Example 1
<Manufacture of vacuum insulation materials>
As a base material 5, metal aluminum is evaporated on one side of a biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm by an electron beam heating vacuum deposition apparatus, oxygen gas is introduced therein, and a thickness of 15 nm is introduced. Aluminum oxide was deposited to form a deposited thin film layer 6 made of an inorganic oxide. Next, a coating agent having the following composition was applied by a gravure coating method, and then dried at 120 ° C. for 1 minute to form a coating layer 7 having a thickness of 0.5 μm. The composition of the coating agent is a mixture of “1 liquid” and “2 liquid” in a mixing ratio (wt%) of 60/40.

「1液」:テトラエトキシシラン10.4gに塩酸(0.1N)89.6gを加え、30分間撹拌し加水分解させた固形分3wt%(SiO2換算)の加水分解溶液
「2液」:ポリビニルアルコールの3wt%水/イソプロピルアルコール溶液(水:イソプロピルアルコール重量比で90:10)。
“1 liquid”: Hydrochloric acid solution “2 liquid” having a solid content of 3 wt% (in terms of SiO 2) obtained by adding 89.6 g of hydrochloric acid (0.1N) to 10.4 g of tetraethoxysilane and stirring for 30 minutes for hydrolysis 3 wt% water / isopropyl alcohol solution of alcohol (90:10 by weight of water: isopropyl alcohol).

該バリアフィルムに厚さ12μmのアルミ蒸着ポリエチレンテレフタレートフィルムをウレタン系接着剤を用いて積層、接着した。次いで、アルミ蒸着ポリエチレンテレフタレートフィルムの外面に、厚さ15μmのポリ塩化ビニリデンフィルムをウレタン系接着剤を用いて貼り合せ、更にポリ塩化ビニリデンフィルムの外面に、熱融着層である厚さ40μmの直鎖状低密度ポリエチレンフィルムをウレタン系接着剤を用いて貼り合わせて、真空断熱材用積層体を得た。   An aluminum-deposited polyethylene terephthalate film having a thickness of 12 μm was laminated and bonded to the barrier film using a urethane-based adhesive. Next, a 15 μm-thick polyvinylidene chloride film is bonded to the outer surface of the aluminum vapor-deposited polyethylene terephthalate film using a urethane-based adhesive. A chain low-density polyethylene film was bonded using a urethane adhesive to obtain a laminate for a vacuum heat insulating material.

その後、大気圧、50℃、72時間エージングをして接着剤効果反応を促進させ真空断熱材用積層体を完成させた。   Thereafter, aging was performed at atmospheric pressure and 50 ° C. for 72 hours to promote an adhesive effect reaction, and a laminate for a vacuum heat insulating material was completed.

<真空断熱材の製造>
前記のようにして製造した4辺形の外装材の2枚を、直鎖状低密度ポリエチレンフィルム同士が対向するように重ねて配置し4辺形の3方の端部に、各10mm巾のヒートシールバーにより、前記直鎖状低密度ポリエチレンフィルム同士を熱融着させて150mm×190mmの3方袋に加工した。
不織布を120mm×220mmに切り、100mm×120mmのピロー袋に加工し、多孔質シリカ20gを封入し、芯材を得た。前記3方袋に前記芯材を充填し、前処理乾燥を行った。その後、1.5〜1.6Paに減圧し、減圧を維持したまま3方袋の開口部を10mm巾のインパルスシーラーにより熱融着させて、真空断熱材を製造した。
<Manufacture of vacuum insulation>
Two pieces of the quadrilateral exterior material manufactured as described above are arranged so that the linear low-density polyethylene films are opposed to each other, and the three sides of the quadrilateral are each 10 mm wide. The linear low density polyethylene films were heat-sealed with a heat seal bar and processed into a 150 mm × 190 mm three-sided bag.
The nonwoven fabric was cut into 120 mm × 220 mm, processed into a pillow bag of 100 mm × 120 mm, and 20 g of porous silica was enclosed to obtain a core material. The three-sided bag was filled with the core material and pretreated and dried. Thereafter, the pressure was reduced to 1.5 to 1.6 Pa, and the opening of the three-sided bag was heat-sealed with an impulse sealer having a width of 10 mm while maintaining the reduced pressure to produce a vacuum heat insulating material.

(比較例1)
実施例1において、ポリ塩化ビニリデンフィルムに代えて、厚さ12μmのエチレン−ビニルアルコール共重合体フィルムを使用した他は同様にして真空断熱材を製造した。
(Comparative Example 1)
A vacuum heat insulating material was produced in the same manner as in Example 1 except that a 12 μm thick ethylene-vinyl alcohol copolymer film was used instead of the polyvinylidene chloride film.

(比較例2)
比較例1において、アルミ蒸着ポリエチレンテレフタレートフィルムに代えて、厚さ15μmのアルミ蒸着ポリアミドフィルムを使用した他は同様にして、真空断熱材を製造した。
(Comparative Example 2)
In Comparative Example 1, a vacuum heat insulating material was manufactured in the same manner except that an aluminum-deposited polyamide film having a thickness of 15 μm was used instead of the aluminum-deposited polyethylene terephthalate film.

(比較例3)
比較例1において、アルミ蒸着ポリエチレンテレフタレートフィルムに代えて、厚さ15μmのポリアミドフィルムを使用し、且つ厚さ12μmのエチレン−ビニルアルコール共重合体フィルムに代えて、厚さ12μmのアルミ蒸着エチレン−ビニルアルコール共重合体フィルムを使用した他は同様にして、真空断熱材を製造した。
(Comparative Example 3)
In Comparative Example 1, a polyamide film with a thickness of 15 μm was used instead of the aluminum-deposited polyethylene terephthalate film, and an aluminum-deposited ethylene-vinyl with a thickness of 12 μm was used instead of the ethylene-vinyl alcohol copolymer film with a thickness of 12 μm. A vacuum heat insulating material was produced in the same manner except that an alcohol copolymer film was used.

(比較例4)
比較例3において、上記バリアフィルムに代えて、厚さ25μmのポリアミドフィルムを使用し、且つ厚さ15μmのポリアミドフィルムに代えて、厚さ12μmのアルミ蒸着ポリエチレンテレフタレートフィルムを使用した他は同様にして、真空断熱材を製造した。
(Comparative Example 4)
In Comparative Example 3, a polyamide film having a thickness of 25 μm was used instead of the barrier film, and an aluminum-deposited polyethylene terephthalate film having a thickness of 12 μm was used instead of the polyamide film having a thickness of 15 μm. A vacuum insulation was produced.

(評価)
<ガスバリア性評価>
上記実施例および比較例で得られた真空断熱材の外装材について、ガスバリア性の評価を行った。ガスバリア性の評価はJIS K7129に準じて温度40℃相対湿度差90%における水蒸気透過度の測定を行った。
(Evaluation)
<Gas barrier property evaluation>
Gas barrier properties were evaluated for the vacuum insulation materials obtained in the above Examples and Comparative Examples. The gas barrier property was evaluated by measuring water vapor permeability at a temperature of 40 ° C. and a relative humidity difference of 90% according to JIS K7129.

さらに上記実施例および比較例で得られた真空断熱材の外装材について、耐屈曲性の評価を行った。耐屈曲性の評価は次のようにして行った。
<ゲルボ試験>
210mm×297mmの試験片の297mmの両端を貼り合わせて円筒状に丸め、筒状にした試験片の両端を固定ヘッドと駆動ヘッドで保持し、440度のひねりを加えながら固定ヘッドと駆動ヘッドの間隔を7インチから3.5インチに狭めて、さらにひねりを加えたままヘッドの間隔を1インチまで狭め、その後ヘッドの間隔を3.5インチまで広げて、さらにひねりを戻しながらヘッドの間隔を7インチまで広げるという往復運動を40回/minの速さで、25℃で300回行った。
さらにゲルボ試験を行った試験片について、JIS K7129に準じて温度40℃相対湿度差90%における水蒸気透過度の測定を行った。
Further, the vacuum resistance of the vacuum insulation material obtained in the above examples and comparative examples was evaluated. Evaluation of bending resistance was performed as follows.
<Gelbo test>
The two 297 mm ends of a 210 mm × 297 mm test piece are bonded together and rounded into a cylindrical shape, and both ends of the cylindrical test piece are held by a fixed head and a drive head, and a 440 degree twist is applied to the fixed head and the drive head. Decrease the distance from 7 inches to 3.5 inches, further reduce the head distance to 1 inch with additional twist, then increase the head distance to 3.5 inches, and then adjust the head distance while returning the twist. The reciprocating motion of expanding to 7 inches was performed 300 times at 25 ° C. at a speed of 40 times / min.
Furthermore, about the test piece which performed the gelbo test, the water-vapor-permeation rate in the temperature of 40 degreeC relative humidity difference 90% was measured according to JISK7129.

これらの評価結果を下記表1に示す。   The evaluation results are shown in Table 1 below.

表1を見ると、実施例1のゲルボ試験前の水蒸気透過度は、0.1g/m・day以下であって、比較例と同レベルの値を示した。一方、実施例1のゲルボ試験後の水蒸気透過度は0.19g/m・dayであって、比較例のいずれよりも低い値を示した。これは本発明による真空断熱用積層体にアルミ蒸着フィルムおよび塩化ビニリデンフィルム、
を配置した効果であると考えられる。よって、本発明による真空断熱材用積層体は、高温高湿度下での水蒸気透過度は良好であって、ゲルボ後の水蒸気透過度も、屈曲試験に対する耐性がより良好であることを示している。
When Table 1 was seen, the water-vapor permeability before the gelbo test of Example 1 was 0.1 g / m < 2 > * day or less, and showed the same level value as the comparative example. On the other hand, the water vapor permeability after the gelbo test of Example 1 was 0.19 g / m 2 · day, which was lower than any of the comparative examples. This is because the vacuum-deposited laminate according to the present invention has an aluminum deposited film and a vinylidene chloride film,
It is thought that this is the effect of arranging. Therefore, the laminate for vacuum heat insulating material according to the present invention has good water vapor permeability under high temperature and high humidity, and the water vapor permeability after gelbo also shows better resistance to bending test. .

<内圧測定>
実施例1および比較例1〜4で作製した真空断熱材の内圧、および60℃相対湿度差90%環境で保存した後の内圧を測定した。内圧の測定は、特開昭61−107126に準じて行った。真空チャンバー内に真空断熱材をセットし、真空チャンバー内を減圧すると、真空断熱材の外装材が膨らむ。この外装材の変位を変位センサが検知し、その際のチャンバーの内圧を真空断熱材の内圧として算出した。
<Internal pressure measurement>
The internal pressure of the vacuum heat insulating material produced in Example 1 and Comparative Examples 1 to 4 and the internal pressure after storage in a 90 ° C. relative humidity difference 90% environment were measured. The internal pressure was measured according to JP-A 61-107126. When the vacuum heat insulating material is set in the vacuum chamber and the inside of the vacuum chamber is decompressed, the vacuum heat insulating material is expanded. The displacement sensor detected the displacement of the exterior material, and the internal pressure of the chamber at that time was calculated as the internal pressure of the vacuum heat insulating material.

これらの評価結果を下記表2に示す。   The evaluation results are shown in Table 2 below.

表2を見ると、実施例1は保存期間が20日以上になると、最も低い値を示した。これにより、実施例1は比較例1〜4よりも高湿度下での断熱効果を維持できると言える。 As shown in Table 2, Example 1 showed the lowest value when the storage period was 20 days or more. Thereby, it can be said that Example 1 can maintain the heat insulation effect under higher humidity than Comparative Examples 1-4.

これらの結果から本発明によれば、ガスバリア性が高く、高湿に曝される場所でも断熱性能を維持でき、屈曲によるガスバリア性能の劣化を起こしにくい、真空断熱材用積層体およびそれを用いた真空断熱材を提供することが可能であることを検証することができた。   From these results, according to the present invention, there was used a laminate for a vacuum heat insulating material, which has high gas barrier properties, can maintain heat insulation performance even in a place exposed to high humidity, and hardly causes deterioration of gas barrier performance due to bending, and the same. It was possible to verify that it was possible to provide vacuum insulation.

1・・・真空断熱材
2・・・真空断熱材用積層体
3・・・芯材
4・・・バリアフィルム
5・・・基材
6・・・蒸着薄膜層
7・・・被膜層
8・・・蒸着薄膜層
9・・・被膜層
10・・・アルミ蒸着フィルム
11・・・ポリ塩化ビニリデンフィルム
12・・・熱融着層
13・・・接着層
DESCRIPTION OF SYMBOLS 1 ... Vacuum heat insulating material 2 ... Laminated body 3 for vacuum heat insulating materials ... Core material 4 ... Barrier film 5 ... Base material 6 ... Deposition thin film layer 7 ... Coating layer 8 ..Vapor deposition thin film layer 9 ... Coating layer 10 ... Aluminum vapor deposition film 11 ... Polyvinylidene chloride film 12 ... Heat bonding layer 13 ... Adhesion layer

Claims (6)

断熱芯材を真空断熱材用積層体で被覆し、内部を脱気し真空状態とした真空断熱材に用いられる真空断熱材用積層体において、該真空断熱材用積層体の、水蒸気透過度が0.1g/m・day以下、屈曲後の水蒸気透過度が0.5g/m・day以下であることを特徴とする真空断熱材用積層体。 In a vacuum insulation material laminate used for a vacuum insulation material in which a heat insulation core material is coated with a laminate for vacuum insulation material, and the inside is degassed to be in a vacuum state, the water vapor permeability of the laminate for vacuum insulation material is A laminate for a vacuum heat insulating material, characterized by 0.1 g / m 2 · day or less and a water vapor permeability after bending of 0.5 g / m 2 · day or less. 前記真空断熱材用積層体が、プラスチック基材の少なくとも片面に、金属又は無機酸化物或いはそれらの混合物である蒸着薄膜層を積層したバリアフィルム、アルミ蒸着フィルム、塩化ビニリデンフィルム、熱融着層の順に積層されたことを特徴とする請求項1に記載の真空断熱材用積層体。   The laminate for a vacuum heat insulating material is a barrier film in which a vapor-deposited thin film layer made of a metal, an inorganic oxide, or a mixture thereof is laminated on at least one surface of a plastic substrate, an aluminum vapor-deposited film, a vinylidene chloride film, a heat fusion layer The laminate for a vacuum heat insulating material according to claim 1, wherein the laminate is laminated in order. 前記真空断熱材用積層体が、プラスチック基材の少なくとも片面に、金属又は無機酸化物或いはそれらの混合物である蒸着薄膜層、水溶性高分子と(a)1種以上のアルコキシドまたはその加水分解物、または両者、あるいは(b)塩化錫の少なくともいずれか1つを含む水溶液、あるいは水/アルコール混合溶液を主剤とするコーティング剤からなる被膜層とを積層したバリアフィルム、アルミ蒸着フィルム、塩化ビニリデンフィルム、熱融着層の順に積層されたことを特徴とする請求項1に記載の真空断熱材用積層体。   The laminate for a vacuum heat insulating material is formed on at least one surface of a plastic substrate, a vapor-deposited thin film layer which is a metal or an inorganic oxide or a mixture thereof, a water-soluble polymer and (a) one or more alkoxides or a hydrolyzate thereof , Or both, or (b) a barrier film in which an aqueous solution containing at least one of tin chloride, or a coating layer comprising a coating agent mainly composed of a water / alcohol mixed solution is laminated, an aluminum deposited film, and a vinylidene chloride film The laminated body for a vacuum heat insulating material according to claim 1, wherein the laminated body is laminated in the order of a thermal fusion layer. 前記熱融着層が、直鎖状低密度ポリエチレンフィルムであることを特徴とする請求項1〜請求項3のいずれかに記載の真空断熱材用積層体。   The said heat fusion layer is a linear low density polyethylene film, The laminated body for vacuum heat insulating materials in any one of Claims 1-3 characterized by the above-mentioned. 前記熱融着層の密度が、0.934g/cm以下であることを特徴とする請求項4に記載の真空断熱材用積層体。 The laminate for a vacuum heat insulating material according to claim 4, wherein the density of the heat-fusible layer is 0.934 g / cm 3 or less. 真空断熱材において、前記請求項1〜請求項5のいずれかに記載の真空断熱材用積層体を用いてなることを特徴とする真空断熱材。   In a vacuum heat insulating material, The vacuum heat insulating material formed using the laminated body for vacuum heat insulating materials in any one of the said Claims 1-5.
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WO2020122065A1 (en) * 2018-12-11 2020-06-18 凸版印刷株式会社 Layered body for vacuum thermal insulation material and vacuum thermal insulation material using same

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JP2000320786A (en) * 1999-05-14 2000-11-24 Matsushita Electric Ind Co Ltd Vacuum thermal insulation material
JP2004130654A (en) * 2002-10-10 2004-04-30 Toppan Printing Co Ltd Vacuum heat insulating material
JP2009079762A (en) * 2007-09-06 2009-04-16 Nippon Synthetic Chem Ind Co Ltd:The Vacuum heat insulating structure and its manufacturing method
JP2014035011A (en) * 2012-08-08 2014-02-24 Dainippon Printing Co Ltd Laminate for vacuum heat insulation material
JP2014200964A (en) * 2013-04-03 2014-10-27 凸版印刷株式会社 Exterior material for a vacuum heat insulating material

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JP2000320786A (en) * 1999-05-14 2000-11-24 Matsushita Electric Ind Co Ltd Vacuum thermal insulation material
JP2004130654A (en) * 2002-10-10 2004-04-30 Toppan Printing Co Ltd Vacuum heat insulating material
JP2009079762A (en) * 2007-09-06 2009-04-16 Nippon Synthetic Chem Ind Co Ltd:The Vacuum heat insulating structure and its manufacturing method
JP2014035011A (en) * 2012-08-08 2014-02-24 Dainippon Printing Co Ltd Laminate for vacuum heat insulation material
JP2014200964A (en) * 2013-04-03 2014-10-27 凸版印刷株式会社 Exterior material for a vacuum heat insulating material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020122065A1 (en) * 2018-12-11 2020-06-18 凸版印刷株式会社 Layered body for vacuum thermal insulation material and vacuum thermal insulation material using same
CN113474589A (en) * 2018-12-11 2021-10-01 凸版印刷株式会社 Laminate for vacuum insulation material and vacuum insulation material using same
EP3896325A4 (en) * 2018-12-11 2022-01-26 Toppan Printing Co., Ltd. Layered body for vacuum thermal insulation material and vacuum thermal insulation material using same

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