JPH08338683A - Vacuum insulation material - Google Patents
Vacuum insulation materialInfo
- Publication number
- JPH08338683A JPH08338683A JP8091519A JP9151996A JPH08338683A JP H08338683 A JPH08338683 A JP H08338683A JP 8091519 A JP8091519 A JP 8091519A JP 9151996 A JP9151996 A JP 9151996A JP H08338683 A JPH08338683 A JP H08338683A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- vacuum
- gas
- absorbent
- heat insulating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y02B80/12—
Landscapes
- Thermal Insulation (AREA)
- Refrigerator Housings (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、冷凍機、冷蔵庫等に使
用される真空断熱材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vacuum heat insulating material used in refrigerators, refrigerators and the like.
【0002】[0002]
【従来の技術】これまでに冷蔵庫、冷凍庫等の断熱材と
して、プラスチックフイルム等よりなるガスバリア性の
ある密閉された容器(以下「ガスバリア性密閉容器」と
称す)内に、形状維持や対流防止のためのコア材(また
は骨材という)としてパーライト等の無機材料や発泡ポ
リウレタン等の有機材料を、1torr以下の真空度で
真空包装し、熱伝導率0.01kcal/m.h.℃以
下にした真空断熱材が考えられている。しかしこれらの
真空断熱材は、わずかではあるが空気、水分がガスバリ
ア性密閉容器内に侵入し、時間の経過とともにガスバリ
ア性密閉容器内の真空度が少しずつ低下し、それに応じ
て熱伝導率が大きくなり、高度な断熱性を維持できない
という問題があった。またコア材として発泡ポリウレタ
ン等を用いた系では、コア材製造時の溶媒や発泡のため
に使用されたガス、あるいはコア材自身が分解して発生
する炭酸ガスなどの酸性ガスがガスバリア性密閉容器内
の真空度を低下させていた。このようにしてガスバリア
性密閉容器内に空気、水分が侵入し、あるいは酸性ガス
等が発生すると真空度が低下し、真空断熱材としての性
能が徐々に損なわれ、冷凍庫や冷蔵庫の場合、結果的に
使用電力が増し、ランニングコストの高いものとなって
いた。2. Description of the Related Art Up to now, as a heat insulating material for refrigerators, freezers, etc., a shape-containing and convection-preventing structure has been used in a sealed container having a gas barrier property (hereinafter referred to as "gas barrier closed container") made of a plastic film or the like. As a core material (or aggregate) for this purpose, an inorganic material such as pearlite or an organic material such as foamed polyurethane is vacuum-packed at a vacuum degree of 1 torr or less to obtain a thermal conductivity of 0.01 kcal / m. h. A vacuum heat insulating material having a temperature of ℃ or less is considered. However, in these vacuum insulation materials, air and moisture intrude into the gas-barrier closed container to a small extent, and the degree of vacuum in the gas-barrier closed container gradually decreases with the passage of time. There was a problem that it became large and it was not possible to maintain a high degree of heat insulation. Further, in a system using polyurethane foam or the like as the core material, the gas used for the solvent during the production of the core material, the gas used for foaming, or the acidic gas such as carbon dioxide gas generated by the decomposition of the core material itself is a gas barrier closed container. The degree of vacuum inside was lowered. In this way, when air and moisture enter the gas-barrier closed container, or when acidic gas or the like is generated, the degree of vacuum is lowered, and the performance as a vacuum heat insulating material is gradually impaired. Moreover, the power consumption was increased and the running cost was high.
【0003】これら諸問題を解決する従来の技術として
は、特開昭58ー104081公報にパーライト等の多
孔質骨材と空気を吸着するモレキュラーシーブス等の吸
着材の混合物を充填し、かつ内部を真空引きしたガスバ
リア性密閉容器からなる断熱材が開示されている。しか
し開示された吸着性物質は事実上水分のみを吸着しほと
んど空気を吸着しない欠点があった。As a conventional technique for solving these problems, Japanese Patent Application Laid-Open No. 58-104081 discloses that a mixture of a porous aggregate such as pearlite and an adsorbent such as molecular sieves that adsorbs air is filled and the inside is filled. A heat insulating material including a vacuumed gas-barrier closed container is disclosed. However, the disclosed adsorptive substance has a drawback that it adsorbs practically only water and hardly adsorbs air.
【0004】特開昭59ー225275公報にはシリカ
ゲル、ゼオライト等の水分吸着物質が開示されている。
しかしこれらの水分吸着物質は単に吸着により水分を除
去するものであるため、吸着した水分が時間の経過や、
温度の変化により離脱する欠点があった。Japanese Patent Application Laid-Open No. 59-225275 discloses a moisture adsorbing substance such as silica gel and zeolite.
However, since these water-adsorbing substances simply remove water by adsorption, the adsorbed moisture may be
There was a defect that it detached due to changes in temperature.
【0005】また特開昭63ー105392公報には断
熱材に鉄粉が添加含有されている真空断熱材が開示され
ている。しかしこの場合の鉄粉と酸素の反応には水分が
必要であり、鉄粉上に水分が存在しない場合は酸素吸収
反応が生起しないという問題があった。また反応を十分
に進行させるために鉄粉に予め水分を存在させるとかえ
って真空断熱材中で水分が気化し、逆にガスバリア性密
閉容器内の真空度が悪化し真空断熱材の断熱性能の低下
を招くという欠点があった。Further, Japanese Patent Laid-Open No. 63-105392 discloses a vacuum heat insulating material containing iron powder added to the heat insulating material. However, in this case, the reaction between the iron powder and oxygen requires water, and there is a problem that the oxygen absorption reaction does not occur if there is no water on the iron powder. In addition, if water is present in the iron powder in advance in order to allow the reaction to proceed sufficiently, the water vaporizes in the vacuum heat insulating material, conversely the vacuum degree in the gas barrier closed container deteriorates and the heat insulating performance of the vacuum heat insulating material deteriorates. There was a drawback of inviting.
【0006】[0006]
【発明が解決しようとする課題】本発明は、真空断熱材
の断熱性能の低下を抑制し本来有している断熱性能を維
持する真空断熱材を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a vacuum heat insulating material which suppresses the deterioration of the heat insulating performance of the vacuum heat insulating material and maintains the heat insulating performance originally possessed.
【0007】[0007]
【課題を解決するための手段】本発明者らは、酸素の吸
収に水分を必要としない酸素吸収剤、脱湿剤と酸性ガス
吸収剤を併用することにより、上記目的を達成すること
ができることを見い出した。つまり、真空断熱材中に侵
入する酸素、水分及び発生する炭酸ガスなどの酸性ガス
を除去することで、真空度の低下を防止し、断熱性能を
維持できることを見い出した。本発明はガスバリア性密
閉容器内に骨材となるコア材及び酸素の吸収に水分を必
要としない酸素吸収剤、脱湿剤と酸性ガス吸収剤を封
入、または添加することを特徴とする真空断熱材であ
る。すなわち、本発明は、ガスバリア性密閉容器、コア
材、酸素の吸収に水分を必要としない酸素吸収剤、脱湿
剤と酸性ガス吸収剤から構成される真空断熱材である。
また本発明は、酸素の吸収に水分を必要としない酸素吸
収剤が、不飽和脂肪酸化合物および/または不飽和基を
有する鎖状炭化水素重合物の主剤と酸素吸収促進物質を
含む酸素吸収剤である。また、本発明は、酸性ガス吸収
剤がアルカリ金属またはアルカリ土類金属の酸化物、水
酸化物、炭酸塩、有機酸塩、有機アミン類より選ばれる
少なくとも一種以上である。Means for Solving the Problems The present inventors can achieve the above object by using an oxygen absorbent, a dehumidifying agent and an acid gas absorbent which do not require water for absorbing oxygen. Found out. That is, it has been found that by removing oxygen, moisture, and generated acid gases such as carbon dioxide gas that enter the vacuum heat insulating material, it is possible to prevent the vacuum degree from lowering and maintain the heat insulating performance. The present invention is a vacuum insulation characterized by enclosing or adding a core material as an aggregate and an oxygen absorbent, a dehumidifying agent and an acid gas absorbent which do not require water to absorb oxygen, in a gas barrier closed container. It is a material. That is, the present invention is a vacuum heat insulating material including a gas barrier closed container, a core material, an oxygen absorbent that does not require moisture to absorb oxygen, a dehumidifying agent and an acidic gas absorbent.
Further, the present invention is an oxygen absorbent which does not require water for absorbing oxygen, wherein the oxygen absorbent contains a main component of a chain hydrocarbon polymer having an unsaturated fatty acid compound and / or an unsaturated group and an oxygen absorption promoter. is there. In the present invention, the acidic gas absorbent is at least one selected from oxides, hydroxides, carbonates, organic acid salts and organic amines of alkali metals or alkaline earth metals.
【0008】[0008]
【発明の実施の形態】本発明に用いられる酸素吸収剤の
主剤は酸素の吸収に水分を必要としないものであれば特
に制限を受けるものではないが、不飽和脂肪酸化合物や
不飽和基を有する鎖状炭化水素等の不飽和有機化合物、
ポリアミドやポリオレフィン等の熱可塑性重合物を主剤
とし、遷移金属塩等の酸素吸収促進物質を含む酸素吸収
剤が例示されるが、不飽和脂肪酸化合物および/または
不飽和基を有する鎖状炭化水素重合物を主剤とし、酸素
吸収促進物質を含む酸素吸収剤が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The main agent of the oxygen absorbent used in the present invention is not particularly limited as long as it does not require water to absorb oxygen, but it has an unsaturated fatty acid compound or an unsaturated group. Unsaturated organic compounds such as chain hydrocarbons,
Examples of the oxygen absorber include a thermoplastic polymer such as polyamide or polyolefin as a main agent and an oxygen absorption promoter such as a transition metal salt. An unsaturated fatty acid compound and / or a chain hydrocarbon polymerization having an unsaturated group An oxygen absorbent containing a substance as a main agent and containing an oxygen absorption promoting substance is preferable.
【0009】ここで用いられる不飽和脂肪酸化合物は、
炭素数が10以上で炭素間に2重結合を持った不飽和脂
肪酸、または、該不飽和脂肪酸の塩もしくはエステルで
ある。炭素数が10以下の場合は、低圧にした場合、そ
の蒸気圧が無視できなくなり十分に圧力が低下せずに不
都合である。該不飽和脂肪酸およびその脂肪酸の塩もし
くはエステルには、置換基、例えば水酸基、ホルミル基
等を有していても良い。また、不飽和脂肪酸化合物は必
ずしも純物質である必要はない。The unsaturated fatty acid compound used here is
It is an unsaturated fatty acid having 10 or more carbon atoms and having a double bond between carbons, or a salt or ester of the unsaturated fatty acid. When the carbon number is 10 or less, when the pressure is reduced to a low pressure, the vapor pressure cannot be ignored and the pressure is not sufficiently lowered, which is inconvenient. The unsaturated fatty acid and the salt or ester of the fatty acid may have a substituent such as a hydroxyl group and a formyl group. Further, the unsaturated fatty acid compound does not necessarily have to be a pure substance.
【0010】不飽和脂肪酸化合物の例として、オレイン
酸、リノール酸、リノレン酸、アラキドン酸、パリナリ
ン酸、ダイマー酸、またはリシノール酸等の不飽和脂肪
酸、およびこれらのエステルを含有する大豆油、桐油、
アマニ油、ゴマ油、綿実油等の油脂、エステル類、金属
塩が挙げられる。また、不飽和脂肪酸として植物油、動
物油から得られる脂肪酸、すなわち、アマニ油脂肪酸、
大豆油脂肪酸、桐油脂肪酸、糠油脂肪酸、胡麻油脂肪
酸、綿実油脂肪酸、菜種油脂肪酸、トール油脂肪酸等も
用いられる。これらの不飽和脂肪酸化合物は、単独で用
いてもよいし2種類以上混合してもよい。Examples of unsaturated fatty acid compounds include unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, parinaric acid, dimer acid, and ricinoleic acid, and soybean oil, tung oil containing these esters,
Examples include oils and fats such as linseed oil, sesame oil, cottonseed oil, esters, and metal salts. Moreover, vegetable oil as an unsaturated fatty acid, a fatty acid obtained from animal oil, that is, linseed oil fatty acid,
Soybean oil fatty acid, tung oil fatty acid, bran oil fatty acid, sesame oil fatty acid, cottonseed oil fatty acid, rapeseed oil fatty acid, tall oil fatty acid and the like are also used. These unsaturated fatty acid compounds may be used alone or in combination of two or more.
【0011】また、不飽和基を有する鎖状炭化水素重合
物とは、炭素数10以上で炭素原子間に2重結合を1つ
以上を有した重合物およびその誘導体である。炭素数が
10以下の場合は、不飽和脂肪酸化合物の場合と同様に
低圧にした場合、その蒸気圧が無視できなくなり十分に
圧力が低下せずに不都合である。該誘導体は、置換基と
して、例えば水酸基、アミノ基、ホルミル基、カルボキ
シル基等が存在しても良い。不飽和基を有する鎖状炭化
水素重合物を例示すれば、ブタジエン、イソプレン、
1,3ペンタジエンなどのオリゴマーや重合体あるいは
共重合体が挙げられる。これらの不飽和基を有する鎖状
炭化水素重合物は、単独で用いてもよいし2種類以上を
混合して用いてもよい。不飽和基を有する鎖状炭化水素
重合物は、必ずしも純物質である必要はなく、その製造
時に混入してくる溶媒などの不純物は、常識的な範囲で
許容される。The chain hydrocarbon polymer having an unsaturated group is a polymer having 10 or more carbon atoms and at least one double bond between carbon atoms and its derivatives. When the number of carbon atoms is 10 or less, the vapor pressure cannot be ignored and the pressure is not sufficiently lowered, which is inconvenient, when the pressure is set to a low pressure as in the case of the unsaturated fatty acid compound. The derivative may have, for example, a hydroxyl group, an amino group, a formyl group or a carboxyl group as a substituent. Examples of the chain hydrocarbon polymer having an unsaturated group include butadiene, isoprene,
Examples thereof include oligomers, polymers and copolymers such as 1,3 pentadiene. These chain hydrocarbon polymers having an unsaturated group may be used alone or in combination of two or more. The chain hydrocarbon polymer having an unsaturated group does not necessarily have to be a pure substance, and impurities such as a solvent mixed during the production thereof are allowed within a common sense.
【0012】本発明に用いられる主剤の酸素吸収を促進
する物質としては、有機化合物の酸化を促進する金属塩
やラジカル開始剤を例示することができる。金属塩とし
ては、Cu、Fe、Co、Ni、Cr、Mn等の遷移金
属塩が好ましく、遷移金属塩として、例えば不飽和脂肪
酸金属塩が好適に用いられる。Examples of the substance that promotes the oxygen absorption of the main agent used in the present invention include metal salts and radical initiators that promote the oxidation of organic compounds. As the metal salt, transition metal salts such as Cu, Fe, Co, Ni, Cr and Mn are preferable, and as the transition metal salt, for example, unsaturated fatty acid metal salt is preferably used.
【0013】本発明で主剤及び酸素吸収促進物質が液状
物質である場合はこれらを担持させることが好ましく、
担体物質としては、天然パルプ、合成パルプからなる紙
や合成紙、不織布、多孔フイルム、シリカゲル、アルミ
ナ、活性炭、モレキュラーシーブス等の合成ゼオライ
ト、モルデナイト、エリオナイト等の天然ゼオライト、
パーライト、活性白土等の粘土鉱物等が例示される。ま
た担体物質として、脱湿剤に使用するものを選び、担体
に脱湿能をもたせることも実用的な使用方法であり、ま
た担体としてコア材に液状の主剤及び酸素吸収促進物質
を直接担持させることもできる。In the present invention, when the main agent and the oxygen absorption promoting substance are liquid substances, it is preferable to support them.
As the carrier substance, natural pulp, paper or synthetic paper made of synthetic pulp, non-woven fabric, porous film, silica gel, alumina, activated carbon, synthetic zeolite such as molecular sieves, mordenite, natural zeolite such as erionite,
Examples include clay minerals such as pearlite and activated clay. It is also a practical use method to select a carrier substance to be used as a dehumidifying agent and to make the carrier have a dehumidifying ability. Further, as the carrier, the core material directly carries the liquid main component and the oxygen absorption promoting substance. You can also
【0014】酸素吸収剤における各成分の割合は、用い
る物質の種類により適宜選ばれるが、主剤100重量部
に対し、酸化促進物質は、0.01〜40重量部、好ま
しくは0.1〜10重量部の範囲であり、担体物質は、
1〜5000重量部、好ましくは10〜1000重量部
の範囲である。The proportion of each component in the oxygen absorbent is appropriately selected depending on the type of substance used, but 0.01 to 40 parts by weight, preferably 0.1 to 10 parts by weight of the oxidation promoting substance relative to 100 parts by weight of the main agent. Parts by weight and the carrier material is
It is in the range of 1 to 5000 parts by weight, preferably 10 to 1000 parts by weight.
【0015】本発明に用いられる酸素吸収剤、脱湿剤及
び酸性吸収剤は混合して用いても良いし別々の状態で分
けて用いても良い。これらは適宜、粉状、粒状、錠剤
状、シート状等の形態で用いられる。これらは包装材料
で包まずに直接コア材中に添加される場合もあるが、取
扱いを容易にするため通常は例えば紙又は不織布を基材
とする通気性包装材料で包装された包装体としてガスバ
リア性容器内に封入される。包装体の形態は、特に限定
されるものではないが、目的に応じて、小袋状、シート
状、ブリスター包装した形態が選ばれる。The oxygen absorbent, the dehumidifying agent and the acidic absorbent used in the present invention may be mixed and used, or may be used separately in different states. These are appropriately used in the form of powder, granules, tablets, sheets and the like. These may be added directly to the core material without being wrapped with a packaging material, but for ease of handling, they are usually gas barriers, for example, as a package packaged with a breathable packaging material based on paper or nonwoven fabric. It is enclosed in a sex container. The form of the package is not particularly limited, but a pouch, a sheet, or a blister-wrapped form is selected according to the purpose.
【0016】本発明で用いられる脱湿剤としては、天然
パルプ、合成パルプからなる紙や合成紙、シリカゲル、
アルミナ、活性炭、ゼオライト、パーライト、活性白
土、生石灰、酸化バリウム、塩化カルシウム、臭化バリ
ウム、硫酸カルシウム、塩化マグネシウム、酸化マグネ
シウム、硫酸マグネシウム、硫酸アルミニウム、硫酸ナ
トリウム、炭酸ナトリウム、炭酸カリウム、塩化亜鉛等
が例示される。The dehumidifying agent used in the present invention includes paper made of natural pulp and synthetic pulp, synthetic paper, silica gel,
Alumina, activated carbon, zeolite, perlite, activated clay, quick lime, barium oxide, calcium chloride, barium bromide, calcium sulfate, magnesium chloride, magnesium oxide, magnesium sulfate, aluminum sulfate, sodium sulfate, sodium carbonate, potassium carbonate, zinc chloride, etc. Is exemplified.
【0017】本発明で用いられる酸性ガス吸収剤として
は、主剤の反応やコア材より発生する酸性ガスやガスバ
リア性密閉容器内に侵入してくる酸性ガスを吸収又は吸
着できる物質であればよく、例えば、アルカリ金属また
はアルカリ土類金属の酸化物、水酸化物、炭酸塩、有機
酸塩、有機アミン類が用いられる。また、上記の担体物
質又は脱湿剤に酸性ガス吸収剤を選びその機能をもたせ
ることもでき、この場合には改めて酸性ガス吸収剤を加
える必要はない。The acidic gas absorbent used in the present invention may be any substance capable of absorbing or adsorbing the acidic gas generated from the reaction of the main agent or the core material and the acidic gas penetrating into the gas barrier closed container, For example, oxides, hydroxides, carbonates, organic acid salts and organic amines of alkali metals or alkaline earth metals are used. It is also possible to select an acidic gas absorbent as the above-mentioned carrier substance or dehumidifying agent and to make it function, and in this case, it is not necessary to add the acidic gas absorbent again.
【0018】本発明に用いられるコア材としては、ポリ
ウレタンやポリスチレン等のプラスチックの連続発泡
体、シリカ、珪藻土、パーライト、炭酸マグネシウム、
珪酸カルシウム等の無機質微粉末、珪酸カルシウム板や
アスベスト板等の多孔質成形板並びにガラス繊維やセラ
ミック繊維やポリエステル繊維などの繊維状物が例示さ
れ、中でもシリカ粉末あるいはポリウレタンの連続発泡
体が好ましい。これらのコア材は一種で用いてもかまわ
ないし、必要に応じて複数種用いることも可能である。Examples of the core material used in the present invention include continuous foams of plastics such as polyurethane and polystyrene, silica, diatomaceous earth, perlite, magnesium carbonate,
Examples include inorganic fine powders such as calcium silicate, porous molded plates such as calcium silicate plates and asbestos plates, and fibrous substances such as glass fibers, ceramic fibers, and polyester fibers. Among them, silica powder or polyurethane continuous foam is preferable. One kind of these core materials may be used, or a plurality of kinds may be used if necessary.
【0019】本発明に用いられるガスバリア性密閉容器
は、ポリ塩化ビニリデン、ポリビニルアルコール、ポリ
エステル、ポリプロピレン、ポリアミド、ポリエチレン
等にアルミニウムなどの金属箔ないしは金属、酸化珪素
などを蒸着したフィルムを、少なくとも一種以上、一層
以上ラミネートしたものが使用される。また最内層のシ
ーラント材としてはポリエチレン、ポリプロピレン等の
ヒートシール可能な樹脂が使用される。The gas barrier airtight container used in the present invention is at least one kind of a film obtained by vapor-depositing a metal foil such as aluminum or a metal foil such as polyvinylidene chloride, polyvinyl alcohol, polyester, polypropylene, polyamide, polyethylene, etc., or silicon oxide. A laminate of more than one layer is used. A heat-sealable resin such as polyethylene or polypropylene is used as the innermost layer sealant material.
【0020】酸素吸収剤、脱湿剤及び酸性ガス吸収剤の
使用量はガスバリア性密閉容器のガスバリア性能、コア
材の種類に応じて適宜選ばれる。酸素吸収剤は、少なく
ともガスバリア性密閉容器内の空間容積の酸素及びガス
バリア性密閉容器内に侵入してくる酸素を吸収すること
が出来る量であり、コア材100重量部に対し0.1〜
10重量部、好ましくは0.5〜5重量部が使用され
る。また、脱湿剤は少なくともガスバリア性密閉容器内
の空間容積の水分及びガスバリア性密閉容器内に侵入し
てくる水分を吸収することができる量であり、コア材1
00重量部に対し0.5〜50重量部、好ましくは1〜
20重量部が使用される。酸性ガス吸収剤は少なくとも
ガスバリア性密閉容器内の空間容積の酸性ガス、ガスバ
リア性密閉容器内に侵入してくる酸性ガス及び酸素吸収
剤やコア材等から発生する酸性ガスを吸収することがで
きる量であり、コア材100重量部に対し0.5〜20
重量部、好ましくは1〜10重量部が使用される。The amounts of the oxygen absorbent, the dehumidifying agent and the acid gas absorbent used are appropriately selected depending on the gas barrier performance of the gas barrier closed container and the type of the core material. The oxygen absorbent is an amount capable of absorbing at least oxygen in the space volume in the gas barrier closed container and oxygen invading the gas barrier closed container, and is 0.1 to 100 parts by weight of the core material.
10 parts by weight, preferably 0.5-5 parts by weight are used. Further, the dehumidifying agent is an amount capable of absorbing at least the water in the space volume in the gas barrier closed container and the water entering the gas barrier closed container.
0.5 to 50 parts by weight, preferably 1 to 100 parts by weight
20 parts by weight are used. The amount of acid gas absorbent can absorb at least the space gas in the gas barrier closed container, the acid gas entering the gas barrier closed container and the acid gas generated from the oxygen absorbent or core material. Is 0.5 to 20 with respect to 100 parts by weight of the core material.
Parts by weight, preferably 1 to 10 parts by weight are used.
【0021】[0021]
【実施例】以下に本発明の具体的実施例を示し、本発明
をさらに詳細に説明する。なお、本発明は実施例に限定
されるものではない。なお熱伝導率の測定は昭和電工
(株)製QTM型熱伝導率計を用いて、13℃と35℃
との温度差における熱伝導率を測定した。EXAMPLES The present invention will be described in more detail below by showing specific examples of the present invention. The present invention is not limited to the embodiments. The thermal conductivity was measured using Showa Denko Co., Ltd. QTM type thermal conductivity meter at 13 ° C and 35 ° C.
The thermal conductivity was measured at the temperature difference between and.
【0022】(実施例1)大豆油1g、ナフテン酸コバ
ルト0.2gの混合物にゼオライト3.5gを加えブレ
ンダーで混合後25℃で10分間静置し、流動性のある
粉粒体を得た。得られた粉粒体4.7gと生石灰2.5
g、消石灰1.0gとを混合した。これをゲッタとす
る。上記ゲッタ5重量部を複数の通気細孔を有するポリ
エチレンテレフタレート/ポリプロピレンよりなる小袋
に充填して開口部をヒートシールし、ゲッタ包装袋とし
たものを、コア材である乾燥したパーライト粉末(平均
粒径3マイクロ)100重量部と共に、延伸ポリプロピ
レン/アルミ蒸着ポリエチレンテレフタレート/ポリエ
チレンよりなるバリア性容器に入れ、これをヒートシー
ル装置を具備した真空包装装置内において0.1tor
rの真空度に排気した状態で、袋の開口部をヒートシー
ルして密封し、サイズ300×300mm、厚さ20m
mの真空断熱材を得た。この真空断熱材を40℃、95
%RHの雰囲気に90日間放置した後の熱伝導率を測定
した結果を表1に示す。Example 1 To a mixture of 1 g of soybean oil and 0.2 g of cobalt naphthenate, 3.5 g of zeolite was added, mixed with a blender and allowed to stand at 25 ° C. for 10 minutes to obtain a fluid granular material. . Obtained powder and granules 4.7 g and quick lime 2.5
g and 1.0 g of slaked lime were mixed. This is a getter. 5 parts by weight of the getter was filled in a small bag made of polyethylene terephthalate / polypropylene having a plurality of air-permeable pores, the opening was heat-sealed, and a getter packaging bag was obtained by using dried perlite powder (average particles) as a core material. (3 micron diameter) 100 parts by weight, and put in a barrier container made of stretched polypropylene / aluminum-deposited polyethylene terephthalate / polyethylene, and 0.1 torr in a vacuum packaging device equipped with a heat-sealing device.
While evacuating to a vacuum degree of r, the opening of the bag is heat-sealed and sealed, and the size is 300 × 300 mm and the thickness is 20 m.
m vacuum insulation was obtained. This vacuum insulation material is 40 ℃, 95
Table 1 shows the results of measuring the thermal conductivity after leaving it in the atmosphere of% RH for 90 days.
【0023】(実施例2〜10)表1に記載した構成で
実施例1と同様に真空断熱材を得て、熱伝導率を測定し
た結果を表1に示す。(Examples 2 to 10) A vacuum heat insulating material having the structure shown in Table 1 was obtained in the same manner as in Example 1, and the results of measuring the thermal conductivity are shown in Table 1.
【0024】(比較例1〜5)表2に記載した構成で実
施例1と同様に真空断熱材を得て、熱伝導率を測定した
結果を表2に示す。表1、表2から明らかなように40
℃、95%RHの雰囲気に90日間放置した場合、本発
明の酸素吸収剤を配置または添加含有した真空断熱材の
熱伝導率の変化は僅かであり、断熱性能の劣化に対して
優れた効果を有することが明らかである。(Comparative Examples 1 to 5) Vacuum heat insulating materials having the constitutions shown in Table 2 were obtained in the same manner as in Example 1 and the results of measuring the thermal conductivity are shown in Table 2. As apparent from Tables 1 and 2, 40
When left in an atmosphere of 90 ° C. and 95% RH for 90 days, the change in the thermal conductivity of the vacuum heat insulating material in which the oxygen absorbent of the present invention is arranged or added is slight, which is an excellent effect on the deterioration of the heat insulating performance. It is clear that
【0025】実施例1〜実施例13を表1に示す。Table 1 shows Examples 1 to 13.
【表1】表1 実施例1 実施例2 実施例3 実施例4 実施例5 主剤 大豆油 トール 油脂 大豆油 トール 油脂 胡麻油 0.61 肪酸0.61 0.61 肪酸0.61 0.05 酸素吸収 ナフテン酸Co ナフテン酸Co トール 油脂 トール 油脂 トール 油脂 促進物質 0.12 0.12 肪酸Co 0.12 肪酸Co 0.02 肪酸Mn 0.02 担体物質 ゼオライト ゼオライト ゼオライト ゼオライト 酸化アルミ 2.1 2.1 2.1 0.9 0.5 脱湿剤 生石灰 生石灰 生石灰 セ゛オライト セ゛オライト 1.5 1.5 1.5 5.0 0.5 酸性ガス 消石灰 消石灰 消石灰 生石灰 生石灰 吸収剤 0.61 0.61 0.61 6.5 0.5 ケ゛ッタ の包装 小袋包装 小袋包装 小袋包装 小袋包装 小袋包装 コア材 パーライト パーライト パーライト ホ゜リウレタン 微粉シリカ 100 100 100 100 100 初期熱伝導率 0.005 0.005 0.005 0.005 0.005 40℃,95%RH 90日放置後 0.006 0.006 0.006 0.006 0.006 熱伝導率の単位:Kcal/m.h.℃ 主剤等の単位 :重量部 ポリウレタン :ポリウレタンの連続発泡体 表1続き 実施例6 実施例7 実施例8 実施例9 実施例10 主剤 綿実油 アマニ 油 オレイン酸 リノール酸 リノレン酸 0.05 0.05 0.61 0.61 0.61 酸素吸収 ナフテン酸Co ナフテン酸Co オクチル酸Co オクチル酸Mn オレイン酸Fe 促進物質 0.001 0.0002 0.12 0.12 0.12 担体物質 ゼオライト ゼオライト ゼオライト ゼオライト ゼオライト 0.5 0.5 2.1 2.1 2.1 脱湿剤 セ゛オライト セ゛オライト セ゛オライト 活性炭 塩化Ca 0.5 0.5 30 1.5 1.5 酸性ガス 生石灰 生石灰 酸化Mg 塩化Mg 水酸化Na 吸収剤 0.5 0.5 0.61 20 0.61 ケ゛ッタ の包装 小袋包装 小袋包装 小袋包装 小袋包装 小袋包装 コア材 ポリウレタン ポリウレタン パーライト パーライト パーライト 100 100 100 100 100 初期熱伝導率 0.005 0.005 0.007 0.005 0.005 40℃,95%RH 90日放置後 0.006 0.007 0.008 0.007 0.007 熱伝導率の単位:Kcal/m.h.℃ 主剤等の単位 :重量部 表1続き 実施例11 実施例12 実施例13 主剤 大豆油/液状イソフ゜レン 大豆油/液状フ゛タシ゛エン 大豆油 0.61 0.61 0.61 酸素吸収 ナフテン酸Co ナフテン 酸Co ナフテン酸Co 促進物質 0.12 0.12 0.12 担体物質 セ゛オライト セ゛オライト セ゛オライト 2.1 2.1 2.1 脱湿剤 生石灰 生石灰 生石灰 1.5 1.5 1.5 酸性ガス 消石灰 消石灰 消石灰 吸収剤 0.61 0.61 0.61 ケ゛ッタ の包装 小袋包装 小袋包装 小袋にせず コア材 ハ゜ーライト ハ゜ーライト ハ゜ーライト 100 100 100 初期熱伝導率 0.005 0.005 0.005 40℃,95%RH 90日放置後 0.006 0.006 0.006 熱伝導率の単位:Kcal/m.h.℃ 主剤等の単位 :重量部[Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Main ingredient Soybean oil Tall oil and fat Soybean oil Tall oil and fat Sesame oil 0.61 Fatty acid 0.61 0.61 Fatty acid 0.61 0.05 Oxygen absorption Naphthenic acid Co Naphthenic acid Co tall oil and fat Thor oil and fat Thor oil and fat promoting substance 0.12 0.12 Fatty acid Co 0.12 Fatty acid Co 0.02 Fatty acid Mn 0.02 Carrier material Zeolite Zeolite Zeolite Zeolite Aluminum oxide 2.1 2.1 2.1 0.9 0.5 Dehumidifying agent Quick lime Quick lime Quick lime Zeolite Zeolite 1.5 1.5 1.5 5.0 0.5 Acid gas Slaked lime Slaked lime Slaked lime Quick lime Quick lime absorbent 0.61 0.61 0.61 6.5 0.5 Ghetter wrapping Pouch wrap Pouch wrap Pouch wrap Pouch wrap Pouch wrap Core material Perlite Perlite Perlite Polyurethane Polyurethane Fine silica 100 100 100 100 100 Initial thermal conductivity 0.005 0.005 0.005 0.005 0.005 40 ° C, 95% RH 90 days left 0.006 0.006 0.006 0.006 0.006 Thermal conductivity unit: Kcal / m . h. Unit of main agent etc .: parts by weight Polyurethane: continuous foam of polyurethane Table 1 Continuation Example 6 Example 7 Example 8 Example 9 Example 10 Main agent Cottonseed oil Linseed oil Oleic acid Linoleic acid Linolenic acid 0.05 0.05 0.61 0.61 0.61 Oxygen absorption Naphthenic acid Co Naphthenic acid Co Octylic acid Co Octylic acid Mn Oleic acid Fe promoting substance 0.001 0.0002 0.12 0.12 0.12 Support material Zeolite Zeolite Zeolite Zeolite 0.5 0.5 2.1 2.1 2.1 Dehumidifying agent Zeolite Zeolite Activated carbon Ca 0.5 0.5 30 1.5 1.5 Acid gas Quick lime Quick lime Oxidized Mg Chloride Mg Absorbed sodium hydroxide 0.5 0.5 0.61 20 0.61 Getta packaging Pouch packaging Pouch packaging Pouch packaging Pouch packaging Pouch packaging Core material Polyurethane Polyurethane Perlite Perlite Perlite 100 100 100 100 100 Initial thermal conductivity 0.005 0.005 0.007 0.005 0.005 40 ℃, 95% RH 90 days after leaving 0. 006 0.007 0.008 0.007 0.007 Unit of thermal conductivity: Kcal / m. h. Unit of main ingredient: parts by weight Table 1 continued Example 11 Example 12 Example 13 Main ingredient Soybean oil / Liquid isoprene Soybean oil / Liquid soybean oil Soybean oil 0.61 0.61 0.61 Oxygen absorption Co Naphthenic acid Co Naphthenic acid Co Naphthenic acid Co accelerator 0.12 0.12 0.12 Carrier material Geolite Zeolite Geolite 2.1 2.1 2.1 Dehumidifying agent Quick lime Quick lime Quick lime 1.5 1.5 1.5 Acid gas Slaked lime Slaked lime Slaked lime Absorber 0.61 0.61 0.61 Getta packaging Small bag packaging Small bag packaging Core material pearl light pearl light pearl light 100 100 100 Initial heat conduction Rate 0.005 0.005 0.005 40 ° C, 95% RH 90 days after storage 0.006 0.006 0.006 Thermal conductivity unit: Kcal / m. h. ℃ Unit of main agent: parts by weight
【0026】比較例1〜比較例5を表2に示す。Table 2 shows Comparative Examples 1 to 5.
【表2】表2 比較例1 比較例2 比較例3 比較例4 比較例5 主剤 なし 鉄粉 なし なし なし 5 酸素吸収 ──── ──── ──── ──── ──── 促進物質 担体物質 ──── ──── ──── ──── ──── 脱湿剤 ──── ──── シリカケ゛ル 5 ──── ──── 酸性ガス ──── ──── ──── ──── ──── 吸収剤 ケ゛ッタ の包装 なし 小袋包装 小袋包装 なし なし コア材 ハ゜ーライト ハ゜ーライト ハ゜ーライト 微粉シリカ ホ゜リウレタン 100 100 100 100 100 初期熱伝導率 0.004 0.004 0.005 0.005 0.005 40℃,95%RH 90日放置後 0.038 0.016 0.019 0.030 0.026 熱伝導率の単位:Kcal/m.h.℃ コア材等の単位:重量部 比較例2の鉄粉:比表面積 2.5m2 /g 平均粒径 120ミクロン[Table 2] Table 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Main ingredient None Iron powder None None None None 5 Oxygen absorption ──── ──── ──────── ─── ─ Accelerating substance Carrier substance ──── ──── ──── ──── ──── Dehumidifying agent ──── ──── Silica gel 5 ──── ──── Acidic gas ──── ──── ──── ──── ──── Absorbent getter packaging None Pouch packaging Pouch packaging None None Core material pearlite pearlite pearlite fine silica silica 100 100 100 100 100 Initial heat conduction Rate 0.004 0.004 0.005 0.005 0.005 40 ° C, 95% RH 90 days after storage 0.038 0.016 0.019 0.030 0.026 Thermal conductivity unit: Kcal / m. h. ℃ Units such as core material: parts by weight Iron powder of Comparative Example 2: specific surface area 2.5 m 2 / g average particle size 120 microns
【0027】[0027]
【発明の効果】本発明はガスバリア性密閉容器、形状維
持や対流防止のためのコア材、酸素の吸収に水分を必要
としない酸素吸収剤、脱湿剤及び酸性ガス吸収剤で構成
される真空断熱材で、ガスバリア性密閉容器内に徐々に
侵入するガス、また充填された断熱材より徐々に発生す
るガスを吸収し、初期のガスバリア性密閉容器内の真空
度をできる限り保ち、真空断熱材の初期の断熱性能を維
持することができ、実用的価値は大きい。INDUSTRIAL APPLICABILITY The present invention is a vacuum container composed of a gas-barrier closed container, a core material for maintaining shape and preventing convection, an oxygen absorbent that does not require water to absorb oxygen, a dehumidifying agent and an acidic gas absorbent. The heat insulating material absorbs the gas that gradually enters the gas barrier closed container and the gas that is gradually generated from the filled heat insulating material, and maintains the initial degree of vacuum in the gas barrier closed container as much as possible. It is possible to maintain the initial insulation performance of, and its practical value is great.
Claims (3)
吸収に水分を必要としない酸素吸収剤、脱湿剤及び酸性
ガス吸収剤から構成される真空断熱材。1. A vacuum heat insulating material comprising a gas-barrier closed container, a core material, an oxygen absorbent that does not require moisture to absorb oxygen, a dehumidifying agent, and an acidic gas absorbent.
収剤が不飽和脂肪酸化合物および/または不飽和基を有
する鎖状炭化水素重合物を主剤とし、酸素吸収促進物質
を含む酸素吸収剤である請求項1に記載の真空断熱材2. An oxygen absorbent which does not require water for absorbing oxygen, which is mainly composed of an unsaturated fatty acid compound and / or a chain hydrocarbon polymer having an unsaturated group and which contains an oxygen absorption promoter. The vacuum heat insulating material according to claim 1.
アルカリ土類金属の酸化物、水酸化物、炭酸塩、有機酸
塩、有機アミン類より選ばれる少なくとも一種以上であ
る請求項1に記載の真空断熱材。3. The acidic gas absorbent is at least one selected from oxides, hydroxides, carbonates, organic acid salts and organic amines of alkali metals or alkaline earth metals. Vacuum insulation.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP09151996A JP3580334B2 (en) | 1995-04-14 | 1996-04-12 | Vacuum insulation |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7-89209 | 1995-04-14 | ||
JP8920995 | 1995-04-14 | ||
JP09151996A JP3580334B2 (en) | 1995-04-14 | 1996-04-12 | Vacuum insulation |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH08338683A true JPH08338683A (en) | 1996-12-24 |
JP3580334B2 JP3580334B2 (en) | 2004-10-20 |
Family
ID=26430638
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP09151996A Expired - Fee Related JP3580334B2 (en) | 1995-04-14 | 1996-04-12 | Vacuum insulation |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11106539A (en) * | 1997-10-03 | 1999-04-20 | Mitsubishi Gas Chem Co Inc | Getter for vacuum heat insulator and its manufacture |
JP2010242975A (en) * | 2010-07-13 | 2010-10-28 | Toshiba Home Technology Corp | Insulating material and its manufacturing method |
JP2013015222A (en) * | 2012-08-28 | 2013-01-24 | Toshiba Home Technology Corp | Method of manufacturing heat insulating material |
WO2016143781A1 (en) * | 2015-03-10 | 2016-09-15 | 株式会社 東芝 | Vacuum insulated panel, core material, and refrigerator |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102015008123A1 (en) * | 2014-11-25 | 2016-05-25 | Liebherr-Hausgeräte Lienz Gmbh | Vakuumdämmkörper |
-
1996
- 1996-04-12 JP JP09151996A patent/JP3580334B2/en not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11106539A (en) * | 1997-10-03 | 1999-04-20 | Mitsubishi Gas Chem Co Inc | Getter for vacuum heat insulator and its manufacture |
JP2010242975A (en) * | 2010-07-13 | 2010-10-28 | Toshiba Home Technology Corp | Insulating material and its manufacturing method |
JP2013015222A (en) * | 2012-08-28 | 2013-01-24 | Toshiba Home Technology Corp | Method of manufacturing heat insulating material |
WO2016143781A1 (en) * | 2015-03-10 | 2016-09-15 | 株式会社 東芝 | Vacuum insulated panel, core material, and refrigerator |
KR20170121239A (en) * | 2015-03-10 | 2017-11-01 | 도시바 라이프스타일 가부시키가이샤 | Vacuum insulation panel, core material, refrigerator |
Also Published As
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