JP2004052774A - Vacuum heat insulating material, refrigerating and cooling/heating apparatus using the same, vacuum heat insulating material core material, and its manufacturing method - Google Patents

Vacuum heat insulating material, refrigerating and cooling/heating apparatus using the same, vacuum heat insulating material core material, and its manufacturing method Download PDF

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JP2004052774A
JP2004052774A JP2002192615A JP2002192615A JP2004052774A JP 2004052774 A JP2004052774 A JP 2004052774A JP 2002192615 A JP2002192615 A JP 2002192615A JP 2002192615 A JP2002192615 A JP 2002192615A JP 2004052774 A JP2004052774 A JP 2004052774A
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heat insulating
insulating material
vacuum heat
binder
core material
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JP3490426B1 (en
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Yoshihide Hirai
平井　善英
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Panasonic Holdings Corp
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Matsushita Refrigeration Co
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Priority to JP2002192615A priority Critical patent/JP3490426B1/en
Priority to TW092114811A priority patent/TW593919B/en
Priority to US10/514,809 priority patent/US7571582B2/en
Priority to AU2003241723A priority patent/AU2003241723A1/en
Priority to EP03730754.3A priority patent/EP1510747B1/en
Priority to PCT/JP2003/006915 priority patent/WO2003102460A1/en
Priority to MXPA04011825A priority patent/MXPA04011825A/en
Priority to CNB038126265A priority patent/CN1308611C/en
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a vacuum heat insulating material having excellent heat insulating performance and productivity, lightweight and high in rigidity and plane accuracy in a refrigerator, a freezer or a heat/cold insulating apparatus for an automatic vending machine or the like, and to provide a vacuum heat insulating material core material used for the vacuum heat insulating material, its manufacturing method and further the refrigerator formed of a heat insulating case body of high heat insulating performance and energy-saving with excellent appearance quality. <P>SOLUTION: The vacuum heat insulating material comprises a board-like core material and an envelope material enveloping the core material, and is closed after decompressing the interior. The board-like core material is formed of a laminated body of nonwoven fiber webs, and a hardened layer is formed at least on one side surface of the core material by heat-fixing the fiber with a binder. The vacuum heat insulating material is disposed on the outer case side in a space formed by the outer case and an inner case so that the hardened layer side face of the vacuum heat insulating material faces the inner surface of the outer case, and a heat insulating foam material is filled in a space excluding the vacuum heat insulating material to acquire the refrigerator of excellent heat insulating performance and appearance quality. <P>COPYRIGHT: (C)2004,JPO

Description

【０００１】
【発明の属する技術分野】
本発明は、断熱を必要とするもの、例えば冷蔵庫、保温保冷容器、自動販売機、電気湯沸かし器、車両、及び住宅等の断熱材として使用可能な真空断熱材に関する。
【０００２】
【従来の技術】
近年、地球温暖化防止の観点から省エネルギーが強く望まれており、家庭用電化製品についても省エネルギー化は緊急の課題となっている。特に、冷蔵庫、冷凍庫、自動販売機等の保温保冷機器では熱を効率的に利用するという観点から、優れた断熱性能を有する断熱材が求められている。
【０００３】
一般的な断熱材として、グラスウールなどの繊維材やウレタンフォームなどの発泡体が用いられている。しかし、これらの断熱材の断熱性を向上するためには断熱材の厚さを増す必要があり、断熱材を充填できる空間に制限があって、省スペースや空間の有効利用が必要な場合には適用することができない。
【０００４】
そこで、高性能な断熱材として真空断熱材が提案されている。これは、スペーサの役割を持つ芯材を、ガスバリア性を有する外被材中に挿入し、内部を減圧にして封止した断熱材である。真空断熱材としては、例えば特開平９−１３８０５８号公報に開示されているように、芯材として、グラスウール等の繊維質材を有機系バインダーを用いて固め成形したものを用いることができる。
【０００５】
ところで、真空断熱材を冷蔵庫などの断熱箱体に適用する場合は、外箱と内箱によって形成される発泡断熱材を、充填する空間の外箱側か、内箱側か、外箱と内箱との中間位置のいずれかに配置することができるが、実際は、外箱側に配置する。具体的には、外箱内面に真空断熱材を両面テープやホットメルトなどの接着剤を用いて接着することが多い。
【０００６】
真空断熱材を内箱側に配置することが少ない理由は、内箱側に配置すれば、真空断熱材の適用面積を小さくすることができるというメリットはあるが、内箱は外箱に比べて変形しやすく、内箱の外面は外箱の内面に比べて凹凸があるため、真空断熱材を強固に内箱の外面に固定することが困難な上に、発泡断熱材を充填した時に、真空断熱材と内箱との間に空洞が形成されやすく、空洞形成に起因して内箱が変形したり、断熱性能が低下するという問題があるからである。
【０００７】
また、真空断熱材を外箱と内箱との中間位置に配置することが少ない理由は、外箱と内箱との中間位置に配置すれば、外箱または内箱に近接して発泡断熱材に埋まる冷媒管、配水管、電気配線などの存在物がある面にもその存在物を避けて真空断熱材を適用できるというメリットはあるが、真空断熱材を外箱と内箱との中間位置に固定するために、部品点数が増加し、作業性が悪いという問題や、発泡断熱材を充填した時に、真空断熱材とその固定部材とが発泡断熱材の流動の抵抗となるだけでなく、発泡断熱材の流れを真空断熱材が内箱側と外箱側とに分流させるため、断熱箱体の壁厚の薄肉化が困難で、発泡断熱材の充填密度のバラツキが生じ、空洞が形成されやすく、空洞形成に起因して外箱または内箱が変形したり、断熱性能が低下する可能性があるという問題があるからである。
【０００８】
【発明が解決しようとする課題】
しかしながら、真空断熱材の芯材として、グラスウール等の繊維とバインダーを用いて成形した際に、バインダーがガラス繊維全体にわたって分散し、繊維成形体の内部も均一に結着されてしまう芯材を用いた場合は、芯材の固体熱伝導率が大きくなり、真空断熱材の断熱性能が悪化するという問題があった。
【０００９】
さらに、真空断熱材作製時に排気抵抗が大きくなり、真空断熱材内部の真空度が下がりにくいため、所定の断熱性能を得るには排気時間が長くなり、真空断熱材の生産性が悪化するという問題があった。
【００１０】
また、特開昭６２−１４７２５号公報には、連続気泡構造を有する硬質ウレタンフォームを芯材とする提案がなされているが、完全連続気泡構造の断熱体を得るために、硬質ウレタンフォームブロックの表面に形成された独立気泡を有する高密度のスキン層を取り除く必要があることから、製品歩留まりが悪化し、工業的に安価に製造することができない問題点があった。
【００１１】
一方、断熱箱体の外箱内面に真空断熱材を配置する場合は、真空断熱材の接着面の凹凸が外箱外面の凹凸となって現れやすく、特に家庭用冷蔵庫では、比較的大きな平面で構成される外箱の外観品質（平面精度）は、シビアであり、商品価値に大きな影響を与える。
【００１２】
そこで、従来では、真空断熱材の接着面の凹凸の外箱への影響を少なくするために、真空断熱材の接着面の凹凸がなくなるように（真空断熱材の接着面と外箱内面との間に空間が発生しないように）厚めの接着剤層を設けたり、凹凸を吸収する軟質部材を介在させたり、厚さのわりに面積が大きい真空断熱材は反りが発生しやすいため、１平面を１枚の真空断熱材で覆うことを諦めて、やむを得ず複数の真空断熱材を使用しており、外箱の外観品質（平面精度）と断熱箱体の断熱性能を高い次元で両立させるために、剛性が高く平面精度が高い真空断熱材が求められていた。
【００１３】
そこで、本発明は、冷蔵庫、冷凍庫、自動販売機等の保温保冷機器において、熱を効率的に利用させることの可能な、断熱性能に優れるとともに、軽量かつ生産性に優れる真空断熱材を提供することを目的とする。また、本発明は、剛性が高く平面精度が高い真空断熱材を提供することを目的とする。また、本発明は、断熱性能の高い断熱箱体からなり省エネルギーで外観品質に優れた冷蔵庫を提供することを目的とする。また、本発明は、真空断熱材芯材、さらには該真空断熱材芯材の製造方法を提供することを目的とする。
【００１４】
【課題を解決するための手段】
上記課題を解決するため、本発明の真空断熱材は、ボード状芯材と、該芯材を外包する外被材とからなり、内部を減圧後密閉した真空断熱材であって、前記ボード状芯材が繊維不織ウエブの積層体からなり、該芯材の少なくとも片側表面に前記繊維がバインダーにより熱固定された硬化層が形成されてなることを特徴とする。
【００１５】
繊維不織ウエブの積層材料を用いることにより、繊維不織ウエブ各層間の熱移動が行われ難く断熱性に優れた真空断熱材が得られると共に、表面に形成された硬化層によりハンドリング性が良好となり、また表面平滑性が良好になることで取付時の安定性や断熱性が向上する。一方、内層には殆んど硬化されない層が形成されることで、内層での熱伝導率の低下により断熱効果が向上する。また、繊維不織ウエブを用いているため、芯材全体に連続開孔構造が形成され、この連続開孔構造により減圧容器中での減圧時に外被材と成形体との層間の残存空気が膨張し、溶着周縁部が破れ外被材を設けた効果が失われる事態を回避することができるため、品質が安定化する。
【００１６】
本発明の真空断熱材においては、前記ボード状芯材の密度が１００〜４００ｋｇ／ｍ３の範囲であることが好ましい。密度が１００ｋｇ／ｍ３以上の場合は芯材を構成する材料の割合を確保できるため、実用上十分な強度を付与することが可能となり、一方密度が４００ｋｇ／ｍ３以下の場合は断熱材に占める芯材の割合を低く抑えることができるため、断熱性が良好となる。
【００１７】
また、本発明の真空断熱材においては、前記ボード状芯材の表面硬度が１５〜７０であることが好ましい。表面硬度が１５以上であればハンドリング性や表面平滑性を確保することができ、一方表面硬度が７０以下であれば冷蔵庫等を廃棄した後の断熱材の廃棄処理がし易くなる。
【００１８】
この表面硬度は、芯材の表面に硬化層が形成されることにより発現されるものであるが、硬化層は前記繊維がバインダーにより熱固定される、すなわち繊維がバインダーにより結着されることによって形成される。該硬化層は、空隙割合が小さく、繊維とバインダーとの結着により形成されるため剛性が高い。したがって、芯材の少なくとも片面（好ましくは両面）にかかる硬化層を形成することにより、芯材の剛度が向上し、ハンドリング性が良好になる。また、芯材の硬度が高くなることで、外被材にて外包後内部を減圧密閉した後でも、断熱材表面の陥没や大きな凹凸が殆んど発生することなく表面の平滑性を保つことができるため、冷凍・冷温機器への取付時の接着性が向上し、断熱効果がより一層良好となる。
【００１９】
本発明の真空断熱材においては、前記バインダーが無機材料からなることが好ましい。バインダーに無機材料を用いることにより、バインダーからの経時的な発生ガスが少なくなり、真空断熱材の経時的断熱性能が向上する。
【００２０】
また、前記バインダーが、ホウ酸、ホウ酸塩、リン酸、リン酸塩およびこれらの加熱生成物からなる化合物群から選択される少なくとも１種の化合物であることがさらに好ましい。これらの化合物はそれ自身でガラス状物質を形成するため、より硬化層を形成しやすく、特に無機繊維と親和性がよくマイグレーションをおこしにくい。
【００２１】
本発明の真空断熱材においては、前記硬化層が繊維不織ウエブの積層体表面に水を噴霧することにより形成されたものであってもよい。この硬化層は、繊維不織ウエブ積層体の表面に単に水を噴霧することで形成されるもので、水の付着によって繊維から溶出する物質（バインダー）により繊維を結着するものである。水を噴霧する方法では内層まで完全に水が浸透することなく内層は結着強度が弱いものとなるので、内層ほど柔軟な芯材を得ることができる。
【００２２】
前記の繊維としては無機繊維が好ましく、特にグラスウールもしくはグラスファイバーが好ましい。
【００２３】
また、本発明の真空断熱材においては、前記外被材がプラスチック−金属箔ラミネートフィルムであることが好ましい。芯材をラミネートフィルムで被覆することにより断熱効果が向上し、特に、金属箔を内層にしプラスチックを外層にすることにより、金属箔による熱伝導が少なく優れた断熱性能が得られるとともに、断熱箱体への取り付けが容易になり、発泡断熱材との親和性が高くなることで、断熱効果がより一層向上する。
【００２４】
したがって、本発明の真空断熱材は、上記特有の構成を有することより、熱伝導率が０．００１５〜０．００２５Ｗ／ｍＫの範囲にある。この断熱性能は、従来のウレタン系断熱材の１０倍、グラスウールの２０倍に相当するものであり、極めて高いレベルにある。
【００２５】
次に、本発明の冷凍機器および冷温機器は、外箱と、内箱と、前記外箱と前記内箱によって形成される空間に発泡断熱材と真空断熱材とを有し、前記真空断熱材を前記空間に配置し、前記真空断熱材以外の前記空間に発泡断熱材を充填してなる冷凍機器および冷温機器であって、前記真空断熱材が上記本発明の真空断熱材であることを特徴とする。
【００２６】
外箱と内箱とからなる空間に、本発明の断熱性能に優れた真空断熱材を配置し、それ以外の空間に発泡断熱材を充填することにより、断熱性能に優れた冷凍機器および冷温機器を得ることができる。
【００２７】
また、本発明の冷蔵庫は、外箱と、内箱と、前記外箱と前記内箱によって形成される空間に発泡断熱材と真空断熱材とを有し、前記真空断熱材を前記空間の前記外箱側に配置し、前記真空断熱材以外の前記空間に発泡断熱材を充填してなる冷蔵庫であって、前記真空断熱材が上記本発明の真空断熱材であり、前記真空断熱材の前記硬化層側の面が前記外箱の内面に対向していることを特徴とする。
【００２８】
本発明の真空断熱材は、芯材の内側層のバインダー濃度を薄くして、芯材内部まで均一なバインダー濃度の芯材を使った従来の真空断熱材よりも軽く、断熱性能を高くできる。また、本発明の真空断熱材は、芯材の表面に硬化層が形成されているため剛性が高い。また、本発明の真空断熱材は、平滑な金型のプレス機で圧縮加熱して芯材に硬化層を形成することにより、硬化層側の表面の平面精度を高くすることができる。また、本発明の真空断熱材は、軽量で剛性が高く平面精度が高いため広い面積のものが使用できる。
【００２９】
そして、外箱と内箱とからなる空間の外箱側に、本発明の軽量で剛性が高く断熱性能に優れ平面精度が高い真空断熱材を広い面積で配置し、それ以外の空間に発泡断熱材を充填することにより、外箱の外観品質（平面精度）と断熱箱体の断熱性能を高い次元で両立させることができ、省エネルギーで外観品質に優れた冷蔵庫を得ることができる。
【００３０】
また、本発明の冷蔵庫においては、前記外箱の内面における冷媒配管が配設された部分に対して、前記硬化層側の面に前記外被材の外側からプレスで前記冷媒配管を収納可能な溝を形成した前記真空断熱材を、前記溝内に前記冷媒配管が収まるように配置することが好ましい。本発明の真空断熱材は、芯材の内側層のバインダー濃度を薄くして、芯材の内側層を柔らかくすることにより、真空断熱材製造後に外被材の上からプレスで真空断熱材の表面に溝を形成することができる。そして、外箱の内面における冷媒配管が配設された部分に対しても、冷媒配管を避けて複数の小さい真空断熱材を配置することなく、冷媒配管を覆うように大きい真空断熱材を配置することができるため、少ない枚数の真空断熱材で、外箱と冷媒配管の熱が庫内に伝わるのを効率よく断熱でき、省エネルギーに優れた冷蔵庫を得ることができる。
【００３１】
なお、本発明の真空断熱材は、ホットメルトなどの接着剤で外箱に固定することができ、その接着剤の層の厚みは、７０〜１３０μｍの範囲であることが好ましい。１３０μｍを超える厚さの接着剤の層を設けることは、接着剤の無駄であり、接着剤は発泡断熱材より熱を伝えやすいため、断熱性能の低下につながる。また、接着剤の層を７０μｍ未満にすると、接着の信頼性が低下する。
【００３２】
また、本発明の真空断熱材芯材は、繊維不織ウエブの積層体からなり、該芯材の少なくとも片側表面には前記繊維がバインダーにより熱固定された硬化層が形成されてなることを特徴とする。
【００３３】
一般に、バインダーによっては成形体表面層にのみ硬化層を形成し、内部に浸透した少量のバインダーがマイグレーションにより表面層にその大部分が移動し、内部にはほとんど硬化層を形成しないこともある。この場合は、内部に割れを生じ、成形体全体としての強度低下が懸念される。しかし、例えば繊維をボード状に形成した後、表面にバインダーを塗布して圧縮加熱することによりボード状成形体を得る方法によれば、表面層においては、塗布したバインダーが硬化した濃度の大きい層を形成し、内部は浸透した少量のバインダーがあまりマイグレーションをおこさず表面層の内側で硬化する。その結果、ボードの厚み方向に対してバインダー濃度の異なる成形体を得ることができ、かつボード内部でも少量のバインダーが硬化した、強度的にも優れたボード状成形体を得ることができる。
【００３４】
したがって、本発明の真空断熱材芯材の製造方法は、繊維を所定形状になるように積層するステップと、積層した繊維ウエブの外面の少なくとも片面にバインダー水溶液あるいは水を塗布するステップと、バインダーを塗布した積層繊維ウエブを１００℃以下の温度で圧縮するステップと、圧縮した積層繊維ウエブを１００℃以上の温度で加熱圧縮するステップとを含むことを特徴とする。
【００３５】
【発明の実施の形態】
本発明の真空断熱材は、ボード状芯材と、該芯材を外包する外被材とからなり、内部を減圧後密閉した真空断熱材であって、前記ボード状芯材が繊維不織ウエブの積層体からなり、該芯材の少なくとも片側表面には前記繊維がバインダーにより熱固定された硬化（固化）層が形成されてなるものである。かかるボード状芯材は、その表面硬度が１５〜７０であることが好ましいが、この表面硬度は外被材によるパッケージング前の芯材の表面硬度を表したものである。したがって、外被材によるパッケージング後の真空断熱材としての表面硬度は、５０〜８０であることが好ましく、望ましくは６０〜７５の範囲であるのが良い。
【００３６】
また、真空断熱材使用後に外被材を破ることにより取り出された状態での芯材の表面硬度は、１５〜５０であることが好ましく、望ましくは２０〜４０の範囲であるのがよい。表面硬度が小さすぎる場合はハンドリング性が悪く、廃棄処理工程における作業効率が低下するおそれがあり、一方、芯材の耐久性等を考慮すれば多少の硬度低下があるとしても、表面硬度が高すぎる場合は硬化（固化）層を別途切り取る等の処理が必要となり、工程が煩雑化するおそれがある。
【００３７】
なお本発明において、硬度はデュロメーターにより芯材の表面の硬さを測定したときの値で定義され、数値が大きいほど硬く小さいほど柔らかいを意味する。
【００３８】
本発明の真空断熱材においては、ボード状芯材の少なくとも片側の表面に、前記繊維がバインダーにより結着されてなる硬化（固化）層が形成されているため、硬化層が形成された外層と内層におけるバインダー濃度が異なる。より具体的には、本発明の真空断熱材は、ボード状成形体の厚み方向における表面層のバインダー濃度が他層よりも高い。表面層のバインダー濃度を他層よりも大きくすることにより、上記の効果に加え、表面平滑性に優れた芯材が得られ、外観的にも優れた真空断熱材が得られる。
【００３９】
また、表面層以外の内部にバインダーの濃度が低い部分を設けることにより、内部の固体熱伝導を小さくすることができ、断熱性能が向上する。さらに、バインダー濃度が小さい部分の排気抵抗が小さくなり、排気時の真空度を下がりやすくすることができ、真空断熱材の生産性の向上が期待できる。このように、成形体の厚み方向においてバインダー濃度の異なる芯材を用いることにより、芯材剛性、断熱性能、生産性に優れた真空断熱材を得ることができる。
【００４０】
本発明におけるボード状芯材は、繊維不織ウエブ積層体をボード化したものであれば、特に限定はされない。該芯材を構成する繊維は、上記本発明のボード状芯材の特性を満足しうるものであれば、有機繊維あるいは無機繊維のいずれでもよい。繊維としては、例えば、グラスウール、グラスファイバー、アルミナ繊維、シリカアルミナ繊維、シリカ繊維、ロックウール、炭化ケイ素繊維等の無機繊維、あるいは木綿等の天然繊維、ポリエステル、ナイロン、アラミド等の合成繊維等の有機繊維などを挙げることができ、公知の材料を使用することができる。圧縮加熱の際の耐熱性の点からは無機繊維が望ましい。中でも、耐候性が高く、耐水性が良好である点より、グラスウール、グラスファイバーが好ましく用いられる。特に、耐候性、耐水性に優れる点より、ホウ素含有ガラスを素材とするものが望ましい。
【００４１】
本発明において用いる繊維は、その繊維径は特に限定するものではないが、連続開孔構造を形成することができ、かつ表面硬度が高く軽量な芯材を得る観点より、０．１〜２０μｍ、好ましくは１〜１０μｍ、さらに好ましくは２〜７μｍであるのがよい。また、積層体の剥離等を防止する観点より、平均繊維長が５〜１５ｍｍのものが好ましく用いられるが、これに限定されない。
【００４２】
繊維材料には、本発明のボード状芯材の特性を損なわない範囲で、粉末を添加してもよい。粉末としては、例えば、シリカ、パーライト、カーボンブラック等の無機粉末、あるいは合成樹脂粉末等の有機粉末などをあげることができる。また、ウレタンフォーム、フェノールフォーム、スチレンフォーム等の発泡樹脂の粉砕物等、公知の材料を適宜使用することができる。
【００４３】
本発明で用いるバインダーとしては、無機あるいは有機バインダー等を使用できる。具体的には、コロイダルシリカ、アルミナゾル、水ガラス、セッコウ、ホウ酸またはその塩、酸化ホウ素、リン酸またはその塩、ケイ酸ナトリウム、アルキルシリケート等の無機バインダー、あるいはフェノール樹脂、尿素樹脂、メラミン樹脂、キシレン樹脂、フラン樹脂、エポキシ樹脂等の熱硬化性樹脂、あるいは酢酸ビニル、アクリル系樹脂等の熱可塑性樹脂、あるいは天然物接着剤等の有機バインダーをあげることができる。これらを単独または混合して使用したり、あるいはこれらを水あるいは公知の有機溶媒で希釈して使用することも可能である。中でも、無機バインダーが好ましく、特に、ホウ酸、ホウ酸塩、リン酸、リン酸塩、あるいはそれらの加熱生成物のうち少なくとも一種の化合物を含むことが好ましい。
【００４４】
ホウ酸系化合物としては、例えば、ホウ酸、メタホウ酸、酸化ホウ素、四ホウ酸ナトリウムの各水和物あるいは無水物等のホウ酸ナトリウム類、ホウ酸アンモニウム、ホウ酸リチウム類、ホウ酸マグネシウム類、ホウ酸カルシウム類、ホウ酸アルミニウム類、ホウ酸亜鉛類、過ホウ酸塩類、アルキルホウ酸、ボロキシン誘導体等があげられる。
【００４５】
リン酸系化合物としては、例えば、リン酸、五酸化二リン等の酸化リン、第一リン酸塩、第二リン酸塩、第三リン酸塩、ピロリン酸塩、トリポリリン酸塩、メタリン酸塩等のリン酸塩、それらのナトリウム塩、カリウム塩、アンモニウム塩、マグネシウム塩、アルミニウム塩等があげられる。
【００４６】
これらのうち、ガラス形成物あるいは水溶性物質が好ましい。例えば、ホウ酸、メタホウ酸、酸化ホウ素、ホウ砂、リン酸、第一リン酸アルミニウム、ヘキサメタリン酸ナトリウム等である。
【００４７】
成形体のバインダーとして用いボード状繊維成形体を作製する場合は、上記の化合物を１種あるいは２種以上混合して、あるいはその他のバインダーを混合して、あるいはそれらを希釈して使用する。
【００４８】
前記芯材材料へのバインダー付着方法としては、特に限定するものではないが、前記バインダーまたはその希釈液を塗布または噴霧したりして付着させる。具体的には、芯材材料をある程度成形した後にバインダーを噴霧し、その後加熱圧縮することにより、ボード状成形体の厚み方向に対してバインダー濃度の異なる成形体を得ることができる。
【００４９】
また、繊維の繊維化時にバインダーやその希釈液を噴霧し、ボードのある部分にはバインダー濃度の大きい繊維を、その他の部分にはバインダー濃度の小さい繊維あるいはバインダーのない繊維を配置し、その後繊維積層体を圧縮加熱等により固形化させることにより、成形体の厚み方向に対しバインダー濃度の異なるボードを得ることも可能である。繊維積層体を用いることにより、各層間の熱移動がしにくくなるため、断熱性が向上する。
【００５０】
また、上記バインダーを用いることなく、繊維不織ウエブ積層体表面に水を噴霧し、水の付着によって繊維から溶出する物質（バインダー）により繊維を結着させてもよい。この場合は、内層まで完全に水が浸透することなく内層は結着強度が弱いものとなるので、内層ほど柔軟な芯材を得ることができる。
【００５１】
あるいは、バインダー濃度の大きいボード状成形体とバインダー濃度の小さいボード状成形体を２枚以上組み合わせることにより、厚み方向に濃度の異なる芯材を得ることも可能である。
【００５２】
バインダー濃度は、芯材に対しバインダーの固形分が０．１ｗｔ％以上２０ｗｔ％以下となるようにバインダーを付着させることが望ましい。バインダー量が多くなると、バインダーからの発生ガスの増加や固体熱伝導率の増加が懸念され、真空断熱材の断熱性能に悪影響を及ぼすことが考えられるからである。一方、バインダー量が少ないと、繊維積層体の固形化が不十分となるからである。
【００５３】
バインダー濃度は、ボード状成形体の厚み方向において異なっていることが好ましいが、バインダー濃度の小さい部分に固体熱伝導率、排気抵抗の低減効果を、大きい部分にボードの剛性を付与するという効果をそれぞれもたせることができる。特に、ボード状成形体の少なくとも片面の表面層、あるいは両面の表面層のバインダー濃度が大きいボード状成形体が好ましく、これにより、真空断熱材にしたときに表面性が良好となる。バインダーを付着させた後、積層成形体を圧縮あるいは加熱圧縮することによりボード化する。
【００５４】
この場合、ボード状芯材の密度（密度）が１００〜４００ｋｇ／ｍ３となるように加圧することが望ましく、ボード内での密度は異なっていてもよい。密度が１００ｋｇ／ｍ３より小さいと成形体としての形状を保持しにくくなり、４００ｋｇ／ｍ３より大きくなると固体熱伝導率が大きくなり真空断熱材の断熱性能が悪化することが考えられるからである。ボードの密度（密度）は、好ましくは１２０〜３００ｋｇ／ｍ３であり、さらに好ましくは１５０〜２５０ｋｇ／ｍ３の範囲であるのがよい。
【００５５】
なお、ボード状芯材の熱伝導率は、平均温度２４℃にて、０．０３０〜０．０３８Ｗ／ｍＫの範囲であり、好ましくは０．０３３〜０．０３７Ｗ／ｍＫの範囲であるのがよい。また、ボード状芯材は、取扱性、生産性等を考慮すると、ある程度の剛性を有することが望ましい。芯材の厚み（２枚以上積層した場合は合計厚み）は、特に限定はないが、通常５〜２０ｍｍ厚のものが用いられる。
【００５６】
本発明における外被材としては、特に限定はなく、少なくともガスバリア層および熱融着層を有するものであればよく、必要に応じて表面保護層等を設けてもよい。
【００５７】
前記ガスバリア層としては、金属箔、あるいは金属、あるいは無機酸化物、あるいはダイヤモンドライクカーボン蒸着をしたプラスチックフィルム等を用いることができるが、気体透過を低減する目的で用いるものであれば、特に限定するものではない。
【００５８】
上記金属箔としては、アルミニウム、ステンレス、鉄等の箔を用いることができるが、特に限定するものではない。
【００５９】
また、前記金属等の蒸着を行う基材となるプラスチックフィルムの材料は、特に限定するものではないが、ポリエチレンテレフタレート、エチレン−ビニルアルコール共重合体樹脂、ポリエチレンナフタレート、ナイロン、ポリアミド、ポリイミドなどへの蒸着が好ましい。
【００６０】
前記プラスチックフィルム上への金属蒸着の材料は、アルミニウム、コバルト、ニッケル、亜鉛、銅、銀、あるいはそれらの混合物等があげられるが、特に限定するものではない。
【００６１】
また、前記プラスチックフィルム上への無機酸化物蒸着の材料は、シリカ、アルミナ等があげられるが、特に限定するものではない。
【００６２】
また、熱溶着層としては、低密度ポリエチレンフィルム、鎖状低密度ポリエチレンフィルム、高密度ポリエチレンフィルム、ポリプロピレンフィルム、ポリアクリロニトリルフィルム、無延伸ポリエチレンテレフタレートフィルム、エチレン−ビニルアルコール共重合体フィルム、あるいはそれらの混合体等を用いることができるが、特に限定するものではない。
【００６３】
また、ガスバリア層の外面に表面保護層を設けることも可能である。
【００６４】
表面保護層としては、ナイロンフィルム、ポリエチレンテレフタレートフィルム、ポリプロピレンフィルムの延伸加工品などが利用でき、さらに外側にナイロンフィルムなどを設けると可とう性が向上し、耐折り曲げ性などが向上する。
【００６５】
以上のようなフィルムをラミネートして用いる。中でも、プラスチック−金属箔ラミネートフィルムが好ましく用いられる。また、外被材として鉄板、ステンレス板、亜鉛板等の金属板を用いた金属容器を使用してもよい。
【００６６】
外被材の袋形状は、四方シール袋、ガゼット袋、三方シール袋、ピロー袋、センターテープシール袋等、特に限定するものでない。また、金属板を直方体に成型して用いる等の方法がある。
【００６７】
また、さらに真空断熱体の信頼性を向上させる場合は、ガス吸着剤や水分吸着剤等のゲッター物質を使用することも可能である。
【００６８】
本発明の真空断熱材の製造においては、まず外被材を作製し、その後外被材中に芯材を挿入し内部を減圧し封止してもよく、あるいは、減圧槽中に芯材とロール状あるいはシート状のラミネートフィルムからなる外被材を設置し、ロール状あるいはシート状の外被材を芯材に沿わした状態にしてから外被材を熱融着することにより真空断熱材を作製してもよく、あるいは、芯材を挿入した外被材内を直接減圧にして外被材開口部を封止することにより真空断熱材を製造する、あるいは金属板で成形した容器にボード状の芯材を挿入し、真空ポンプと前記金属容器とを管で結んで容器内を減圧とし、その後管を封止し切ることにより真空断熱材とする等の方法があるが、特に指定するものではない。また、ボード状芯材は外被材挿入前に水分乾燥を行ってもよく、また外被材挿入時に吸着剤を一緒に挿入してもよい。
【００６９】
本発明の真空断熱材は、表面に硬化層が形成されていることにより、減圧処理後も表面平滑性に優れたものが得られる。なお、表面粗さは、ＪＩＳ　Ｂ　０６０１により求めることができる。
【００７０】
また、本発明の真空断熱材は、冷凍機器や冷温機器の断熱材として好ましく用いられる。その場合は、冷凍機器や冷温機器の外箱と内箱とによって形成される空間に発泡断熱体と真空断熱材とを配置するが、前記真空断熱材を前記空間に配置し、前記真空断熱材以外の前記空間に発泡断熱材を充填する。例えば冷蔵庫に適用した場合、冷蔵庫の外箱と内箱の間の空間の外箱側または内箱側に真空断熱材を貼付しその他の空間に樹脂発泡体を充填する、あるいは真空断熱体と発泡樹脂体とを一体発泡した断熱体を冷蔵庫の外箱と内箱の間の空間に配設する、あるいはドア部に同様に使用する、あるいは仕切り板に使用する等、その使用方法は特に指定するものではないが、機械室と内箱との間、あるいは冷凍室の周囲に前記真空断熱材を用いることは、特に断熱効率に優れ、低電力量で冷蔵庫を運転できるため望ましい。
【００７１】
冷蔵庫等の冷凍機器や冷温機器に真空断熱材を貼付する場合は、真空断熱材と外箱との間の空洞形成を防止して断熱効果を高める点より、真空断熱材の硬化層側の面を冷蔵庫の外箱の内面に対向させて固定するのが好ましい。固定には、両面テープやホットメルトなどの接着剤を用いることができるが、接着の信頼性が高い点より、ホットメルト接着剤が好ましく用いられる。ホットメルト接着剤の種類は特に限定されず、エチレン−酢酸ビニル共重合樹脂、ポリアミド樹脂、ポリエステル樹脂、合成ゴム等をベースとするものがあげられる。
【００７２】
前記の樹脂発泡体としては、例えば硬質ウレタンフォーム、フェノールフォームやスチレンフォームなどを使用することができるが、特に限定するものではない。
【００７３】
また、例えば硬質ウレタンフォームを発泡する際に用いる発泡剤としては、特に限定するものではないが、オゾン層保護、地球温暖化防止の観点から、シクロペンタン、イソペンタン、ｎ−ペンタン、イソブタン、ｎ−ブタン、水（炭酸ガス発泡）、アゾ化合物、アルゴン等が望ましく、特に断熱性能の点からシクロペンタンが特に望ましい。
【００７４】
また、冷凍機器・冷温機器に使用する冷媒は、フロン１３４ａ、イソブタン、ｎ−ブタン、プロパン、アンモニア、二酸化炭素、水等、特に指定するものではない。
【００７５】
本発明において、冷凍機器および冷温機器は、動作温度帯である−３０℃から常温で断熱を必要とする機器の代表として示したものであり、例えば保冷車、電子冷却を利用した冷蔵庫等や、自動販売等のより高温までの範囲で温冷熱を利用した冷温機器や、ガス機器あるいはクーラーボックス等動力を必要としない機器も含むものである。
【００７６】
さらに、本発明の真空断熱材は、パソコン、ジャーポット、炊飯器等に使用することも可能である。
【００７７】
次に本発明の真空断熱材芯材の製造方法を説明する。本発明の製造方法においては、繊維ウエブを所定形状になるように積層するステップと、積層した繊維ウエブの外面の少なくとも片面に水で希釈したバインダー水溶液（あるいは水）を塗布するステップと、バインダーを塗布した積層繊維ウエブを１００℃以下の温度で圧縮するステップと、圧縮した積層繊維ウエブを１００℃以上の温度で加熱圧縮するステップとを含む。繊維ウエブを所定の形状になるように積層し、積層した繊維ウエブの外面に水で希釈したバインダー水溶液（あるいは水）を塗布する。このとき、積層繊維の片面、あるいは両面、あるいは全表面等任意の外面に、水で希釈したバインダー水溶液（あるいは水）を塗布する。その後、バインダーを塗布した積層繊維ウエブを１００℃以下の温度で圧縮するが、これは水分の蒸発しにくい常温圧縮の方が好ましい。
【００７８】
ここで、バインダー水溶液の濃度は、バインダーの種類、塗布量、添加量によって変動するため一概に規定することはできないが、水への溶解性を考慮すると０．５〜２０重量％とするのが望ましい。バインダー水溶液の塗布量は、特に限定するものではないが、繊維積層体１００重量部に対し５０重量部以上３００重量部以下の割合で使用することが好ましい。使用量が５０重量部より少ないと水溶液が繊維積層体の内部に浸透しにくく、３００重量部より多いと、この後の加熱圧縮工程で余分な水分が液体状態で流出し、それと共にバインダーも流出するためバインダーにロスが発生するからである。
【００７９】
その後、積層繊維を１００℃以上の温度で加熱圧縮するが、これは水分を蒸発させること、およびバインダーを硬化させることが目的であり、バインダー硬化温度以上で加熱することが望ましい。加熱圧縮時にバインダーが積層体内部に浸透しすぎるのを防止したり、繊維の溶融を防止する観点より、６００℃以下であることが好ましい。
【００８０】
一般に、繊維化時にバインダーを塗布した繊維を用いて成形体を作製すると、成形体内で均一なバインダー分布を有するボードを得やすく、濃度勾配を有する成形体を得ることは困難である。しかし、本発明の製造方法によれば、繊維を所定形状に積層し、その積層した繊維の少なくとも一面にバインダーを塗布し、それを１００℃以下すなわち水分蒸発以下の温度にて一度圧縮することにより表面層はバインダー濃度が大きく内部はバインダー濃度が小さい状態にし、その後１００℃以上の温度で圧縮加熱して水分を蒸発させることにより、厚み方向にバインダー濃度が異なり、しかも成形体内部でも少量のバインダーが結着した芯材を得やすく強度的にも優れた芯材を得ることができる。
【００８１】
【実施例】
以下、実施例及び比較例を用いて本発明を更に具体的に説明するが、本発明は本実施例のみに限定されるものではない。
【００８２】
（実施例１）
図１は本発明の一実施例における真空断熱材の断面図である。１は真空断熱材であり、ボード状芯材２を外被材３中に挿入し、内部を減圧として密封し、真空断熱材１としている。
【００８３】
ボード状芯材２は、まず平均繊維径５μｍ、平均繊維長１０ｍｍ、真比重２．５ｇ／ｃｍ３のグラスウール４を所定密度になるまで積層した。バインダーは、グラスウール１００重量部に対し、バインダー５として水ガラス１０重量部を水９０重量部に溶解し、水ガラス水溶液１００重量部としたものを使用した。この水ガラス水溶液を、噴霧装置にて、積層したグラスウール４の両表面に噴霧し、その後４５０℃の熱風循環炉の中で密度が２３０ｋｇ／ｍ３となるように２０分間プレスし、ボード状芯材２を得た。ボード状芯材の密度は２３５ｋｇ／ｍ３、熱伝導率は０．３５Ｗ／ｍＫであった。
【００８４】
このボード状芯材２の断面図を図２に示す。ボード内面層はあまりバインダー５が残留しておらず、ボード外層にて多くのバインダーが硬化し、表面に硬化層が形成されているのが確認できた。この芯材の表面硬度を測定したところ６５であった。
【００８５】
また、ボード状芯材の表面の外観をオリンパス製光学顕微鏡ＢＨ−２（倍率：５８０倍）で観察したものを図１１に示した。交差した繊維がバインダーにより結着し硬化しているのがわかる。
【００８６】
外被材２は、２枚のラミネートフィルムを三方シールにて製袋した。前記２枚のラミネートフィルムのうち、１枚は熱融着層として直鎖状低密度ポリエチレンフィルム（以下、ＬＬＤＰＥと称す）が５０μｍ、ガスバリア層として厚み１５μｍのエチレン−ビニルアルコール共重合体フィルム（以下、ＥＶＯＨと称す）に膜厚４５０オングストロームのアルミ蒸着を形成したフィルムと、厚み１２μｍのポリエチレンテレフタレートフィルム（以下、ＰＥＴと称す）に４５０オングストロームのアルミ蒸着を形成したフィルムをアルミ蒸着面同士貼り合わせたフィルムからなり、熱融着層のＬＬＤＰＥとガスバリア層のＥＶＯＨをドライラミネートしている。また、他の１枚は、熱融着層は厚み５０μｍのＬＬＤＰＥ、その上にガスバリア層として厚み６μｍのアルミ箔、さらに保護層として厚み１２μｍのナイロン，最外層として厚み１２μｍのナイロンにより構成されている。
【００８７】
前記ボード状芯材２を１４０℃の乾燥炉で１時間乾燥し、外被材３中に挿入し、内部を３Ｐａまで５分間減圧し封止した。
【００８８】
以上のようにして作製した真空断熱材１の熱伝導率は、平均温度２４℃にて０．００２２Ｗ／ｍＫであり、その表面硬度は７０であった。
【００８９】
また、経時信頼性を確認するため加速試験による断熱材の劣化を評価したが、１０年経過条件での熱伝導率は平均温度２４℃にて０．００５Ｗ／ｍＫであった。この真空断熱材の外被材を破って芯材を取り出し、その表面硬度を測定したところ６０であった。
【００９０】
（実施例２）
図３に示す構造の真空断熱材を作製した。外被材３中に、ボード状芯材２Ａを挿入し、内部を減圧として密封し、真空断熱材とした。ボード状芯材２Ａは、まず平均繊維径５μｍ、平均繊維長１０ｍｍ、真比重２．５ｇ／ｃｍ３のグラスウール４を所定密度になるまで積層した。バインダー５Ａは、グラスウール１００重量部に対し、バインダーとしてホウ酸３重量部を水９７重量部に溶解し、ホウ酸水溶液１００重量部としたものを使用した。このホウ酸水溶液を、噴霧装置にて、積層したグラスウール４の両表面に噴霧し、それを一度常温でプレスした。その後３５０℃の熱風循環炉の中で密度が２３０ｋｇ／ｍ３となるように２０分間プレスし、ボード状芯材２Ａを得た。このボード状芯材の密度は２３３ｋｇ／ｍ３、熱伝導率は０．３４Ｗ／ｍＫであった。
【００９１】
このボード状芯材２Ａの断面図を図４に示す。ボード内面層も、外層よりは弱いがバインダーにより結着しており、外層に向けてバインダー量が増大しており、表面に硬化層が形成されているのが確認できた。この芯材の表面硬度を測定したところ４５であった。
【００９２】
前記ボード状芯材２Ａを１４０℃の乾燥炉で１時間乾燥し、外被材３中に挿入し、内部を３Ｐａまで５分間減圧し封止した。なお、外被材３は、実施例１にて使用した外被材と同様のものを用いた。
【００９３】
以上のようにして作製した真空断熱材の熱伝導率は、平均温度２４℃にて０．００２Ｗ／ｍＫであり、その表面硬度は６０であった。
【００９４】
また、経時信頼性を確認するため加速試験による断熱材の劣化を評価したが、１０年経過条件での熱伝導率は平均温度２４℃にて０．００５Ｗ／ｍＫであった。この真空断熱材の外被材を破って芯材を取り出し、その表面硬度を測定したところ３５であった。
【００９５】
この真空断熱材は、実施例１で得た真空断熱材と比較して、バインダーをホウ酸としたこと、および加熱圧縮前に常温プレスしていることから、芯材内部にもバインダーが残留しているため、芯材内部での割れが起きず、強度的に向上した。
【００９６】
（実施例３）
図５に示す構造の真空断熱材を作製した。外被材３中にボード状芯材２Ｂを挿入し、内部を減圧として密封し、真空断熱材とした。ボード状芯材２Ｂは３枚のボードからなっている。そのうち２枚（２１Ｂ）は、平均繊維径５μｍ、平均繊維長１０ｍｍ、真比重２．５ｇ／ｃｍ３のグラスウール４を所定密度になるまで積層したものを、バインダー５Ｂはグラスウール１００重量部に対し、バインダーとしてホウ酸５重量部を水９５重量部に溶解し、ホウ酸水溶液１００重量部としたものを使用した。このホウ酸水溶液を、噴霧装置にて、積層したグラスウール４の両表面に噴霧し、それを一度常温でプレスした。その後３５０℃の熱風循環炉の中で密度が２３０ｋｇ／ｍ３となるように２０分間プレスした。もう１枚（２２Ｂ）は、平均繊維径５μｍ、平均繊維長１０ｍｍのグラスウール４を３５０℃にて圧縮加熱してものを使用した。前記のバインダーを用いたボード状芯材（２１Ｂ）の表面に硬化層が形成されているのが確認でき、その表面硬度は４５であった。
【００９７】
これら３枚のボードを、外側がホウ酸を用いたボード（２１Ｂ）、内側にグラスウールのみを用いたボード（２２Ｂ）を重ね、ボード状芯材２Ｂとした。このボード状芯材２Ｂの断面図を図６に示す。なお、外被材３は、実施例１にて使用した外被材と同様のものを用いた。このボード状芯材の密度は１９０ｋｇ／ｍ３、熱伝導率は０．３４Ｗ／ｍＫであった。
【００９８】
前記ボード状芯材２Ｂを１４０℃の乾燥炉で１時間乾燥し、外被材２中に挿入し、内部を３Ｐａまで５分間減圧し封止した。
【００９９】
以上のようにして作製した真空断熱材１Ｂの熱伝導率は、平均温度２４℃にて０．００１９Ｗ／ｍＫであり、その表面硬度は６０であった。
【０１００】
また、経時信頼性を確認するため加速試験による断熱材の劣化を評価したが、１０年経過条件での熱伝導率は、平均温度２４℃にて０．００５Ｗ／ｍＫであった。この真空断熱材の外被材を破って芯材を取り出し、その表面硬度を測定したところ３５であった。
【０１０１】
表面層にホウ酸バインダーつきのボードを、内部層にグラスウールのみのボードを用いたことにより、内部層にバインダーがないことから固体熱伝導率が小さく断熱性能に優れた芯材を得ることができた。
【０１０２】
（実施例４）
図７は本発明の一実施例における冷凍冷蔵庫の断面図、図８は同冷凍冷蔵庫の断熱箱体の天井面部分の要部拡大断面図である。６は冷蔵庫、７は冷蔵庫を形成する断熱箱体、１Ａは真空断熱材である。本実施例では、真空断熱材１Ａは、箱体内部の外箱８側に、芯材２Ａの硬化層を形成した側の面が外箱８の内面に対向するように配置している。
【０１０３】
また、本実施例では、外箱８の内面における冷媒配管２１が配設された部分に対して、芯材２Ａの硬化層を形成した側の面に外被材３の外側からプレスで冷媒配管２１を収納可能な溝２２を形成した真空断熱材１Ａを、溝２２内に冷媒配管２１が収まるように配置する。
【０１０４】
また、本実施例では、真空断熱材１Ａを、熱可塑性のゲル状のホットメルト形接着剤２３で外箱８に固定する。その接着剤２３の層の厚みは、約１００μｍとしているが、７０〜１３０μｍの範囲であることが好ましい。接着剤２３はローラーなどを用いて真空断熱材１Ａにおける外箱に接着させる面に均一に過不足なく塗布しておく。
【０１０５】
断熱箱体７は、鉄板をプレス成型した外箱８とＡＢＳ樹脂を真空成型した内箱９とがフランジを介して構成される箱体内部にあらかじめ真空断熱材１Ａを配設し、前記真空断熱材１Ａ以外の空間部を、硬質ウレタンフォーム１０にて発泡充填したものである。硬質ウレタンフォーム１０は、発泡剤としてシクロペンタンを使用している。
【０１０６】
断熱箱体７は、仕切り板１２にて区切られており、上部が冷蔵室１３、下部が冷凍室１４となっている。仕切り板１２にはダンパ１５が取り付けられている。
【０１０７】
１６は冷蔵庫内に配置された蒸発器であり、圧縮機１８、凝縮器１９、キャピラリチューブ２０とを順次環状に接続し、冷凍サイクルを形成する。冷凍サイクル内には冷媒であるイソブタンが封入されている。
【０１０８】
蒸発器は冷蔵室１３および冷凍室１４の２カ所に設け、それらを直列にまた並列に繋ぎ冷凍サイクルを形成してもよい。
【０１０９】
また、冷蔵庫６にはドア体１１が取り付けられており、ドア体１１の内部に真空断熱材１Ａが配設され、真空断熱材以外の空間部は硬質ウレタンフォーム１０にて発泡充填されている。
【０１１０】
真空断熱材１Ａは実施例２に示したものと同様の構成である。このように構成された冷蔵庫の消費電力量を測定したところ、真空断熱材を装着しない冷蔵庫よりも２５％低下しており、断熱効果を確認した。
【０１１１】
（比較例１）
図９は本発明の一比較例における真空断熱材の断面図である。１ａは真空断熱材であり、ボード状芯材２ａを外被材３ａ中に挿入し、内部を減圧として密封し、真空断熱材１ａとしている。外被材３ａの材料構成は実施例１にて使用した外被材３と同じであり、三方シールにて製袋し、外被材３ａとしている。
【０１１２】
ボード状芯材２ａは、グラスウール４ａ（実施例１で用いたものと同じ）の繊維化後に、繊維表面にバインダー５ａが均一に付着するように噴霧した。バインダー水溶液はグラスウール１００重量部に対し、バインダーとしてフェノール樹脂１０重量部を水９０重量部に溶解し、フェノール水溶液１００重量部としたものを使用した。このバインダー付き原綿を、所定密度になるように積層し、その後２００℃の熱風循環炉の中で密度が２３０ｋｇ／ｍ３となるように２０分間プレスした。このボード状芯材の表面硬度を測定したところ７５であった。また、このボード状芯材の密度は２４０ｋｇ／ｍ３、熱伝導率は０．３２Ｗ／ｍＫであった。
【０１１３】
前記ボード状芯材２ａを１４０℃の乾燥炉で１時間乾燥し、外被材２ａ中に挿入し、内部を３Ｐａまで１０分間減圧し封止した。ボード状芯材２ａの断面図を図１０に示す。
【０１１４】
以上のようにして作製した真空断熱材１ａの熱伝導率は、平均温度２４℃にて０．００３Ｗ／ｍＫであり、その表面硬度は８０であった。
【０１１５】
また、経時信頼性を確認するため加速試験による断熱材の劣化を評価したが、１０年経過条件での熱伝導率は、平均温度２４℃にて０．０２１Ｗ／ｍＫであった。この真空断熱材の外被材を破って芯材を取り出し、その表面硬度を測定したところ７５であった。
【０１１６】
実施例１と比較して、バインダーとしてフェノール樹脂を用いたこと、およびボード内で均一硬化していることから、初期、経時性能共に悪化する。
【０１１７】
（比較例２）
図９は本発明の一比較例における真空断熱材の断面図である。１ｂは真空断熱材であり、ボード状芯材２ｂを外被材３ｂ中に挿入し、内部を減圧として密封し、真空断熱材１ｂとした。外被材３ｂの材料構成は実施例１にて使用した外被材３と同じであり、三方シールにて製袋し、外被材３ｂとした。
【０１１８】
ボード状芯材２ｂは、グラスウール４ｂ（実施例２で用いたものと同じ）の繊維化後に、繊維表面にバインダー５ｂが均一に付着するように噴霧した。バインダーはグラスウール１００重量部に対し、バインダーとしてホウ酸３重量部を水９７重量部に溶解し、ホウ酸水溶液１００重量部としたものを使用した。このバインダー付き原綿を、所定密度になるように積層し、その後３５０℃の熱風循環炉の中で密度が２３０ｋｇ／ｍ３となるように２０分間プレスした。
【０１１９】
前記ボード状芯材２ｂを１４０℃の乾燥炉で１時間乾燥し、外被材２ｂ中に挿入し、内部を３Ｐａまで１０分間減圧し封止した。ボード状芯材２ｂの断面図を図１０に示す。また、このボード状芯材の密度は２３３ｋｇ／ｍ３、熱伝導率は０．３４Ｗ／ｍＫであった。このボード状芯材の表面硬度を測定したところ、４５であった。
【０１２０】
以上のようにして作製した真空断熱材１ｂの熱伝導率は、平均温度２４℃にて０．００２５Ｗ／ｍＫであり、その表面硬度は６０であった。
【０１２１】
また、経時信頼性を確認するため加速試験による断熱材の劣化を評価したが、１０年経過条件での熱伝導率は、平均温度２４℃にて０．０１５Ｗ／ｍＫであった。この真空断熱材の外被材を破って芯材を取り出し、その表面硬度を測定したところ、３５であった。
【０１２２】
実施例２と比較して、バインダーを均一硬化させたことから、初期性能が悪化すると共に、排気時間も長時間必要になった。
【０１２３】
【発明の効果】
以上説明したとおり、本発明によれば、成型しやすくハンドリング性に優れるとともに、表面硬度が高く表面平滑性に優れ、かつ固体熱伝導率の小さい断熱性に優れた真空断熱材が得られる。
【０１２４】
また、真空断熱材芯材の少なくとも片側の表面に、繊維がバインダーにより結着されてなる硬化層が形成されているため、芯材に剛性が付与され取扱いが容易になるとともに、表面平滑性が良好となり、真空断熱材製造時の生産性が向上する。また、芯材の厚み方向において繊維を結着するバインダーの濃度が、表面層において他層よりも大きく、内部では小さい部分が設けられているため、内部の固体熱伝導が小さくなり、断熱性能が向上する。さらに、バインダー濃度が小さい部分の排気抵抗が少なくなり、排気時の真空度を下がりやすくすることができ、真空断熱材の生産性向上が期待できる。
【０１２５】
また、本発明の冷凍機器、冷温機器によれば、外箱と内箱とからなる空間に、本発明の断熱性能に優れた真空断熱材を配置し、それ以外の空間に発泡断熱材を充填することにより、断熱性能に優れた冷凍機器および冷温機器を得ることができる。
【０１２６】
また、本発明の真空断熱材芯材の製造方法によれば、厚み方向にバインダー濃度が異なり、しかも成形体内部でも少量のバインダーが結着した本発明の芯材を得やすく、強度的にも優れた芯材を得ることができる。
【０１２７】
また、本発明の冷蔵庫によれば、外箱と内箱とからなる空間の外箱側に、本発明の軽量で剛性が高く断熱性能に優れ平面精度が高い真空断熱材を広い面積で配置し、それ以外の空間に発泡断熱材を充填することにより、外箱の外観品質（平面精度）と断熱箱体の断熱性能を高い次元で両立させることができ、省エネルギーで外観品質に優れた冷蔵庫を得ることができる。
【０１２８】
また、本発明の真空断熱材は、真空断熱材製造後に外被材の上からプレスで真空断熱材の表面に溝を形成することができるため、外箱の内面における冷媒配管が配設された部分に対しては、冷媒配管に合った溝を形成した真空断熱材を配置することにより、少ない枚数の真空断熱材を使って、省エネルギーに優れた冷蔵庫を得ることができる。
【図面の簡単な説明】
【図１】本発明の一実施例における真空断熱材の断面模式図である。
【図２】本発明の一実施例におけるボード状芯材の断面模式図である。
【図３】本発明の一実施例における真空断熱材の断面模式図である。
【図４】本発明の一実施例におけるボード状芯材の断面模式図である。
【図５】本発明の一実施例における真空断熱材の断面模式図である。
【図６】本発明の一実施例におけるボード状芯材の断面模式図である。
【図７】本発明の一実施例における冷凍冷蔵庫の断面模式図である。
【図８】冷凍冷蔵庫の断熱箱体の天井面部分の要部拡大断面図である。
【図９】本発明の一比較例における真空断熱材の断面模式図である。
【図１０】本発明の一比較例におけるボード状芯材の断面模式図である。
【図１１】実施例１のボード状芯材の表面の外観を観察した光学顕微鏡写真である。
【符号の説明】
１　真空断熱材
２　ボード状芯材
３　外被材
４　グラスウール
５　バインダー
６　冷蔵庫
７　断熱箱体
８　外箱
９　内箱
１０　硬質ウレタンフォーム
１１　ドア体
１２　仕切り板
１３　冷蔵室
１４　冷凍室
１５　ダンパ
１６　蒸発器
１７　機械室
１８　圧縮機
１９　凝縮器
２０　キャピラリチューブ
２１　冷媒配管
２２　溝
２３　ホットメルト形接着剤[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a vacuum heat insulating material that can be used as a heat insulating material for things that require heat insulation, for example, refrigerators, heat insulating and cold containers, vending machines, electric water heaters, vehicles, and houses.
[0002]
[Prior art]
In recent years, energy saving is strongly desired from the viewpoint of preventing global warming, and energy saving is an urgent issue for household appliances. In particular, a heat insulating material having excellent heat insulating performance is required from the viewpoint of efficiently using heat in a heat and cold insulation device such as a refrigerator, a freezer, and a vending machine.
[0003]
As general heat insulating materials, fiber materials such as glass wool and foams such as urethane foam are used. However, in order to improve the heat insulation of these heat insulating materials, it is necessary to increase the thickness of the heat insulating material, and there is a limit to the space that can be filled with the heat insulating material, and when space saving and effective use of the space are necessary. Is not applicable.
[0004]
Therefore, vacuum heat insulating materials have been proposed as high performance heat insulating materials. This is a heat insulating material in which a core material serving as a spacer is inserted into a jacket material having a gas barrier property and the inside is sealed under reduced pressure. As a vacuum heat insulating material, for example, as disclosed in JP-A-9-138058, a core material obtained by solidifying a fiber material such as glass wool with an organic binder can be used.
[0005]
By the way, when applying a vacuum heat insulating material to a heat insulating box such as a refrigerator, the foam heat insulating material formed by the outer box and the inner box is either the outer box side of the space to be filled, the inner box side, or the outer box and the inner box. Although it can arrange | position in either the intermediate | middle position with a box, actually arrange | positions in the outer box side. Specifically, a vacuum heat insulating material is often bonded to the inner surface of the outer box using an adhesive such as double-sided tape or hot melt.
[0006]
The reason why the vacuum insulation material is rarely arranged on the inner box side is that if it is arranged on the inner box side, there is a merit that the application area of the vacuum insulation material can be reduced, but the inner box is compared to the outer box. It is easy to deform and the outer surface of the inner box is uneven compared to the inner surface of the outer box, so it is difficult to firmly fix the vacuum heat insulating material to the outer surface of the inner box, and when filling with foam heat insulating material, This is because a cavity is easily formed between the heat insulating material and the inner box, and there is a problem that the inner box is deformed due to the formation of the cavity or the heat insulating performance is lowered.
[0007]
In addition, the reason why the vacuum heat insulating material is rarely disposed at an intermediate position between the outer box and the inner box is that the foam heat insulating material is close to the outer box or the inner box if it is disposed at an intermediate position between the outer box and the inner box. There is a merit that the vacuum insulation material can be applied to the surface where there are existences such as refrigerant pipes, water distribution pipes, electrical wiring, etc. embedded in the vacuum insulation material, but the vacuum insulation material is positioned between the outer box and the inner box. In addition to the problem that the number of parts increases and workability is poor, and when the foam insulation is filled, the vacuum insulation and its fixing member not only resist flow resistance of the foam insulation, Because the vacuum insulation material divides the flow of the foam insulation material into the inner box side and the outer box side, it is difficult to reduce the wall thickness of the insulation box, resulting in variations in the packing density of the foam insulation material, and the formation of cavities The outer box or inner box is deformed due to the formation of cavities, and the heat insulation performance is reduced. This is because there is a problem that the possibility is there that.
[0008]
[Problems to be solved by the invention]
However, as the core material of the vacuum heat insulating material, a core material in which the binder is dispersed throughout the glass fiber and the inside of the fiber molded body is uniformly bound when formed using a fiber such as glass wool and a binder. In such a case, there is a problem that the solid thermal conductivity of the core material is increased and the heat insulating performance of the vacuum heat insulating material is deteriorated.
[0009]
In addition, the exhaust resistance increases during vacuum insulation material production, and the degree of vacuum inside the vacuum insulation material is difficult to decrease, so the exhaust time is long to obtain the prescribed insulation performance, and the productivity of the vacuum insulation material deteriorates. was there.
[0010]
Japanese Patent Application Laid-Open No. 62-14725 has proposed that a hard urethane foam having an open-cell structure is used as a core material. Since it is necessary to remove the high-density skin layer having closed cells formed on the surface, there is a problem in that the product yield deteriorates and it cannot be manufactured industrially at low cost.
[0011]
On the other hand, when the vacuum heat insulating material is arranged on the inner surface of the outer box of the heat insulating box, the unevenness of the adhesion surface of the vacuum heat insulating material tends to appear as the unevenness of the outer surface of the outer box. The appearance quality (planar accuracy) of the outer box is severe and has a great influence on the commercial value.
[0012]
Therefore, conventionally, in order to reduce the influence of the unevenness of the bonding surface of the vacuum heat insulating material on the outer box, the unevenness of the bonding surface of the vacuum heat insulating material is eliminated (the relationship between the bonding surface of the vacuum heat insulating material and the inner surface of the outer box). Since a thick adhesive layer is provided, a soft member that absorbs unevenness is interposed, or a vacuum heat insulating material with a large area instead of thickness is likely to warp, To give up covering with a single vacuum insulation material, and unavoidably using a plurality of vacuum insulation materials, in order to achieve a high level of external appearance quality (planar accuracy) and heat insulation performance of the insulation box body, There has been a demand for a vacuum heat insulating material having high rigidity and high planar accuracy.
[0013]
Accordingly, the present invention provides a vacuum heat insulating material that is capable of efficiently utilizing heat and that has excellent heat insulating performance, light weight, and high productivity in a heat insulating and cold-retaining device such as a refrigerator, a freezer, and a vending machine. For the purpose. Another object of the present invention is to provide a vacuum heat insulating material having high rigidity and high planar accuracy. Moreover, an object of this invention is to provide the refrigerator which consists of a heat insulation box with high heat insulation performance, and was excellent in appearance quality with energy saving. Moreover, an object of this invention is to provide the manufacturing method of a vacuum heat insulating material core material, and also this vacuum heat insulating material core material.
[0014]
[Means for Solving the Problems]
In order to solve the above problems, the vacuum heat insulating material of the present invention is a vacuum heat insulating material comprising a board-shaped core material and a jacket material that encloses the core material, the inside of which is sealed after decompression, and the board-shaped The core material is composed of a laminate of non-woven fiber webs, and a hardened layer in which the fibers are thermally fixed with a binder is formed on at least one surface of the core material.
[0015]
By using the laminated material of the fibrous nonwoven web, heat transfer between each layer of the fibrous nonwoven web is difficult, and a vacuum heat insulating material excellent in heat insulation is obtained, and the handling property is good due to the cured layer formed on the surface. In addition, since the surface smoothness is good, the stability and heat insulation during mounting are improved. On the other hand, since a layer that is hardly cured is formed in the inner layer, the heat insulation effect is improved due to the decrease in the thermal conductivity in the inner layer. In addition, since a non-woven fiber web is used, a continuous hole structure is formed in the entire core material, and this continuous hole structure allows residual air between the outer cover material and the molded body during decompression in the vacuum container. Since the situation which expand | swells and the welding peripheral part is torn and the effect which provided the jacket material is lost can be avoided, quality is stabilized.
[0016]
In the vacuum heat insulating material of the present invention, the density of the board-shaped core material is 100 to 400 kg / m. 3 It is preferable that it is the range of these. Density is 100kg / m 3 In the above case, since the ratio of the material constituting the core material can be secured, it is possible to give practically sufficient strength, while the density is 400 kg / m. 3 In the following cases, since the ratio of the core material to the heat insulating material can be kept low, the heat insulating property is good.
[0017]
Moreover, in the vacuum heat insulating material of this invention, it is preferable that the surface hardness of the said board-shaped core material is 15-70. If the surface hardness is 15 or more, handling properties and surface smoothness can be ensured. On the other hand, if the surface hardness is 70 or less, it becomes easy to dispose of the heat insulating material after discarding the refrigerator or the like.
[0018]
This surface hardness is expressed by the formation of a hardened layer on the surface of the core material. The hardened layer is formed by heat-fixing the fibers with a binder, that is, by binding the fibers with a binder. It is formed. The hardened layer has a small void ratio and is formed by binding of fibers and a binder, and thus has high rigidity. Therefore, by forming the hardened layer on at least one side (preferably both sides) of the core material, the rigidity of the core material is improved and the handling property is improved. In addition, by increasing the hardness of the core material, it is possible to maintain smoothness of the surface of the heat insulating material without causing any depression or large irregularities even after the inside is enveloped with a jacket material and the inside is vacuum-sealed. Therefore, the adhesion at the time of attachment to refrigeration / cooling equipment is improved, and the heat insulation effect is further improved.
[0019]
In the vacuum heat insulating material of the present invention, the binder is preferably made of an inorganic material. By using an inorganic material for the binder, the amount of gas generated with the passage of time from the binder is reduced, and the temporal heat insulation performance of the vacuum heat insulating material is improved.
[0020]
More preferably, the binder is at least one compound selected from the group consisting of boric acid, borate, phosphoric acid, phosphate, and a heated product thereof. Since these compounds themselves form a glassy substance, it is easier to form a hardened layer, and particularly has good affinity with inorganic fibers and is difficult to migrate.
[0021]
In the vacuum heat insulating material of the present invention, the cured layer may be formed by spraying water on the surface of the laminated body of the fibrous nonwoven web. This hardened layer is formed by simply spraying water onto the surface of the fibrous nonwoven web laminate, and binds the fibers with a substance (binder) that elutes from the fibers due to adhesion of water. In the method of spraying water, water does not completely penetrate into the inner layer and the inner layer has a low binding strength. Therefore, a core material that is more flexible as the inner layer can be obtained.
[0022]
The fibers are preferably inorganic fibers, particularly glass wool or glass fibers.
[0023]
Moreover, in the vacuum heat insulating material of this invention, it is preferable that the said jacket material is a plastics-metal foil laminated film. Covering the core material with a laminate film improves the heat insulation effect, and in particular, the metal foil is used as the inner layer and the plastic is used as the outer layer. The heat insulation effect is further improved by the ease of attachment to and the increased affinity with the foam heat insulating material.
[0024]
Therefore, since the vacuum heat insulating material of the present invention has the above-described specific configuration, the thermal conductivity is in the range of 0.0015 to 0.0025 W / mK. This heat insulation performance corresponds to 10 times that of a conventional urethane heat insulating material and 20 times that of glass wool, and is at a very high level.
[0025]
Next, the refrigeration equipment and the cooling / heating equipment of the present invention have an outer box, an inner box, and a foam heat insulating material and a vacuum heat insulating material in a space formed by the outer box and the inner box, and the vacuum heat insulating material. Is placed in the space, and the space other than the vacuum heat insulating material is filled with a foam heat insulating material, and is a refrigeration device and a cooling / heating device, wherein the vacuum heat insulating material is the vacuum heat insulating material of the present invention. And
[0026]
Refrigeration equipment and cooling / heating equipment with excellent heat insulation performance by placing the vacuum heat insulation material with excellent heat insulation performance of the present invention in the space consisting of the outer box and the inner box and filling the other space with foam insulation. Can be obtained.
[0027]
The refrigerator of the present invention has an outer box, an inner box, a foam heat insulating material and a vacuum heat insulating material in a space formed by the outer box and the inner box, and the vacuum heat insulating material is disposed in the space. It is a refrigerator which is arranged on the outer box side and is filled with a foam heat insulating material in the space other than the vacuum heat insulating material, wherein the vacuum heat insulating material is the vacuum heat insulating material of the present invention, and the vacuum heat insulating material The surface of the hardened layer side is opposed to the inner surface of the outer box.
[0028]
The vacuum heat insulating material of the present invention can reduce the binder concentration of the inner layer of the core material, is lighter than the conventional vacuum heat insulating material using the core material having a uniform binder concentration up to the core material, and can improve the heat insulating performance. Moreover, the vacuum heat insulating material of the present invention has high rigidity because a hardened layer is formed on the surface of the core material. Moreover, the vacuum heat insulating material of this invention can make the surface precision of the surface by the side of a hardened layer high by compressing and heating with the press machine of a smooth metal mold | die, and forming a hardened layer in a core material. In addition, the vacuum heat insulating material of the present invention can be used in a wide area because it is lightweight, has high rigidity, and has high planar accuracy.
[0029]
And, on the outer box side of the space consisting of the outer box and the inner box, the vacuum heat insulating material of the present invention is disposed in a wide area with light weight, rigidity, excellent heat insulation performance and high plane accuracy, and foam insulation in other spaces By filling the material, the outer appearance quality (planar accuracy) of the outer box and the heat insulating performance of the heat insulating box can be made compatible at a high level, and a refrigerator that is energy saving and excellent in appearance quality can be obtained.
[0030]
In the refrigerator of the present invention, the refrigerant pipe can be stored by pressing from the outside of the jacket material on the surface of the hardened layer with respect to the portion where the refrigerant pipe is disposed on the inner surface of the outer box. It is preferable that the vacuum heat insulating material in which the groove is formed is arranged so that the refrigerant pipe is accommodated in the groove. The vacuum heat insulating material of the present invention reduces the binder concentration of the inner layer of the core material and softens the inner layer of the core material, so that the surface of the vacuum heat insulating material can be pressed from above the outer cover material after the vacuum heat insulating material is manufactured. Grooves can be formed in. Also, a large vacuum heat insulating material is disposed so as to cover the refrigerant pipe, without arranging a plurality of small vacuum heat insulating materials by avoiding the refrigerant pipe, also on a portion where the refrigerant pipe is disposed on the inner surface of the outer box. Therefore, with a small number of vacuum heat insulating materials, it is possible to efficiently insulate the heat of the outer box and the refrigerant pipe from being transmitted to the inside of the cabinet, and it is possible to obtain a refrigerator with excellent energy saving.
[0031]
In addition, the vacuum heat insulating material of this invention can be fixed to an outer box with adhesives, such as a hot melt, and it is preferable that the thickness of the layer of the adhesive agent is the range of 70-130 micrometers. Providing an adhesive layer having a thickness exceeding 130 μm is a waste of the adhesive, and the adhesive is more likely to conduct heat than the foamed heat insulating material, leading to a decrease in heat insulation performance. On the other hand, if the adhesive layer is less than 70 μm, the reliability of adhesion decreases.
[0032]
The vacuum heat insulating material core material of the present invention comprises a laminate of fiber nonwoven webs, and a cured layer in which the fibers are heat-fixed with a binder is formed on at least one surface of the core material. And
[0033]
In general, depending on the binder, a cured layer is formed only on the surface layer of the molded body, and a small amount of the binder that has penetrated into the inside moves to the surface layer due to migration, and the cured layer is hardly formed inside. In this case, a crack is generated inside, and there is a concern that the strength of the entire molded body is reduced. However, according to the method of obtaining a board-shaped molded body by, for example, forming a fiber in a board shape, and then applying a binder to the surface and compressing and heating it, the surface layer is a layer with a high concentration obtained by curing the applied binder. A small amount of the permeated binder does not migrate so much and hardens inside the surface layer. As a result, it is possible to obtain molded bodies having different binder concentrations with respect to the thickness direction of the board, and to obtain a board-shaped molded body having excellent strength in which a small amount of binder is cured even inside the board.
[0034]
Therefore, the vacuum heat insulating material core manufacturing method of the present invention includes a step of laminating fibers so as to have a predetermined shape, a step of applying an aqueous binder solution or water to at least one side of the outer surface of the laminated fiber web, and a binder. It includes a step of compressing the coated laminated fiber web at a temperature of 100 ° C. or less and a step of heating and compressing the compressed laminated fiber web at a temperature of 100 ° C. or more.
[0035]
DETAILED DESCRIPTION OF THE INVENTION
The vacuum heat insulating material of the present invention is a vacuum heat insulating material comprising a board-shaped core material and a jacket material that encloses the core material, and the inside thereof is sealed after decompression, and the board-shaped core material is a fiber nonwoven web. A hardened (solidified) layer in which the fibers are heat-fixed with a binder is formed on at least one surface of the core material. Such a board-like core material preferably has a surface hardness of 15 to 70, and this surface hardness represents the surface hardness of the core material before packaging by the jacket material. Therefore, the surface hardness as the vacuum heat insulating material after packaging with the outer jacket material is preferably 50 to 80, and desirably 60 to 75.
[0036]
Moreover, it is preferable that the surface hardness of the core material in the state taken out by tearing the jacket material after using the vacuum heat insulating material is 15 to 50, and desirably 20 to 40. If the surface hardness is too small, the handling properties are poor and the work efficiency in the disposal process may be reduced. On the other hand, if the durability of the core material is taken into consideration, the surface hardness is high even if there is a slight decrease in hardness. If it is too large, a process such as cutting off the cured (solidified) layer is necessary, and the process may become complicated.
[0037]
In the present invention, the hardness is defined by a value when the hardness of the surface of the core material is measured with a durometer, and the larger the numerical value, the harder the smaller the value.
[0038]
In the vacuum heat insulating material of the present invention, a hardened (solidified) layer formed by binding the fibers with a binder is formed on the surface of at least one side of the board-shaped core material. The binder concentration in the inner layer is different. More specifically, the vacuum heat insulating material of the present invention has a higher binder concentration in the surface layer in the thickness direction of the board-shaped molded body than in the other layers. By making the binder concentration of the surface layer larger than that of the other layers, a core material excellent in surface smoothness can be obtained in addition to the above effects, and a vacuum heat insulating material excellent in appearance can be obtained.
[0039]
Further, by providing a portion with a low binder concentration inside the surface layer other than the surface layer, the internal solid heat conduction can be reduced, and the heat insulation performance is improved. Furthermore, the exhaust resistance at the portion where the binder concentration is low becomes small, the degree of vacuum at the time of exhaust can be easily lowered, and improvement in productivity of the vacuum heat insulating material can be expected. Thus, the vacuum heat insulating material excellent in core material rigidity, heat insulation performance, and productivity can be obtained by using the core material from which a binder density | concentration differs in the thickness direction of a molded object.
[0040]
The board-shaped core material in the present invention is not particularly limited as long as the non-woven fiber web laminate is made into a board. The fiber constituting the core material may be either an organic fiber or an inorganic fiber as long as the characteristics of the board-shaped core material of the present invention can be satisfied. Examples of the fibers include inorganic fibers such as glass wool, glass fibers, alumina fibers, silica alumina fibers, silica fibers, rock wool, and silicon carbide fibers, natural fibers such as cotton, synthetic fibers such as polyester, nylon, and aramid. An organic fiber etc. can be mentioned and a well-known material can be used. From the viewpoint of heat resistance during compression heating, inorganic fibers are desirable. Among these, glass wool and glass fiber are preferably used because they have high weather resistance and good water resistance. In particular, from the viewpoint of excellent weather resistance and water resistance, those made of boron-containing glass are desirable.
[0041]
The fiber diameter used in the present invention is not particularly limited, but from the viewpoint of obtaining a core material that can form a continuous pore structure and has a high surface hardness and a light weight, 0.1 to 20 μm, Preferably it is 1-10 micrometers, More preferably, it is 2-7 micrometers. In addition, from the viewpoint of preventing peeling of the laminate and the like, those having an average fiber length of 5 to 15 mm are preferably used, but are not limited thereto.
[0042]
You may add a powder to a fiber material in the range which does not impair the characteristic of the board-shaped core material of this invention. Examples of the powder include inorganic powders such as silica, pearlite, and carbon black, and organic powders such as synthetic resin powder. In addition, known materials such as pulverized foamed resin such as urethane foam, phenol foam, and styrene foam can be used as appropriate.
[0043]
As the binder used in the present invention, an inorganic or organic binder can be used. Specifically, colloidal silica, alumina sol, water glass, gypsum, boric acid or its salt, boron oxide, phosphoric acid or its salt, sodium silicate, alkyl silicate, or other inorganic binders, phenol resin, urea resin, melamine resin And thermosetting resins such as xylene resin, furan resin and epoxy resin, thermoplastic resins such as vinyl acetate and acrylic resin, and organic binders such as natural product adhesives. These may be used alone or in combination, or may be diluted with water or a known organic solvent. Among these, an inorganic binder is preferable, and it is particularly preferable that at least one compound of boric acid, borate, phosphoric acid, phosphate, or a heating product thereof is included.
[0044]
Examples of boric acid compounds include boric acid, metaboric acid, boron oxide, sodium tetraborate hydrates and anhydrides such as sodium borate, ammonium borate, lithium borate, and magnesium borate. , Calcium borate, aluminum borate, zinc borate, perborate, alkyl boric acid, boroxine derivative and the like.
[0045]
Examples of phosphoric acid compounds include phosphoric acid, phosphorus oxides such as diphosphorus pentoxide, primary phosphates, secondary phosphates, tertiary phosphates, pyrophosphates, tripolyphosphates, and metaphosphates. And the like, their sodium salts, potassium salts, ammonium salts, magnesium salts, aluminum salts and the like.
[0046]
Of these, glass formers or water-soluble substances are preferred. For example, boric acid, metaboric acid, boron oxide, borax, phosphoric acid, primary aluminum phosphate, sodium hexametaphosphate, and the like.
[0047]
When a board-like fiber molded body is produced as a binder for a molded body, one or more of the above compounds are mixed, or other binders are mixed, or they are diluted.
[0048]
A method for attaching the binder to the core material is not particularly limited, and the binder or a diluted solution thereof is applied or sprayed to be attached. Specifically, after molding the core material to some extent, the binder is sprayed and then heated and compressed to obtain molded bodies having different binder concentrations in the thickness direction of the board-shaped molded body.
[0049]
Also, when the fiber is made into fibers, a binder or a diluted solution thereof is sprayed, fibers with a high binder concentration are arranged in one part of the board, and fibers with a low binder concentration or fibers without a binder are arranged in the other part, and then the fibers It is also possible to obtain boards with different binder concentrations in the thickness direction of the molded body by solidifying the laminate by compression heating or the like. Use of the fiber laminate makes it difficult for heat transfer between the layers to improve heat insulation.
[0050]
Further, without using the binder, water may be sprayed on the surface of the fibrous nonwoven web laminate, and the fibers may be bound by a substance (binder) that is eluted from the fibers due to adhesion of water. In this case, since water does not completely penetrate into the inner layer and the inner layer has a low binding strength, a core material that is more flexible as the inner layer can be obtained.
[0051]
Alternatively, it is possible to obtain core materials having different concentrations in the thickness direction by combining two or more board-shaped molded bodies having a high binder concentration and two or more board-shaped molded bodies having a low binder concentration.
[0052]
The binder concentration is preferably such that the binder is attached to the core material so that the solid content of the binder is 0.1 wt% or more and 20 wt% or less. This is because when the amount of the binder is increased, there is a concern about an increase in gas generated from the binder and an increase in solid thermal conductivity, which may adversely affect the heat insulating performance of the vacuum heat insulating material. On the other hand, when the amount of the binder is small, solidification of the fiber laminate is insufficient.
[0053]
The binder concentration is preferably different in the thickness direction of the board-shaped molded body. However, the effect of reducing the solid thermal conductivity and the exhaust resistance to a portion where the binder concentration is low and the rigidity of the board to be provided to a large portion. Each can be given. In particular, at least one surface layer of the board-shaped molded body or a board-shaped molded body having a high binder concentration in the surface layers on both surfaces is preferable, and thus the surface property is improved when a vacuum heat insulating material is formed. After the binder is attached, the laminated molded body is formed into a board by compression or heat compression.
[0054]
In this case, the density (density) of the board-shaped core material is 100 to 400 kg / m. 3 It is desirable to pressurize so that the density in the board may be different. Density is 100kg / m 3 If it is smaller, it becomes difficult to maintain the shape as a molded body, and 400 kg / m. 3 This is because if it is larger, the solid thermal conductivity is increased and the heat insulating performance of the vacuum heat insulating material is considered to deteriorate. The density (density) of the board is preferably 120 to 300 kg / m. 3 More preferably, 150 to 250 kg / m 3 It is good to be in the range.
[0055]
The thermal conductivity of the board-shaped core material is in the range of 0.030 to 0.038 W / mK, preferably in the range of 0.033 to 0.037 W / mK, at an average temperature of 24 ° C. Good. Moreover, it is desirable that the board-shaped core material has a certain degree of rigidity in consideration of handling properties, productivity, and the like. The thickness of the core (total thickness when two or more layers are laminated) is not particularly limited, but a thickness of 5 to 20 mm is usually used.
[0056]
The covering material in the present invention is not particularly limited as long as it has at least a gas barrier layer and a heat fusion layer, and a surface protective layer or the like may be provided as necessary.
[0057]
As the gas barrier layer, metal foil, metal, inorganic oxide, diamond-like carbon-deposited plastic film, or the like can be used. However, the gas barrier layer is particularly limited as long as it is used for the purpose of reducing gas permeation. It is not a thing.
[0058]
As said metal foil, foils, such as aluminum, stainless steel, and iron, can be used, but it does not specifically limit.
[0059]
In addition, the material of the plastic film serving as a base material on which the metal or the like is deposited is not particularly limited, but to polyethylene terephthalate, ethylene-vinyl alcohol copolymer resin, polyethylene naphthalate, nylon, polyamide, polyimide, and the like. Vapor deposition is preferred.
[0060]
Examples of the material for metal deposition on the plastic film include aluminum, cobalt, nickel, zinc, copper, silver, and mixtures thereof, but are not particularly limited.
[0061]
Examples of the material for depositing the inorganic oxide on the plastic film include silica and alumina, but are not particularly limited.
[0062]
In addition, as the heat welding layer, a low density polyethylene film, a chain low density polyethylene film, a high density polyethylene film, a polypropylene film, a polyacrylonitrile film, an unstretched polyethylene terephthalate film, an ethylene-vinyl alcohol copolymer film, or a film thereof. Although a mixture etc. can be used, it does not specifically limit.
[0063]
It is also possible to provide a surface protective layer on the outer surface of the gas barrier layer.
[0064]
As the surface protective layer, a stretched product of nylon film, polyethylene terephthalate film, polypropylene film, or the like can be used. If a nylon film or the like is further provided on the outer side, flexibility is improved and bending resistance is improved.
[0065]
The film as described above is laminated and used. Among these, a plastic-metal foil laminate film is preferably used. Moreover, you may use the metal container using metal plates, such as an iron plate, a stainless steel plate, and a zinc plate, as a covering material.
[0066]
The bag shape of the jacket material is not particularly limited, such as a four-side seal bag, a gusset bag, a three-side seal bag, a pillow bag, and a center tape seal bag. In addition, there is a method of using a metal plate by forming it into a rectangular parallelepiped.
[0067]
Further, in order to further improve the reliability of the vacuum insulator, it is possible to use a getter substance such as a gas adsorbent or a moisture adsorbent.
[0068]
In the production of the vacuum heat insulating material of the present invention, first, a jacket material may be prepared, and then the core material may be inserted into the jacket material and the inside may be depressurized and sealed. A vacuum insulation material is formed by installing a jacket material made of a roll or sheet laminate film, and then heat-sealing the jacket material after the roll or sheet coat is placed along the core. It may be manufactured, or vacuum insulation material is manufactured by directly reducing the pressure inside the jacket material into which the core material is inserted, and sealing the jacket material opening, or in a board shape in a container formed of a metal plate There is a method such as inserting a core material, connecting the vacuum pump and the metal container with a tube, reducing the pressure inside the container, and then sealing the tube to make a vacuum heat insulating material, etc. is not. Further, the board-shaped core material may be dried with moisture before the jacket material is inserted, and the adsorbent may be inserted together when the jacket material is inserted.
[0069]
Since the vacuum heat insulating material of the present invention has a hardened layer formed on the surface, a material having excellent surface smoothness can be obtained even after the reduced pressure treatment. The surface roughness can be determined according to JIS B 0601.
[0070]
Moreover, the vacuum heat insulating material of the present invention is preferably used as a heat insulating material for refrigeration equipment and cold / hot equipment. In that case, the foam insulation and the vacuum heat insulating material are arranged in the space formed by the outer box and the inner box of the refrigeration equipment and the cooling / heating equipment, the vacuum heat insulating material is arranged in the space, and the vacuum heat insulating material The space other than the above is filled with foam heat insulating material. For example, when applied to a refrigerator, a vacuum heat insulating material is applied to the outer box side or the inner box side of the space between the outer box and the inner box of the refrigerator, and other spaces are filled with resin foam, or the vacuum heat insulating material and the foam are filled. The insulation method in which the resin body is integrally foamed is disposed in the space between the outer box and the inner box of the refrigerator, or used in the same manner as the door, or used as a partition plate. Although it is not a thing, it is desirable to use the said vacuum heat insulating material between a machine room and an inner box, or the circumference | surroundings of a freezer compartment since it is excellent in thermal insulation efficiency and can operate a refrigerator with low electric energy.
[0071]
When affixing vacuum insulation to refrigeration equipment such as refrigerators or cold / hot equipment, the surface on the hardened layer side of the vacuum insulation is better because it prevents the formation of cavities between the vacuum insulation and the outer box to enhance the insulation effect. Is preferably fixed to face the inner surface of the outer box of the refrigerator. For fixing, an adhesive such as a double-sided tape or hot melt can be used, but a hot melt adhesive is preferably used from the viewpoint of high adhesion reliability. The type of hot melt adhesive is not particularly limited, and examples thereof include those based on ethylene-vinyl acetate copolymer resin, polyamide resin, polyester resin, synthetic rubber and the like.
[0072]
Examples of the resin foam include rigid urethane foam, phenol foam, and styrene foam, but are not particularly limited.
[0073]
Further, for example, the foaming agent used when foaming the rigid urethane foam is not particularly limited, but from the viewpoint of protection of the ozone layer and prevention of global warming, cyclopentane, isopentane, n-pentane, isobutane, n- Butane, water (carbon dioxide gas foaming), azo compound, argon and the like are desirable, and cyclopentane is particularly desirable from the viewpoint of heat insulation performance.
[0074]
Further, the refrigerant used for the refrigeration equipment / cold temperature equipment is not particularly specified such as Freon 134a, isobutane, n-butane, propane, ammonia, carbon dioxide, water, and the like.
[0075]
In the present invention, the refrigeration equipment and the cooling / heating equipment are shown as representatives of equipment that requires heat insulation at a room temperature from −30 ° C., which is the operating temperature range, for example, a cold car, a refrigerator using electronic cooling, It includes equipment that does not require power, such as cold equipment that uses hot and cold heat in a range up to higher temperatures, such as automatic sales, and gas equipment or a cooler box.
[0076]
Furthermore, the vacuum heat insulating material of this invention can also be used for a personal computer, a jar pot, a rice cooker, etc.
[0077]
Next, the manufacturing method of the vacuum heat insulating material core material of this invention is demonstrated. In the production method of the present invention, a step of laminating fiber webs to have a predetermined shape, a step of applying an aqueous binder solution (or water) diluted with water to at least one of the outer surfaces of the laminated fiber webs, A step of compressing the coated laminated fiber web at a temperature of 100 ° C. or lower; and a step of heating and compressing the compressed laminated fiber web at a temperature of 100 ° C. or higher. The fiber web is laminated so as to have a predetermined shape, and an aqueous binder solution (or water) diluted with water is applied to the outer surface of the laminated fiber web. At this time, an aqueous binder solution (or water) diluted with water is applied to one or both surfaces of the laminated fiber or an arbitrary outer surface such as the entire surface. Thereafter, the laminated fiber web to which the binder is applied is compressed at a temperature of 100 ° C. or lower, and this is preferably room temperature compression at which moisture is hard to evaporate.
[0078]
Here, the concentration of the aqueous binder solution varies depending on the type of binder, the coating amount, and the added amount, and thus cannot be defined unconditionally. However, considering the solubility in water, the concentration is 0.5 to 20% by weight. desirable. The coating amount of the aqueous binder solution is not particularly limited, but it is preferably used in a proportion of 50 parts by weight or more and 300 parts by weight or less with respect to 100 parts by weight of the fiber laminate. If the amount used is less than 50 parts by weight, the aqueous solution will not easily penetrate into the fiber laminate, and if it is more than 300 parts by weight, excess water will flow out in the liquid state and the binder will also flow out. This is because a loss occurs in the binder.
[0079]
Thereafter, the laminated fiber is heated and compressed at a temperature of 100 ° C. or higher. This is for the purpose of evaporating moisture and curing the binder, and it is desirable to heat the laminated fiber at a temperature higher than the binder curing temperature. The temperature is preferably 600 ° C. or lower from the viewpoint of preventing the binder from penetrating too much into the laminate during heat compression and preventing the fibers from melting.
[0080]
In general, when a molded body is produced using fibers coated with a binder at the time of fiberization, it is easy to obtain a board having a uniform binder distribution in the molded body, and it is difficult to obtain a molded body having a concentration gradient. However, according to the production method of the present invention, the fibers are laminated in a predetermined shape, and a binder is applied to at least one surface of the laminated fibers, and then compressed once at a temperature of 100 ° C. or lower, that is, a moisture evaporation or lower temperature. The surface layer has a high binder concentration and the inside has a low binder concentration. After that, the binder concentration varies in the thickness direction by compressing and heating at a temperature of 100 ° C. or higher, and a small amount of binder is also formed inside the molded body. It is easy to obtain a core material bound to the core material, and a core material excellent in strength can be obtained.
[0081]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples.
[0082]
Example 1
FIG. 1 is a sectional view of a vacuum heat insulating material in one embodiment of the present invention. Reference numeral 1 denotes a vacuum heat insulating material, in which a board-shaped core material 2 is inserted into a jacket material 3 and the inside is sealed under reduced pressure to form a vacuum heat insulating material 1.
[0083]
The board-shaped core material 2 has an average fiber diameter of 5 μm, an average fiber length of 10 mm, and a true specific gravity of 2.5 g / cm. 3 Glass wool 4 was laminated until a predetermined density was reached. The binder used the binder 5 which melt | dissolved 10 weight part of water glass in 90 weight part of water as the binder 5, and made 100 weight part of water glass aqueous solution. This water glass aqueous solution is sprayed on both surfaces of the laminated glass wool 4 with a spraying device, and then the density is 230 kg / m in a hot air circulating furnace at 450 ° C. 3 The board-shaped core material 2 was obtained by pressing for 20 minutes. The density of the board-shaped core material is 235kg / m 3 The thermal conductivity was 0.35 W / mK.
[0084]
A cross-sectional view of the board-like core material 2 is shown in FIG. There was not much binder 5 remaining on the board inner surface layer, and it was confirmed that many binders were cured in the outer layer of the board and a cured layer was formed on the surface. The surface hardness of this core material was measured and found to be 65.
[0085]
Moreover, what observed the external appearance of the surface of the board-shaped core material with Olympus optical microscope BH-2 (magnification: 580 times) was shown in FIG. It can be seen that the crossed fibers are bound and cured by the binder.
[0086]
The jacket material 2 was formed by bag-making two laminated films with a three-side seal. Of the two laminated films, one is a linear low-density polyethylene film (hereinafter referred to as LLDPE) as a heat-sealing layer of 50 μm, and a gas barrier layer of an ethylene-vinyl alcohol copolymer film (hereinafter referred to as 15 μm in thickness). , EVOH) and a film formed by depositing 450 Å of aluminum on a 12 μm thick polyethylene terephthalate film (hereinafter referred to as PET), and a film formed by depositing 450 Å of aluminum on each other. It consists of a film, and LLDPE for the heat-sealing layer and EVOH for the gas barrier layer are dry laminated. The other one is composed of a 50 μm thick LLDPE thermal fusion layer, a 6 μm thick aluminum foil as a gas barrier layer, a 12 μm thick nylon protective layer, and a 12 μm thick nylon outermost layer. Yes.
[0087]
The board-shaped core material 2 was dried in a drying furnace at 140 ° C. for 1 hour, inserted into the jacket material 3, and the inside was reduced to 3 Pa for 5 minutes and sealed.
[0088]
The heat conductivity of the vacuum heat insulating material 1 produced as described above was 0.0022 W / mK at an average temperature of 24 ° C., and its surface hardness was 70.
[0089]
Moreover, although the deterioration of the heat insulating material by the accelerated test was evaluated in order to confirm the reliability over time, the thermal conductivity under the 10-year elapsed condition was 0.005 W / mK at an average temperature of 24 ° C. The vacuum insulation material was broken and the core material was taken out and its surface hardness was measured to be 60.
[0090]
(Example 2)
A vacuum heat insulating material having the structure shown in FIG. 3 was produced. A board-shaped core material 2A was inserted into the jacket material 3, and the inside was sealed under reduced pressure to obtain a vacuum heat insulating material. The board-like core material 2A has an average fiber diameter of 5 μm, an average fiber length of 10 mm, and a true specific gravity of 2.5 g / cm. 3 Glass wool 4 was laminated until a predetermined density was reached. As binder 5A, 100 parts by weight of glass wool was used by dissolving 3 parts by weight of boric acid as a binder in 97 parts by weight of water to make 100 parts by weight of boric acid aqueous solution. This boric acid aqueous solution was sprayed on both surfaces of the laminated glass wool 4 with a spraying device, and once pressed at room temperature. Thereafter, the density is 230 kg / m in a hot air circulating furnace at 350 ° C. 3 Was pressed for 20 minutes to obtain a board-like core material 2A. The density of this board-like core material is 233 kg / m 3 The thermal conductivity was 0.34 W / mK.
[0091]
A cross-sectional view of the board-like core material 2A is shown in FIG. Although the board inner surface layer was weaker than the outer layer, it was bound by the binder, the amount of the binder increased toward the outer layer, and it was confirmed that a hardened layer was formed on the surface. It was 45 when the surface hardness of this core material was measured.
[0092]
The board-like core material 2A was dried in a drying furnace at 140 ° C. for 1 hour, inserted into the jacket material 3, and the inside was reduced to 3 Pa for 5 minutes and sealed. The jacket material 3 was the same as the jacket material used in Example 1.
[0093]
The heat conductivity of the vacuum heat insulating material produced as described above was 0.002 W / mK at an average temperature of 24 ° C., and its surface hardness was 60.
[0094]
Moreover, although the deterioration of the heat insulating material by the accelerated test was evaluated in order to confirm the reliability over time, the thermal conductivity under the 10-year elapsed condition was 0.005 W / mK at an average temperature of 24 ° C. It was 35 when the outer shell material of this vacuum heat insulating material was broken and the core material was taken out and its surface hardness was measured.
[0095]
Compared with the vacuum heat insulating material obtained in Example 1, this vacuum heat insulating material has boric acid as the binder and is pressed at room temperature before heat compression, so that the binder remains inside the core material. As a result, cracks in the core did not occur and the strength was improved.
[0096]
(Example 3)
A vacuum heat insulating material having the structure shown in FIG. 5 was produced. The board-shaped core material 2B was inserted into the jacket material 3, and the inside was sealed under reduced pressure to obtain a vacuum heat insulating material. The board-shaped core material 2B is composed of three boards. Two of them (21B) have an average fiber diameter of 5 μm, an average fiber length of 10 mm, and a true specific gravity of 2.5 g / cm. 3 The binder 5B is obtained by dissolving 5 parts by weight of boric acid as a binder in 95 parts by weight of water and 100 parts by weight of an aqueous boric acid solution. used. This boric acid aqueous solution was sprayed on both surfaces of the laminated glass wool 4 with a spraying device, and once pressed at room temperature. Thereafter, the density is 230 kg / m in a hot air circulating furnace at 350 ° C. 3 Was pressed for 20 minutes. The other sheet (22B) was obtained by compressing and heating glass wool 4 having an average fiber diameter of 5 μm and an average fiber length of 10 mm at 350 ° C. It was confirmed that a hardened layer was formed on the surface of the board-shaped core material (21B) using the binder, and the surface hardness was 45.
[0097]
These three boards were stacked with a board (21B) using boric acid on the outside and a board (22B) using only glass wool on the inside to form a board-like core material 2B. A cross-sectional view of the board-like core material 2B is shown in FIG. The jacket material 3 was the same as the jacket material used in Example 1. The density of this board-like core material is 190 kg / m 3 The thermal conductivity was 0.34 W / mK.
[0098]
The board-like core material 2B was dried in a drying furnace at 140 ° C. for 1 hour, inserted into the jacket material 2, and the inside was reduced to 3 Pa for 5 minutes and sealed.
[0099]
The heat conductivity of the vacuum heat insulating material 1B produced as described above was 0.0019 W / mK at an average temperature of 24 ° C., and its surface hardness was 60.
[0100]
Moreover, although the deterioration of the heat insulating material by the accelerated test was evaluated in order to confirm the reliability over time, the thermal conductivity under the 10-year elapsed condition was 0.005 W / mK at an average temperature of 24 ° C. It was 35 when the outer shell material of this vacuum heat insulating material was broken and the core material was taken out and its surface hardness was measured.
[0101]
By using a board with a boric acid binder for the surface layer and a board made only of glass wool for the inner layer, there was no binder in the inner layer, so a core material with low solid thermal conductivity and excellent heat insulating performance could be obtained. .
[0102]
Example 4
FIG. 7 is a cross-sectional view of a refrigerator-freezer according to an embodiment of the present invention, and FIG. 8 is an enlarged cross-sectional view of a main part of a ceiling surface portion of a heat insulating box of the refrigerator-freezer. 6 is a refrigerator, 7 is a heat insulating box forming the refrigerator, and 1A is a vacuum heat insulating material. In this embodiment, the vacuum heat insulating material 1 </ b> A is arranged on the outer box 8 side inside the box so that the surface on which the hardened layer of the core material 2 </ b> A is formed faces the inner surface of the outer box 8.
[0103]
Further, in the present embodiment, the refrigerant pipe 21 is pressed from the outside of the jacket material 3 on the surface on the side where the hardened layer of the core material 2A is formed with respect to the portion where the refrigerant pipe 21 is disposed on the inner surface of the outer box 8. The vacuum heat insulating material 1 </ b> A in which the groove 22 that can accommodate 21 is formed is disposed so that the refrigerant pipe 21 is accommodated in the groove 22.
[0104]
In this embodiment, the vacuum heat insulating material 1 </ b> A is fixed to the outer box 8 with a thermoplastic gel-like hot melt adhesive 23. The thickness of the layer of the adhesive 23 is about 100 μm, but is preferably in the range of 70 to 130 μm. The adhesive 23 is uniformly and thoroughly applied to the surface to be bonded to the outer box of the vacuum heat insulating material 1A using a roller or the like.
[0105]
The heat insulating box body 7 is provided with a vacuum heat insulating material 1A in advance inside a box body in which an outer box 8 formed by press-molding an iron plate and an inner box 9 formed by vacuum-molding ABS resin are provided via a flange. A space other than the material 1 </ b> A is foam-filled with a rigid urethane foam 10. The rigid urethane foam 10 uses cyclopentane as a foaming agent.
[0106]
The heat insulation box 7 is divided by a partition plate 12, and the upper part is a refrigerator compartment 13 and the lower part is a freezer compartment 14. A damper 15 is attached to the partition plate 12.
[0107]
Reference numeral 16 denotes an evaporator disposed in the refrigerator, which sequentially connects the compressor 18, the condenser 19, and the capillary tube 20 in an annular manner to form a refrigeration cycle. Isobutane, which is a refrigerant, is enclosed in the refrigeration cycle.
[0108]
The evaporators may be provided at two locations of the refrigerator compartment 13 and the freezer compartment 14 and connected in series or in parallel to form a refrigeration cycle.
[0109]
Further, a door body 11 is attached to the refrigerator 6, a vacuum heat insulating material 1 </ b> A is disposed inside the door body 11, and a space other than the vacuum heat insulating material is filled with foam with a hard urethane foam 10.
[0110]
The vacuum heat insulating material 1A has the same configuration as that shown in the second embodiment. When the electric power consumption of the refrigerator comprised in this way was measured, it was falling 25% from the refrigerator which does not equip a vacuum heat insulating material, and the heat insulation effect was confirmed.
[0111]
(Comparative Example 1)
FIG. 9 is a cross-sectional view of a vacuum heat insulating material in one comparative example of the present invention. 1a is a vacuum heat insulating material, and the board-shaped core material 2a is inserted into the outer cover material 3a, and the inside is sealed as a reduced pressure to form a vacuum heat insulating material 1a. The material configuration of the jacket material 3a is the same as that of the jacket material 3 used in the first embodiment, and a bag is made with a three-way seal to form the jacket material 3a.
[0112]
The board-like core material 2a was sprayed so that the binder 5a was uniformly attached to the fiber surface after fiberizing the glass wool 4a (same as that used in Example 1). The binder aqueous solution used was prepared by dissolving 10 parts by weight of a phenol resin as a binder in 90 parts by weight of water and 100 parts by weight of a phenol aqueous solution with respect to 100 parts by weight of glass wool. This raw cotton with binder is laminated so as to have a predetermined density, and then the density is 230 kg / m in a 200 ° C. hot air circulating furnace. 3 Was pressed for 20 minutes. It was 75 when the surface hardness of this board-shaped core material was measured. The density of this board-shaped core material is 240 kg / m. 3 The thermal conductivity was 0.32 W / mK.
[0113]
The board-like core material 2a was dried in a drying furnace at 140 ° C. for 1 hour, inserted into the jacket material 2a, and the inside was reduced to 3 Pa for 10 minutes and sealed. A cross-sectional view of the board-shaped core material 2a is shown in FIG.
[0114]
The vacuum heat insulating material 1a produced as described above had a thermal conductivity of 0.003 W / mK at an average temperature of 24 ° C. and a surface hardness of 80.
[0115]
Moreover, although the deterioration of the heat insulating material by an accelerated test was evaluated in order to confirm the reliability over time, the thermal conductivity under a 10-year elapsed condition was 0.021 W / mK at an average temperature of 24 ° C. It was 75 when the outer shell material of this vacuum heat insulating material was broken and the core material was taken out and its surface hardness was measured.
[0116]
Compared with Example 1, since the phenol resin was used as the binder and the resin was uniformly cured in the board, both the initial performance and the aging performance were deteriorated.
[0117]
(Comparative Example 2)
FIG. 9 is a cross-sectional view of a vacuum heat insulating material in one comparative example of the present invention. 1b is a vacuum heat insulating material, the board-shaped core material 2b was inserted into the jacket material 3b, and the inside was sealed under reduced pressure to obtain a vacuum heat insulating material 1b. The material configuration of the jacket material 3b is the same as that of the jacket material 3 used in Example 1, and a bag was made with a three-way seal to obtain a jacket material 3b.
[0118]
The board-like core material 2b was sprayed so that the binder 5b uniformly adhered to the fiber surface after fiberizing the glass wool 4b (same as that used in Example 2). As the binder, 100 parts by weight of glass wool was used by dissolving 3 parts by weight of boric acid as a binder in 97 parts by weight of water to obtain 100 parts by weight of an aqueous boric acid solution. This raw cotton with a binder is laminated so as to have a predetermined density, and then the density is 230 kg / m in a hot air circulating furnace at 350 ° C. 3 Was pressed for 20 minutes.
[0119]
The board-like core material 2b was dried in a drying furnace at 140 ° C. for 1 hour, inserted into the jacket material 2b, and the inside was reduced to 3 Pa for 10 minutes and sealed. A cross-sectional view of the board-like core material 2b is shown in FIG. The density of this board-shaped core material is 233 kg / m. 3 The thermal conductivity was 0.34 W / mK. The surface hardness of this board-like core material was measured and found to be 45.
[0120]
The heat conductivity of the vacuum heat insulating material 1b produced as described above was 0.0025 W / mK at an average temperature of 24 ° C., and its surface hardness was 60.
[0121]
Moreover, although the deterioration of the heat insulating material by an accelerated test was evaluated in order to confirm reliability over time, the thermal conductivity under a 10-year elapsed condition was 0.015 W / mK at an average temperature of 24 ° C. It was 35 when the outer shell material of this vacuum heat insulating material was broken and the core material was taken out and its surface hardness was measured.
[0122]
Compared with Example 2, since the binder was uniformly cured, the initial performance was deteriorated and the exhaust time was required for a long time.
[0123]
【The invention's effect】
As described above, according to the present invention, it is possible to obtain a vacuum heat insulating material that is easy to mold and excellent in handling properties, has high surface hardness, excellent surface smoothness, and excellent heat insulating properties with low solid thermal conductivity.
[0124]
In addition, since a cured layer formed by binding fibers with a binder is formed on the surface of at least one side of the vacuum heat insulating material core material, rigidity is imparted to the core material to facilitate handling, and surface smoothness is achieved. It becomes good and productivity at the time of vacuum heat insulating material manufacture improves. In addition, since the concentration of the binder that binds the fibers in the thickness direction of the core material is larger in the surface layer than in the other layers and a small portion is provided inside, the internal solid heat conduction becomes small, and the heat insulation performance improves. Furthermore, the exhaust resistance at the portion where the binder concentration is low is reduced, the degree of vacuum at the time of exhaust can be easily lowered, and the productivity improvement of the vacuum heat insulating material can be expected.
[0125]
In addition, according to the refrigeration equipment and cooling / heating equipment of the present invention, the vacuum heat insulating material excellent in heat insulating performance of the present invention is arranged in the space consisting of the outer box and the inner box, and the other spaces are filled with the foam heat insulating material. By doing so, a refrigeration apparatus and a cooling / heating apparatus having excellent heat insulation performance can be obtained.
[0126]
In addition, according to the method for manufacturing a vacuum heat insulating material core material of the present invention, it is easy to obtain the core material of the present invention in which the binder concentration is different in the thickness direction and a small amount of binder is bound inside the molded body, and also in terms of strength. An excellent core material can be obtained.
[0127]
Further, according to the refrigerator of the present invention, the vacuum heat insulating material of the present invention, which is lightweight, rigid and has excellent heat insulation performance and high plane accuracy, is arranged in a wide area on the outer box side of the space consisting of the outer box and the inner box. By filling the other space with foam insulation, the exterior quality (planar accuracy) of the outer box and the insulation performance of the heat insulation box can be balanced at a high level. Obtainable.
[0128]
In addition, since the vacuum heat insulating material of the present invention can form a groove on the surface of the vacuum heat insulating material by pressing from above the outer cover material after the vacuum heat insulating material is manufactured, the refrigerant piping on the inner surface of the outer box is provided. For the portion, by arranging a vacuum heat insulating material in which a groove matching the refrigerant pipe is formed, a refrigerator with excellent energy saving can be obtained using a small number of vacuum heat insulating materials.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view of a vacuum heat insulating material in one embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view of a board-like core material in one embodiment of the present invention.
FIG. 3 is a schematic cross-sectional view of a vacuum heat insulating material in one embodiment of the present invention.
FIG. 4 is a schematic cross-sectional view of a board-like core material in one embodiment of the present invention.
FIG. 5 is a schematic sectional view of a vacuum heat insulating material in one embodiment of the present invention.
FIG. 6 is a schematic cross-sectional view of a board-like core material in one embodiment of the present invention.
FIG. 7 is a schematic sectional view of a refrigerator-freezer in one embodiment of the present invention.
FIG. 8 is an enlarged cross-sectional view of the main part of the ceiling surface portion of the heat insulation box of the refrigerator-freezer.
FIG. 9 is a schematic sectional view of a vacuum heat insulating material in one comparative example of the present invention.
FIG. 10 is a schematic cross-sectional view of a board-like core material in one comparative example of the present invention.
11 is an optical micrograph observing the appearance of the surface of the board-shaped core material of Example 1. FIG.
[Explanation of symbols]
1 Vacuum insulation
2 Board-shaped core
3 Jacket material
4 Glass wool
5 Binder
6 Refrigerator
7 Insulated box
8 Outer box
9 Inner box
10 Hard urethane foam
11 Door body
12 Partition plate
13 Cold room
14 Freezer
15 Damper
16 Evaporator
17 Machine room
18 Compressor
19 Condenser
20 Capillary tube
21 Refrigerant piping
22 groove
23 Hot melt adhesive

Claims (17)

ボード状芯材と、該芯材を外包する外被材とからなり、内部を減圧後密閉した真空断熱材であって、前記ボード状芯材が繊維不織ウエブの積層体からなり、該芯材の少なくとも片側表面に前記繊維がバインダーにより熱固定された硬化層が形成されてなることを特徴とする真空断熱材。A vacuum heat insulating material comprising a board-like core material and a jacket material enclosing the core material, the inside of which is sealed after decompression, wherein the board-like core material comprises a laminate of non-woven fiber webs, A vacuum heat insulating material, wherein a hardened layer in which the fibers are heat-set by a binder is formed on at least one surface of the material. 前記ボード状芯材の密度が、１００〜４００ｋｇ／ｍ３の範囲である請求項１に記載の真空断熱材。The vacuum heat insulating material according to claim 1, wherein the density of the board-shaped core material is in a range of 100 to 400 kg / m 3 . 前記ボード状芯材の表面硬度が、１５〜７０である請求項１または２に記載の真空断熱材芯材。The vacuum heat insulating material core material according to claim 1 or 2, wherein the board-shaped core material has a surface hardness of 15 to 70. 前記バインダーが無機材料からなる請求項１〜３のいずれかに記載の真空断熱材。The vacuum heat insulating material according to any one of claims 1 to 3, wherein the binder is made of an inorganic material. 前記バインダーが、ホウ酸、ホウ酸塩、リン酸、リン酸塩およびこれらの加熱生成物からなる化合物群から選択される少なくとも１種の化合物である請求項４に記載の真空断熱材。The vacuum heat insulating material according to claim 4, wherein the binder is at least one compound selected from the group consisting of boric acid, borate, phosphoric acid, phosphate, and a heating product thereof. 前記硬化層が、繊維不織ウエブの積層体表面に水を噴霧することにより形成されたものである請求項１〜５のいずれかに記載の真空断熱材。The vacuum heat insulating material according to any one of claims 1 to 5, wherein the cured layer is formed by spraying water on a surface of a laminate of fiber nonwoven webs. 前記繊維が、グラスウールもしくはグラスファイバーである請求項１〜６のいずれかに記載の真空断熱材。The vacuum heat insulating material according to any one of claims 1 to 6, wherein the fiber is glass wool or glass fiber. 前記外被材が、プラスチック−金属箔ラミネートフィルムである請求項１〜７のいずれかに記載の真空断熱材。The vacuum jacket according to any one of claims 1 to 7, wherein the jacket material is a plastic-metal foil laminate film. 熱伝導率が０．００１５〜０．００２５Ｗ／ｍＫの範囲である請求項１〜８のいずれかに記載の真空断熱材。The vacuum heat insulating material according to any one of claims 1 to 8, wherein the thermal conductivity is in a range of 0.0015 to 0.0025 W / mK. 外箱と、内箱と、前記外箱と前記内箱によって形成される空間に発泡断熱材と真空断熱材とを有し、前記真空断熱材を前記空間に配置し、前記真空断熱材以外の前記空間に発泡断熱材を充填してなる冷凍機器および冷温機器であって、前記真空断熱材が請求項１〜９のいずれかに記載の真空断熱材であることを特徴とする冷凍機器および冷温機器。An outer box, an inner box, a foam heat insulating material and a vacuum heat insulating material in a space formed by the outer box and the inner box, the vacuum heat insulating material is disposed in the space, and other than the vacuum heat insulating material A refrigeration apparatus and a cooling / heating apparatus in which the space is filled with a foam insulation material, wherein the vacuum insulation material is the vacuum insulation material according to any one of claims 1 to 9. machine. 外箱と、内箱と、前記外箱と前記内箱によって形成される空間に発泡断熱材と真空断熱材とを有し、前記真空断熱材を前記空間の前記外箱側に配置し、前記真空断熱材以外の前記空間に発泡断熱材を充填してなる冷蔵庫であって、前記真空断熱材が請求項１〜９のいずれかに記載の真空断熱材であり、前記真空断熱材の前記硬化層側の面が前記外箱の内面に対向していることを特徴とする冷蔵庫。An outer box, an inner box, a foam heat insulating material and a vacuum heat insulating material in a space formed by the outer box and the inner box, and the vacuum heat insulating material is disposed on the outer box side of the space; It is a refrigerator formed by filling the space other than the vacuum heat insulating material with a foam heat insulating material, and the vacuum heat insulating material is the vacuum heat insulating material according to any one of claims 1 to 9, and the curing of the vacuum heat insulating material. A layer-side surface is opposed to the inner surface of the outer box. 前記外箱の内面における冷媒配管が配設された部分に対して、前記硬化層側の面に前記外被材の外側からプレスで前記冷媒配管を収納可能な溝を形成した前記真空断熱材を、前記溝内に前記冷媒配管が収まるように配置した請求項１１に記載の冷蔵庫。The vacuum heat insulating material in which a groove in which the refrigerant pipe can be accommodated by pressing from the outside of the outer cover material is formed on the surface of the hardened layer with respect to a portion where the refrigerant pipe is disposed on the inner surface of the outer box. The refrigerator according to claim 11, wherein the refrigerant pipe is disposed in the groove. 前記真空断熱材が、前記外箱に接着剤で固定されている請求項１１または１２に記載の冷蔵庫。The refrigerator according to claim 11 or 12, wherein the vacuum heat insulating material is fixed to the outer box with an adhesive. 前記接着剤が、ホットメルトである請求項１３に記載の冷蔵庫。The refrigerator according to claim 13, wherein the adhesive is hot melt. 前記真空断熱材と前記外箱との間の前記接着剤の層の厚みが７０〜１３０μｍである請求項１３または１４に記載の冷蔵庫。The refrigerator according to claim 13 or 14, wherein a thickness of the adhesive layer between the vacuum heat insulating material and the outer box is 70 to 130 µm. 繊維不織ウエブの積層体からなり、該芯材の少なくとも片側表面には前記繊維がバインダーにより熱固定された硬化層が形成されてなることを特徴とする真空断熱材芯材。A vacuum heat insulating material core material comprising a laminate of non-woven fiber webs, wherein a hardened layer in which the fibers are heat-set by a binder is formed on at least one surface of the core material. 繊維を所定形状になるように積層するステップと、積層した繊維ウエブの外面の少なくとも片面にバインダー水溶液あるいは水を塗布するステップと、バインダーを塗布した積層繊維ウエブを１００℃以下の温度で圧縮するステップと、圧縮した積層繊維ウエブを１００℃以上の温度で加熱圧縮するステップとを含むことを特徴とする真空断熱材芯材の製造方法。A step of laminating fibers so as to have a predetermined shape, a step of applying a binder aqueous solution or water to at least one side of the outer surface of the laminated fiber web, and a step of compressing the laminated fiber web coated with the binder at a temperature of 100 ° C. or lower. And a step of heat-compressing the compressed laminated fiber web at a temperature of 100 ° C. or higher.
JP2002192615A 2002-05-31 2002-07-01 Vacuum heat insulating material, and refrigeration equipment, cooling / heating equipment using the same, and vacuum heat insulating material core material and manufacturing method thereof Expired - Fee Related JP3490426B1 (en)

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TW092114811A TW593919B (en) 2002-05-31 2003-05-30 Vacuum heat insulating material and method for producing the same, and refrigerator using the vacuum heat insulating material
AU2003241723A AU2003241723A1 (en) 2002-05-31 2003-06-02 Vacuum thermal insulating material, process for producing the same and refrigerator including the same
EP03730754.3A EP1510747B1 (en) 2002-05-31 2003-06-02 Vacuum thermal insulating material, process for producing the same and refrigerator including the same
US10/514,809 US7571582B2 (en) 2002-05-31 2003-06-02 Vacuum heat insulator, method of manufacturing the same, and refrigerator using the same
PCT/JP2003/006915 WO2003102460A1 (en) 2002-05-31 2003-06-02 Vacuum thermal insulating material, process for producing the same and refrigerator including the same
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JP2019138508A (en) * 2018-02-08 2019-08-22 日立グローバルライフソリューションズ株式会社 refrigerator

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