JP2006291224A - Moisture absorbing formed article - Google Patents

Moisture absorbing formed article Download PDF

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JP2006291224A
JP2006291224A JP2006189059A JP2006189059A JP2006291224A JP 2006291224 A JP2006291224 A JP 2006291224A JP 2006189059 A JP2006189059 A JP 2006189059A JP 2006189059 A JP2006189059 A JP 2006189059A JP 2006291224 A JP2006291224 A JP 2006291224A
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hygroscopic
molded article
article according
hygroscopic molded
sheet
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Yohei Kawaguchi
洋平 川口
Masayuki Fujimori
雅之 藤森
Teruo Uchibori
輝男 内堀
Kanehito Oyama
兼人 大山
Atsushi Nishino
西野  敦
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Dynic Corp
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Dynic Corp
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<P>PROBLEM TO BE SOLVED: To provide a material which can easily and surely absorb moisture invaded in devices such as electronic devices. <P>SOLUTION: The present invention relates to a moisture-absorbing formed article comprising a moisture-absorbing agent and a resin component. The moisture-absorbing formed article comprises the moisture-absorbing agent and the resin component. The shape of the moisture-absorbing formed article is not limited, and may suitably be set in response to the use, use purpose, used site, and the like of a final product, such as a sheet, pellet, plate, film or granular (granules) shape. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、吸湿性成形体に関する。   The present invention relates to a hygroscopic molded article.

電池、キャパシタ(コンデンサ)、表示素子等の電子デバイスは、超小型化・超軽量化の一途をたどっている。これらの電子部品は、必ず外装部の封止工程において、ゴム系シール材あるいはUV硬化性樹脂等の樹脂系接着剤を用いて封止が行われる。ところが、これらの封止方法では、保存中又は使用中にシール材を通過する水分により電子部品の性能劣化が引き起こされる。すなわち、電子デバイス内に侵入した水分により、電子デバイス内部の電子部品が変質又は腐食するおそれがある。例えば、有機電解質を用いる電池又はコンデンサでは、その電解質中に水分が混入すると電気伝導度の変化、侵入水分の電気分解等が起こり、さらに端子間の電圧の降下やガス発生による外装ケースの歪みや漏液を生じることがある。このように、電子デバイス内に侵入した水分により、電子デバイスの性能安定性・信頼性を維持することが困難となっている。   Electronic devices such as batteries, capacitors (capacitors), and display elements are continually becoming smaller and lighter. These electronic components are always sealed using a resin-based adhesive such as a rubber-based sealing material or a UV curable resin in the sealing process of the exterior portion. However, in these sealing methods, the performance of the electronic component is deteriorated by moisture passing through the sealing material during storage or use. That is, there is a possibility that the electronic components inside the electronic device may be deteriorated or corroded by moisture that has entered the electronic device. For example, in a battery or capacitor using an organic electrolyte, if moisture is mixed in the electrolyte, the electrical conductivity changes, electrolysis of intruded moisture, etc., and the outer case distortion due to voltage drop or gas generation between terminals May cause leakage. As described above, it is difficult to maintain the performance stability and reliability of the electronic device due to moisture that has entered the electronic device.

また、これを解決するためにハーメチクシール又は金属溶接を行うことも考えられる。ところが、これらの技術では、外装ケースの膨れや内部減圧による歪み、ひいては内部の機能材料の化学変化が引き起こされる。   In order to solve this problem, it is conceivable to perform hermetic sealing or metal welding. However, in these techniques, the outer case swells or is distorted by internal decompression, and as a result, the internal functional material is chemically changed.

他方、これらの電子デバイスを組み立てる工程では、全工程にわたって湿度を0に維持することは事実上不可能であるため、例えば電子デバイス完成後のエージング工程中において、組立工程中に電子デバイス中に侵入した水分を吸湿することが必要不可欠となる。ところが、前記のように、電子デバイス内に侵入した水分を確実かつ容易に吸湿する技術は未だ確立されていない。   On the other hand, in the process of assembling these electronic devices, it is virtually impossible to maintain the humidity at 0 throughout the entire process. For example, during the aging process after completion of the electronic device, the electronic device penetrates into the electronic device during the assembly process. It is essential to absorb the moisture. However, as described above, a technique for reliably and easily absorbing moisture that has entered the electronic device has not yet been established.

従って、本発明の主たる目的は、これら従来技術の問題を解消し、電子デバイス等の装置内部に侵入した水分を容易かつ確実に吸湿できる材料を提供することにある。   Therefore, a main object of the present invention is to provide a material that can easily and surely absorb moisture that has entered the inside of an apparatus such as an electronic device by solving these problems of the prior art.

本発明者は、これら従来技術の問題に鑑み、鋭意研究を重ねた結果、特定の吸湿性成形体が上記目的を達成できることを見出し、ついに本発明を完成するに至った。   As a result of intensive studies in view of these problems of the prior art, the present inventor has found that a specific hygroscopic molded body can achieve the above object, and has finally completed the present invention.

すなわち、本発明は、下記の吸湿性成形体に係るものである。
1.吸湿剤及び樹脂成分を含有する吸湿性成形体。
2.吸湿剤が、アルカリ土類金属酸化物及び硫酸塩の少なくとも1種を含む請求項1記載の吸湿性成形体。
3.吸湿剤が、CaO、BaO及びSrOの少なくとも1種である前記項1記載の吸湿性成形体。
4.吸湿剤として、比表面積10m/g以上の粉末が用いられている前記項1記載の吸湿性成形体。
5.吸湿剤として、比表面積40m/g以上の粉末が用いられている前記項1記載の吸湿性成形体。
6.吸湿剤が吸湿性成形体中30〜95重量%含有されている前記項1記載の吸湿性成形体。
7.樹脂成分が、フッ素系、ポリオレフィン系、ポリアクリル系、ポリアクリロニトリル系、ポリアミド系、ポリエステル系及びエポキシ系の少なくとも1種の高分子材料である前記項1記載の吸湿性成形体。
8.さらにガス吸着剤を含有する前記項1記載の吸湿性成形体。
9.ガス吸着剤が、無機多孔質材料からなる前記項8記載の吸湿性成形体。
10.吸湿性成形体表面の一部又は全部に樹脂被覆層が形成されている前記項1記載の吸湿性成形体。
11.樹脂成分がフィブリル化されている前記項1記載の吸湿性成形体。
12.吸湿剤としてCaO、BaO及びSrOの少なくとも1種であって比表面積10m/g以上の粉末が用いられ、かつ、樹脂成分としてフッ素系樹脂が用いられてなる前記項1記載の吸湿性成形体。
13.フッ素系樹脂がフィブリル化されている前記項12記載の吸湿性成形体。
14.前記項1記載の電子デバイス用吸湿性成形体。
That is, the present invention relates to the following hygroscopic molded article.
1. A hygroscopic molded article containing a hygroscopic agent and a resin component.
2. The hygroscopic molded article according to claim 1, wherein the hygroscopic agent contains at least one of an alkaline earth metal oxide and a sulfate.
3. The hygroscopic molded article according to item 1, wherein the hygroscopic agent is at least one of CaO, BaO, and SrO.
4). The hygroscopic molded article according to item 1, wherein a powder having a specific surface area of 10 m 2 / g or more is used as the hygroscopic agent.
5. The hygroscopic molded article according to item 1, wherein a powder having a specific surface area of 40 m 2 / g or more is used as the hygroscopic agent.
6). The hygroscopic molded article according to item 1, wherein the hygroscopic agent is contained in the hygroscopic molded article in an amount of 30 to 95% by weight.
7). Item 2. The hygroscopic molded article according to Item 1, wherein the resin component is at least one polymer material of fluorine, polyolefin, polyacryl, polyacrylonitrile, polyamide, polyester, and epoxy.
8). The hygroscopic molded article according to Item 1, further comprising a gas adsorbent.
9. Item 9. The hygroscopic molded article according to Item 8, wherein the gas adsorbent is made of an inorganic porous material.
10. The hygroscopic molded article according to item 1, wherein a resin coating layer is formed on a part or all of the surface of the hygroscopic molded article.
11. The hygroscopic molded article according to item 1, wherein the resin component is fibrillated.
12 Item 2. The hygroscopic molded article according to Item 1, wherein a powder having at least one of CaO, BaO and SrO having a specific surface area of 10 m 2 / g or more is used as a hygroscopic agent, and a fluororesin is used as a resin component. .
13. Item 13. The hygroscopic molded article according to Item 12, wherein the fluororesin is fibrillated.
14 Item 2. A hygroscopic molded article for an electronic device according to Item 1.

本発明の吸湿性成形体は、吸湿剤及び樹脂成分を含有する。吸湿性成形体の形状は限定的でなく、最終製品の用途、使用目的、使用部位等に応じて適宜設定すれば良く、例えばシート状、ペレット状、板状、フィルム状、粒状(造粒体)等を挙げることができる。   The hygroscopic molded article of the present invention contains a hygroscopic agent and a resin component. The shape of the hygroscopic molded body is not limited, and may be appropriately set according to the use of the final product, the purpose of use, the use site, etc. For example, a sheet shape, a pellet shape, a plate shape, a film shape, a granular shape (granulated material) And the like.

吸湿剤としては、少なくとも水分を吸着できる機能を有するものであれば良いが、特に化学的に水分を吸着するとともに吸湿しても固体状態を維持する化合物が好ましい。このような化合物としては、例えば金属酸化物、金属の無機酸塩・有機酸塩等が挙げられるが、本発明では特にアルカリ土類金属酸化物及び硫酸塩の少なくとも1種を用いることが好ましい。   The hygroscopic agent is not particularly limited as long as it has a function capable of adsorbing at least water, but is preferably a compound that chemically adsorbs water and maintains a solid state even when moisture is absorbed. Examples of such compounds include metal oxides, metal inorganic acid salts and organic acid salts, etc. In the present invention, it is particularly preferable to use at least one of alkaline earth metal oxides and sulfates.

アルカリ土類金属酸化物としては、例えば酸化カルシウム(CaO)、酸化バリウム(BaO)、酸化マグネシウム(MgO)、酸化ストロンチウム(SrO)が挙げられる。   Examples of the alkaline earth metal oxide include calcium oxide (CaO), barium oxide (BaO), magnesium oxide (MgO), and strontium oxide (SrO).

硫酸塩としては、例えば硫酸リチウム(LiSO)、硫酸ナトリウム(NaSO)、硫酸カルシウム(CaSO)、硫酸マグネシウム(MgSO)、硫酸コバルト(CoSO)、硫酸ガリウム(Ga(SO)、硫酸チタン(Ti(SO)、硫酸ニッケル(NiSO)等が挙げられる。その他にも、本発明の吸湿剤として吸湿性を有する有機化合物も使用できる。 Examples of the sulfate include lithium sulfate (Li 2 SO 4 ), sodium sulfate (Na 2 SO 4 ), calcium sulfate (CaSO 4 ), magnesium sulfate (MgSO 4 ), cobalt sulfate (CoSO 4 ), and gallium sulfate (Ga 2 ). (SO 4 ) 3 ), titanium sulfate (Ti (SO 4 ) 2 ), nickel sulfate (NiSO 4 ), and the like. In addition, organic compounds having hygroscopicity can be used as the hygroscopic agent of the present invention.

本発明の吸湿剤としては、アルカリ土類金属酸化物が好ましい。特に、CaO、BaO及びSrOの少なくとも1種が好ましい。最も好ましくはCaOである。   The hygroscopic agent of the present invention is preferably an alkaline earth metal oxide. In particular, at least one of CaO, BaO and SrO is preferable. Most preferred is CaO.

本発明の吸湿剤は、粉末の形態で含有させることが好ましい。この場合、粉末の比表面積(BET比表面積)は、通常10m/g以上、さらには30m/g以上、特に40m/g以上であることが好ましい。このような吸湿剤としては、例えば水酸化カルシウムを900℃以下(好ましくは700℃以下、最も好ましくは500℃以下(特に490〜500℃)で加熱して得られるCaO(粉末)を好適に用いることができる。本発明では、BET比表面積10m/g以上、さらには30m/g以上、特に40m/g以上のCaO粉末を最も好ましく用いることができる。 The hygroscopic agent of the present invention is preferably contained in the form of a powder. In this case, the specific surface area (BET specific surface area) of the powder is usually 10 m 2 / g or more, more preferably 30 m 2 / g or more, and particularly preferably 40 m 2 / g or more. As such a hygroscopic agent, for example, CaO (powder) obtained by heating calcium hydroxide at 900 ° C. or lower (preferably 700 ° C. or lower, most preferably 500 ° C. or lower (especially 490 to 500 ° C.)) is suitably used. In the present invention, a CaO powder having a BET specific surface area of 10 m 2 / g or more, further 30 m 2 / g or more, particularly 40 m 2 / g or more can be most preferably used.

一方、樹脂成分としては、吸湿剤の水分除去作用を妨げないものであれば特に限定的でなく、好ましくは気体透過性高分子材料(すなわち、ガスバリアー性の低い高分子材料)を好適に用いることができる。例えば、フッ素系、ポリオレフィン系、ポリアクリル系、ポリアクリロニトリル系、ポリアミド系、ポリエステル系、エポキシ系、ポリカーボーネート系等の高分子材料が挙げられる。気体透過性は、最終製品の用途、所望の特性等に応じて適宜設定すれば良い。   On the other hand, the resin component is not particularly limited as long as it does not interfere with the moisture removing action of the hygroscopic agent, and preferably a gas-permeable polymer material (that is, a polymer material having a low gas barrier property) is preferably used. be able to. Examples thereof include polymer materials such as fluorine-based, polyolefin-based, polyacryl-based, polyacrylonitrile-based, polyamide-based, polyester-based, epoxy-based, and polycarbonate-based materials. The gas permeability may be appropriately set according to the use of the final product, desired characteristics, and the like.

本発明では、これら高分子材料の中でも、フッ素系、ポリオレフィン系等が好ましい。具体的には、フッ素系としては、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライド、エチレン−テトラフルオロエチレン共重合体等が挙げられる。ポリオレフィン系としては、ポリエチレン、ポリプロピレン、ポリブタジエン、ポリイソプレン等のほか、これらの共重合体等が挙げられる。これら樹脂成分のうち、本発明では、フッ素系樹脂が好ましい。   In the present invention, among these polymer materials, fluorine-based and polyolefin-based materials are preferable. Specifically, examples of the fluorine-based material include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and ethylene-tetrafluoroethylene copolymer. Examples of the polyolefin type include polyethylene, polypropylene, polybutadiene, polyisoprene, and copolymers thereof. Of these resin components, fluorine-based resins are preferred in the present invention.

本発明では、吸湿剤及び樹脂成分の含有量はこれらの種類等に応じて適宜設定すれば良いが、通常は吸湿剤及び樹脂成分の合計量を100重量%として吸湿剤30〜95重量%程度及び樹脂成分70〜5重量%程度にすれば良い。好ましくは吸湿剤50〜85重量%程度及び樹脂成分50〜15重量%、最も好ましくは吸湿剤55〜85重量%程度及び樹脂成分45〜15重量%とすれば良い。   In the present invention, the contents of the hygroscopic agent and the resin component may be appropriately set according to these types and the like, but usually, the total amount of the hygroscopic agent and the resin component is 100% by weight, and the hygroscopic agent is about 30 to 95% by weight. The resin component may be about 70 to 5% by weight. Preferably, the hygroscopic agent is about 50 to 85% by weight and the resin component is 50 to 15% by weight, and most preferably the hygroscopic agent is about 55 to 85% by weight and the resin component is 45 to 15% by weight.

本発明では、その効果を妨げない範囲内で、必要に応じて他の成分を適宜添加することもできる。例えば、ガス吸収性を示す材料(ガス吸着剤)を配合することができる。ガス吸着剤としては、シリカ、アルミナ、合成ゼオライト等の無機多孔質材料を例示することができる。ガス吸着剤の含有量は限定的でないが、通常は吸湿剤及び樹脂成分の合計量100重量部に対して3〜15重量部程度とすれば良い。   In the present invention, other components can be appropriately added as necessary within the range not hindering the effect. For example, a material exhibiting gas absorbability (gas adsorbent) can be blended. Examples of the gas adsorbent include inorganic porous materials such as silica, alumina, and synthetic zeolite. The content of the gas adsorbent is not limited, but is usually about 3 to 15 parts by weight with respect to 100 parts by weight of the total amount of the hygroscopic agent and the resin component.

また、本発明の吸湿性成形体は、必要に応じてその表面上の一部又は全部に樹脂成分を含む樹脂被覆層が形成されていても良い。これにより、吸湿性成形体の吸湿性能を制御することができる。樹脂被覆層の樹脂成分としては、気体透過性の高い材料であれば良く、具体的には吸湿性成形体に含まれる上記樹脂成分と同様のものを採用することができる。好ましくは、上記ポリオレフィン系のものを使用することができる。   In addition, the hygroscopic molded article of the present invention may be provided with a resin coating layer containing a resin component on a part or all of its surface as necessary. Thereby, the hygroscopic performance of a hygroscopic molded object is controllable. The resin component of the resin coating layer may be any material having high gas permeability, and specifically, the same resin component as that contained in the hygroscopic molded article can be employed. Preferably, the above polyolefin-based ones can be used.

上記樹脂成分中には、必要に応じて無機材料又は金属材料からなる粉末を分散させても良い。これにより、急激な温度変化又は湿度変化に対する耐久性等をより高めることができる。特に、マイカ、アルミニウム粉等のリーフィング現象を示す粉末(鱗片状粒子)が好ましい。上記粉末の含有量は特に限定的でないが、通常は樹脂被覆層中30〜50重量%程度とすれば良い。   In the resin component, a powder made of an inorganic material or a metal material may be dispersed as necessary. Thereby, durability etc. with respect to a rapid temperature change or humidity change can be improved more. In particular, powders (scale-like particles) exhibiting a leafing phenomenon such as mica and aluminum powder are preferable. The content of the powder is not particularly limited, but is usually about 30 to 50% by weight in the resin coating layer.

樹脂被覆層の厚さは、所望の吸湿性能、樹脂被覆層で用いる樹脂成分の種類等に応じて適宜設定できるが、通常は0.5〜20μm程度、好ましくは0.5〜10μmとすれば良い。このため、上記粒子の粒径は、一般に樹脂被覆層の厚さよりも小さくなるように設定すれば良い。   The thickness of the resin coating layer can be appropriately set according to the desired moisture absorption performance, the type of resin component used in the resin coating layer, etc., but is usually about 0.5 to 20 μm, preferably 0.5 to 10 μm. good. For this reason, what is necessary is just to set the particle size of the said particle | grain so that it may become smaller than the thickness of a resin coating layer generally.

本発明の吸湿性成形体は、これらの各成分を均一に混合し、所望の形状に成形することによって得られる。この場合、吸湿剤、ガス吸着剤等は予め十分乾燥させてから配合することが好ましい。また、樹脂成分との混合に際しては、必要に応じて加熱して溶融状態としても良い。成形方法は、公知の成形又は造粒方法を採用すれば良く、例えばプレス成形(ホットプレス成形等を含む。)、押し出し成形等のほか、転動造粒機、2軸造粒機等による造粒を適用することができる。   The hygroscopic molded article of the present invention can be obtained by uniformly mixing these components and molding into a desired shape. In this case, it is preferable to mix the moisture absorbent, the gas adsorbent and the like after sufficiently drying them in advance. Further, when mixing with the resin component, it may be heated to a molten state as necessary. As the molding method, a known molding or granulation method may be employed. For example, in addition to press molding (including hot press molding), extrusion molding, etc., granulation by a rolling granulator, a biaxial granulator, or the like. Grain can be applied.

吸湿性成形体がシート状である場合、このシート状成形体をさらに延伸加工したものも吸湿性シートとして好適に用いることができる。延伸加工は、公知の方法に従って実施すれば良く、一軸延伸、二軸延伸等のいずれであっても良い。   When the hygroscopic molded body is in the form of a sheet, a sheet obtained by further stretching the sheet-shaped molded body can be suitably used as the hygroscopic sheet. The stretching process may be performed according to a known method, and may be any one of uniaxial stretching and biaxial stretching.

また、樹脂被覆層を形成する場合、その形成方法は限定的でなく、公知の積層方法等に従って実施すれば良い。例えば、吸湿性成形体がシートである場合は、そのシートの表面及び裏面の少なくとも一方に、予め成形された樹脂被覆層用シート又はフィルムを積層すれば良い。   Moreover, when forming a resin coating layer, the formation method is not limited, What is necessary is just to implement according to a well-known lamination method. For example, when the hygroscopic molded body is a sheet, a resin coating layer sheet or film molded in advance may be laminated on at least one of the front and back surfaces of the sheet.

例えば、図1に示すように、吸湿性シート(1)の裏面に樹脂被覆層(2)を形成することができる。また、図2に示すように、吸湿性シート(1)の表及び裏面に樹脂被覆層(2)(2)を形成することもできる。   For example, as shown in FIG. 1, a resin coating layer (2) can be formed on the back surface of the hygroscopic sheet (1). Moreover, as shown in FIG. 2, resin coating layers (2) and (2) can be formed on the front and back surfaces of the hygroscopic sheet (1).

吸湿性成形体をシート状とする場合のシート厚さは、最終製品の使用目的等に応じて適宜設定すれば良い。例えば、吸湿性成形体をキャパシタ等の電子デバイスに適用する場合は、通常50〜400μm程度、好ましくは100〜200μmとすれば良い。これらシート厚さは、樹脂被覆層を有する場合は、樹脂被覆層を含めた厚さである。   What is necessary is just to set the sheet | seat thickness in the case of making a hygroscopic molded object into a sheet form suitably according to the intended purpose etc. of a final product. For example, when the hygroscopic molded body is applied to an electronic device such as a capacitor, it is usually about 50 to 400 μm, preferably 100 to 200 μm. These sheet thicknesses are the thickness including the resin coating layer when the resin coating layer is provided.

本発明の吸湿性成形体は、樹脂成分がフィブリル化されていることが好ましい。フィブリル化によって、いっそう優れた吸湿性を発揮することができる。フィブリル化は、吸湿性成形体の成形と同時に実施しても良いし、あるいは成形後の加工により実施しても良い。例えば、樹脂成分と吸湿剤とを乾式混合して得られた混合物を圧延することにより樹脂成分のフィブリル化を行うことができる。また例えば、本発明成形体をさらに前記のように延伸加工を施すことによってフィブリル化を行うことができる。より具体的には、CaO、BaO及びSrOの少なくとも1種の吸湿剤粉末とフッ素系樹脂粉末(例えば、ポリテトラフルオロエチレン等)とを乾式混合した後、得られた混合物を圧延することによりフィブリル化された吸湿性成形体を製造することができる。圧延又は延伸は、公知の装置を用いて実施すれば良い。フィブリル化の程度は、最終製品の用途、所望の特性等に応じて適宜調整することができる。吸湿剤粉末は、前記の比表面積を有するものを用いることが好ましい。フッ素系樹脂粉末は限定的でなく、公知又は市販のフッ素系樹脂粉末(粒度)をそのまま使用すれば良い。   In the hygroscopic molded article of the present invention, the resin component is preferably fibrillated. More excellent hygroscopicity can be achieved by fibrillation. Fibrilization may be performed simultaneously with the molding of the hygroscopic molded body, or may be performed by processing after molding. For example, the resin component can be fibrillated by rolling a mixture obtained by dry-mixing the resin component and the hygroscopic agent. Further, for example, fibrillation can be performed by further stretching the molded article of the present invention as described above. More specifically, at least one type of moisture absorbent powder of CaO, BaO, and SrO and a fluorine-based resin powder (for example, polytetrafluoroethylene) are dry-mixed, and then the resulting mixture is rolled to produce fibrils. A hygroscopic molded body can be produced. Rolling or stretching may be performed using a known apparatus. The degree of fibrillation can be appropriately adjusted according to the use of the final product, desired characteristics, and the like. It is preferable to use the moisture absorbent powder having the specific surface area. The fluorine resin powder is not limited, and a known or commercially available fluorine resin powder (particle size) may be used as it is.

本発明の吸湿性成形体は、吸湿が必要な箇所又は部位に常法により設置すれば良い。例えば、電子デバイスの容器内雰囲気中の水分を吸湿する場合は、容器内面の一部又は全部に吸湿性成形体を固定すれば良い。また、有機電解質を用いるキャパシタ、電池等において、有機電解質中の水分を吸湿する場合は、有機電解質中に吸湿性成形体を存在させれば良い。   What is necessary is just to install the hygroscopic molded object of this invention in the location or site | part which needs moisture absorption by a conventional method. For example, when moisture in the atmosphere in the container of the electronic device is absorbed, the hygroscopic molded body may be fixed to part or all of the inner surface of the container. Moreover, in the capacitor | condenser using an organic electrolyte, a battery, etc., when water | moisture content in an organic electrolyte is absorbed, what is necessary is just to make a hygroscopic molded object exist in an organic electrolyte.

上記の固定方法は、容器に確実に固定できる方法であれば特に制限されない。例えば、吸湿性成形体と容器とを公知の粘着テープ、接着剤(好ましくは無溶剤型接着剤)等により貼着する方法、吸湿性成形体を容器に熱融着させる方法、ビス等の固定部材により成形体を容器に固定する方法等が挙げられる。   The fixing method is not particularly limited as long as it can be reliably fixed to the container. For example, a method of adhering the hygroscopic molded body and the container with a known pressure-sensitive adhesive tape, an adhesive (preferably a solvent-free adhesive), a method of heat-sealing the hygroscopic molded body to the container, fixing screws, etc. The method etc. which fix a molded object to a container with a member are mentioned.

例えば、図3に示すように、表及び裏面に樹脂被覆層を有する吸湿性シートにおいて、離型紙(4)を有する接着層(3)をシート上に形成すれば、使用時に離型紙を剥がし、接着層により固定することができる。また、図4に示すように、エチレンビニルアルコールコポリマー(EVOH)等を用いた無溶剤型接着剤(5)により容器に固定することもできる。無溶剤型接着剤は、市販品を用いることもできる。   For example, as shown in FIG. 3, in the hygroscopic sheet having a resin coating layer on the front and back surfaces, if the adhesive layer (3) having the release paper (4) is formed on the sheet, the release paper is peeled off during use, It can be fixed by an adhesive layer. Moreover, as shown in FIG. 4, it can also fix to a container with the solventless type adhesive agent (5) using ethylene vinyl alcohol copolymer (EVOH) etc. A commercially available product can also be used as the solventless adhesive.

本発明によれば、吸湿性成形体を採用しているので、電子デバイス等の装置内部に侵入した水分をより容易かつ確実に除去することができる。   According to the present invention, since the hygroscopic molded body is employed, it is possible to more easily and reliably remove moisture that has entered the inside of an apparatus such as an electronic device.

これにより、乾燥手段の設置を機械化することも可能となる。また、これに伴い、雰囲気内に水分が侵入する機会が減り、当初から高い乾燥状態をもつ雰囲気を作り出すことができる。すなわち、高い乾燥状態でデバイスを製造できるとともに製造後も確実に水分を除去できるので、より安定性・信頼性の高いデバイスを工業的規模で提供することが可能となる。   This also makes it possible to mechanize the installation of the drying means. In addition, the opportunity for moisture to enter the atmosphere is reduced, and an atmosphere having a high dry state can be created from the beginning. That is, since the device can be manufactured in a highly dry state and moisture can be reliably removed after the manufacturing, a device with higher stability and reliability can be provided on an industrial scale.

また、乾燥手段として従来の乾燥剤(粉末)をそのまま用いた場合と異なり、粉末が脱落して容器に散乱するという問題も回避することができる。さらに、粉末を使用する場合は収納部の確保が必要であったが、本発明ではそのような必要がなくなり、デバイスの小型化・軽量化にも貢献することができる。   Further, unlike the case where a conventional desiccant (powder) is used as it is as a drying means, the problem that the powder falls off and is scattered in the container can also be avoided. Furthermore, when powder is used, it is necessary to secure a storage portion. However, in the present invention, such a necessity is eliminated, and the device can be reduced in size and weight.

このような特徴をもつ本発明の吸湿性成形体は、電子材料、機械材料、自動車、通信機器、建築材料、医療材料、精密機器等のさまざまな用途への応用が期待される。   The hygroscopic molded article of the present invention having such characteristics is expected to be applied to various uses such as electronic materials, mechanical materials, automobiles, communication equipment, building materials, medical materials, precision equipment and the like.

以下、実施例を示し、本発明の特徴とするところをより一層明確にする。但し、本発明は、これら実施例に限定されるものではない。   Hereinafter, examples will be shown to further clarify the features of the present invention. However, the present invention is not limited to these examples.

実施例1
シート状の吸湿性成形体を作製した。
Example 1
A sheet-like hygroscopic molded body was produced.

吸湿剤であるCaO粉末(純度99.9%)を900℃で1時間加熱して十分脱水させ、次いで180〜200℃の限率乾燥雰囲気中で冷却し、最終的に室温まで冷却した。得られたCaO(BET比表面積約3m/g)60重量%及び樹脂成分としてポリエチレン(分子量:約10万)40重量%を乾式混合した後、約230℃に加熱して溶融で混練し、この混練物をTダイで押し出してシート状に成形することにより、厚さ300μmのシート状吸湿性成形体を得た。 CaO powder (purity 99.9%) as a hygroscopic agent was sufficiently dehydrated by heating at 900 ° C. for 1 hour, then cooled in a limited dry atmosphere of 180 to 200 ° C., and finally cooled to room temperature. 60% by weight of the obtained CaO (BET specific surface area of about 3 m 2 / g) and 40% by weight of polyethylene (molecular weight: about 100,000) as a resin component were dry-mixed, then heated to about 230 ° C. and kneaded by melting, This kneaded product was extruded with a T-die and formed into a sheet, thereby obtaining a sheet-like hygroscopic molded body having a thickness of 300 μm.

実施例2
実施例1と同じ組成のシート状吸湿性成形体の表及び裏面に同時押出で低密度ポリエチレンからなる樹脂被覆層(各厚さ約3μm)を積層し、合計厚さ300μmとなるようにシートを成形した。
Example 2
A resin coating layer (each thickness of about 3 μm) made of low-density polyethylene is laminated on the front and back surfaces of the sheet-like hygroscopic molded body having the same composition as in Example 1 by coextrusion, and the sheet is formed so that the total thickness becomes 300 μm. Molded.

実施例3
実施例1と同じ組成のシート状吸湿性成形体の表及び裏面に同時押出で低密度ポリエチレンからなる樹脂被覆層(各厚さ約12μm)を積層し、合計厚さ300μmとなるようにシートを成形した。
Example 3
A resin coating layer (each thickness of about 12 μm) made of low-density polyethylene is laminated on the front and back surfaces of the sheet-like hygroscopic molded body having the same composition as in Example 1 by coextrusion, and the sheet is formed so that the total thickness becomes 300 μm. Molded.

試験例1
実施例1〜3で得られたシートについて、吸湿による重量経時変化を調べた。各シート片(縦25mm×横14mm×厚さ300μm)を温度50℃及び相対湿度80%RHの雰囲気下に設置し、一定時間ごとの重量増加率(%)を測定した。重量増加率(%)は、次式により求めた。
重量増加率(%)=(シート片の重量増加/試験前の吸湿剤の重量)×100
その結果を表1及び図5に示す。
Test example 1
About the sheet | seat obtained in Examples 1-3, the weight temporal change by moisture absorption was investigated. Each sheet piece (length 25 mm × width 14 mm × thickness 300 μm) was placed in an atmosphere at a temperature of 50 ° C. and a relative humidity of 80% RH, and the weight increase rate (%) was measured every certain time. The weight increase rate (%) was obtained by the following formula.
Weight increase rate (%) = (weight increase of sheet piece / weight of moisture absorbent before test) × 100
The results are shown in Table 1 and FIG.

Figure 2006291224
Figure 2006291224

なお、図5には、比較のため、2種類の吸湿剤の粉末のみの重量変化を調べた結果も併せて示す。図5中、黒い丸印は酸化カルシウム粉末単独(純度99.9%)、白い丸印は酸化カルシウム粉末単独(純度98.0%)、黒い三角印は実施例1、白い三角印は実施例2、黒い四角印は実施例3をそれぞれ示す。   In addition, in FIG. 5, the result of having investigated the weight change of only the powder of two types of hygroscopic agents is also shown for a comparison. In FIG. 5, black circles indicate calcium oxide powder alone (purity 99.9%), white circles indicate calcium oxide powder alone (purity 98.0%), black triangles indicate Example 1, and white triangles indicate Example. 2. Black square marks indicate Example 3.

図5の結果からも明らかなように、本発明の吸湿性成形体では、適度な吸湿作用が得られることがわかる。これにより、本発明の吸湿性成形体を電子デバイス等に設置した場合、電子デバイス内の初期水分を除去できるとともに、封止剤を通過して侵入してきた水分も確実に除去できることがわかる。   As is apparent from the results of FIG. 5, it can be seen that the hygroscopic molded article of the present invention can obtain an appropriate hygroscopic action. Thereby, when the hygroscopic molded object of this invention is installed in an electronic device etc., it turns out that the initial moisture in an electronic device can be removed and the moisture which penetrate | invaded through the sealing agent can also be removed reliably.

実施例4
吸湿剤としてSrO粉末(粒度10μmパス)60重量%及び樹脂成分としてフッ素系樹脂(ポリテトラフルオロエチレン(PTFE))40重量%を用いた。これらを粉末状態で十分に混合した。得られた混合物を圧延ロールでシート状に圧延成形し、厚さ300μmのシートを得た。得られたシートは、PTFE樹脂がフィブリル化されており、SrOを含有した多孔質構造体となっていた。
Example 4
60% by weight of SrO powder (particle size 10 μm pass) was used as a hygroscopic agent and 40% by weight of a fluororesin (polytetrafluoroethylene (PTFE)) was used as a resin component. These were mixed thoroughly in a powder state. The obtained mixture was rolled and formed into a sheet with a rolling roll to obtain a sheet having a thickness of 300 μm. The obtained sheet was fibrillated with PTFE resin and had a porous structure containing SrO.

実施例5
吸湿剤としてSrO粉末(粒度10μmパス)60重量%及び樹脂成分としてポリエチレン40重量%を使用したほかは、実施例1と同様にして厚さ300μmのシート状吸湿性成形体を得た。
Example 5
A sheet-like hygroscopic molded article having a thickness of 300 μm was obtained in the same manner as in Example 1 except that 60% by weight of SrO powder (particle size 10 μm pass) was used as the hygroscopic agent and 40% by weight of polyethylene was used as the resin component.

実施例6
吸湿剤として実施例1と同じCaO粉末を用いたほかは、実施例4と同様にして厚さ300μmのフィブリル化されたシートを得た。
Example 6
A fibrillated sheet having a thickness of 300 μm was obtained in the same manner as in Example 4 except that the same CaO powder as in Example 1 was used as the hygroscopic agent.

試験例2
実施例4〜5で得られたシートについて、吸湿による重量経時変化を調べた。各シート片(縦25mm×横14mm×厚さ300μm)を温度20℃及び相対湿度65%RHの雰囲気下に設置し、一定時間ごとの重量増加率(%)を測定した。重量増加率は、試験例1と同様にして算出した。その結果を表2及び図6に示す。
Test example 2
About the sheet | seat obtained in Examples 4-5, the weight time-dependent change by moisture absorption was investigated. Each sheet piece (length 25 mm × width 14 mm × thickness 300 μm) was placed in an atmosphere at a temperature of 20 ° C. and a relative humidity of 65% RH, and the weight increase rate (%) was measured every certain time. The weight increase rate was calculated in the same manner as in Test Example 1. The results are shown in Table 2 and FIG.

Figure 2006291224
Figure 2006291224

実施例7
吸湿剤としてBET比表面積48m/gのCaO粉末(粒度10μmパス)60重量%及び樹脂成分としてポリエチレン(分子量:約10万)40重量%を用いた。これらを乾式混合した後、約230℃に加熱して溶融で混練し、この混練物をTダイで押し出してシート状に成形することにより、厚さ300μmのシート状吸湿性成形体を得た。なお、上記CaO粉末は、水酸化カルシウムを窒素ガス中500℃で焼成し、上記比表面積に調整したものを用いた。
Example 7
60% by weight of CaO powder (particle size 10 μm pass) having a BET specific surface area of 48 m 2 / g was used as a hygroscopic agent, and 40% by weight of polyethylene (molecular weight: about 100,000) was used as a resin component. After these were dry-mixed, they were heated to about 230 ° C. and kneaded by melting, and this kneaded product was extruded with a T-die to form a sheet, thereby obtaining a sheet-like hygroscopic molded body having a thickness of 300 μm. The CaO powder was prepared by calcining calcium hydroxide at 500 ° C. in nitrogen gas and adjusting the specific surface area.

実施例8
吸湿剤として実施例7と同じCaO粉末60重量%及び樹脂成分としてフッ素系樹脂(ポリテトラフルオロエチレン(PTFE))粉末40重量%を用いた。これらを粉末状態で十分混合した。得られた混合物を圧延ロールでシート状に圧延成形し、厚さ300μmのシートを得た。得られたシートは、PTFE樹脂がフィブリル化されており、CaOを含有した多孔質構造体となっていた。
Example 8
As the moisture absorbent, 60% by weight of the same CaO powder as in Example 7 and 40% by weight of a fluororesin (polytetrafluoroethylene (PTFE)) powder as the resin component were used. These were mixed well in a powder state. The obtained mixture was rolled and formed into a sheet with a rolling roll to obtain a sheet having a thickness of 300 μm. The obtained sheet was fibrillated with PTFE resin and had a porous structure containing CaO.

試験例3
実施例7及び8で得られたシートについて、吸湿による重量経時変化を調べた。各シート片(縦25mm×横14mm×厚さ300μm)を温度20℃及び相対湿度65%RHの雰囲気下に設置し、一定時間ごとの重量増加率(%)を測定した。重量増加率は、試験例1と同様にして算出した。その結果を表3及び図7に示す。なお、吸湿剤単独(高比表面積CaO)による試験結果も併せて示す。
Test example 3
The sheets obtained in Examples 7 and 8 were examined for changes with time in weight due to moisture absorption. Each sheet piece (length 25 mm × width 14 mm × thickness 300 μm) was placed in an atmosphere at a temperature of 20 ° C. and a relative humidity of 65% RH, and the weight increase rate (%) was measured every certain time. The weight increase rate was calculated in the same manner as in Test Example 1. The results are shown in Table 3 and FIG. In addition, the test result by a hygroscopic agent independent (high specific surface area CaO) is also shown collectively.

Figure 2006291224
Figure 2006291224

試験例4
実施例1及び6で得られたシートについて、試験例3と同様の試験を実施した。その結果を表4及び図8に示す。なお、吸湿剤単独(低比表面積CaO)による試験結果も併せて示す。
Test example 4
About the sheet | seat obtained in Example 1 and 6, the test similar to Test Example 3 was implemented. The results are shown in Table 4 and FIG. In addition, the test result by a hygroscopic agent independent (low specific surface area CaO) is also shown collectively.

Figure 2006291224
Figure 2006291224

実施例9
吸湿剤であるBaO粉末を900℃で1時間加熱して十分脱水させ、次いで180〜200℃の限率乾燥雰囲気中で冷却し、最終的に室温まで冷却した。このBaO60重量%及び樹脂成分としてポリエチレン(分子量:約10万)40重量%を乾式混合した後、約230℃に加熱して溶融で混練し、この混練物をTダイで押し出してシート状に成形することにより、厚さ300μmのシート状吸湿性成形体を得た。
Example 9
BaO powder as a hygroscopic agent was heated at 900 ° C. for 1 hour to sufficiently dehydrate, then cooled in a limited drying atmosphere at 180 to 200 ° C., and finally cooled to room temperature. After 60% by weight of BaO and 40% by weight of polyethylene (molecular weight: about 100,000) as a resin component are dry mixed, the mixture is heated to about 230 ° C. and melted and kneaded, and the kneaded product is extruded with a T-die to form a sheet. As a result, a sheet-like hygroscopic molded article having a thickness of 300 μm was obtained.

実施例10
吸湿剤として実施例9と同じBaO60重量%及び樹脂成分としてフッ素系樹脂(ポリテトラフルオロエチレン(PTFE))40重量%を粉末状態で十分混合した。得られた混合物を圧延ロールでシート状に圧延成形し、厚さ300μmのシートを得た。得られたシートは、PTFE樹脂がフィブリル化されており、BaOを含有した多孔質構造体となっていた。
Example 10
60% by weight of BaO as in Example 9 as a moisture absorbent and 40% by weight of a fluororesin (polytetrafluoroethylene (PTFE)) as a resin component were sufficiently mixed in a powder state. The obtained mixture was rolled and formed into a sheet with a rolling roll to obtain a sheet having a thickness of 300 μm. The obtained sheet had a PTFE resin fibrillated and a porous structure containing BaO.

試験例5
実施例9及び10で得られたシートについて、試験例3と同様の試験を実施した。その結果を表5及び図9に示す。なお、吸湿剤単独による試験結果も併せて示す。
Test Example 5
About the sheet | seat obtained in Example 9 and 10, the test similar to Test Example 3 was implemented. The results are shown in Table 5 and FIG. The test results with the hygroscopic agent alone are also shown.

Figure 2006291224
Figure 2006291224

試験例6
実施例4、6、8及び10で得られたシートについて、試験例3と同様の試験を実施した。その結果を表6及び図10に示す。
Test Example 6
For the sheets obtained in Examples 4, 6, 8 and 10, the same test as in Test Example 3 was performed. The results are shown in Table 6 and FIG.

Figure 2006291224
Figure 2006291224

以上の結果より、本発明吸湿体はいずれも優れた吸湿性を発揮できることがわかる。とりわけ、BET比表面積48m/gという高比表面積のCaO粉末を用いて成形した実施例8の成形体が最も高い吸湿性を示すことがわかる。また、CaOは、安全性が高いという点からも他のものよりも好ましいと言える。 From the above results, it can be seen that any of the hygroscopic bodies of the present invention can exhibit excellent hygroscopicity. In particular, it can be seen that the molded article of Example 8 molded using CaO powder having a high specific surface area of BET specific surface area of 48 m 2 / g exhibits the highest hygroscopicity. Moreover, it can be said that CaO is more preferable than others also from the point that safety is high.

図1は、本発明の吸湿性成形体の一例を示す図である。FIG. 1 is a view showing an example of a hygroscopic molded article of the present invention. 図2は、本発明の吸湿性成形体の一例を示す図である。FIG. 2 is a view showing an example of the hygroscopic molded article of the present invention. 図3は、本発明の吸湿性成形体の一例を示す図である。FIG. 3 is a view showing an example of the hygroscopic molded article of the present invention. 図4は、本発明の吸湿性成形体の一例を示す図である。FIG. 4 is a view showing an example of the hygroscopic molded article of the present invention. 図5は、試験例1における重量経時変化を調べた結果を示す図である。FIG. 5 is a diagram showing the results of examining the weight change with time in Test Example 1. FIG. 図6は、試験例2における重量経時変化を調べた結果を示す図である。FIG. 6 is a diagram showing the results of examining the weight change with time in Test Example 2. FIG. 図7は、試験例3における重量経時変化を調べた結果を示す図である。FIG. 7 is a diagram showing the results of examining the weight change with time in Test Example 3. FIG. 図8は、試験例4における重量経時変化を調べた結果を示す図である。FIG. 8 is a graph showing the results of examining the weight change with time in Test Example 4. 図9は、試験例5における重量経時変化を調べた結果を示す図である。FIG. 9 is a diagram showing the results of examining the weight change with time in Test Example 5. 図10は、試験例6における重量経時変化を調べた結果を示す図である。FIG. 10 is a diagram showing the results of examining the weight change with time in Test Example 6. FIG.

Claims (14)

吸湿剤及び樹脂成分を含有する吸湿性成形体。 A hygroscopic molded article containing a hygroscopic agent and a resin component. 吸湿剤が、アルカリ土類金属酸化物及び硫酸塩の少なくとも1種を含む請求項1記載の吸湿性成形体。 The hygroscopic molded article according to claim 1, wherein the hygroscopic agent contains at least one of an alkaline earth metal oxide and a sulfate. 吸湿剤が、CaO、BaO及びSrOの少なくとも1種である請求項1記載の吸湿性成形体。 The hygroscopic molded article according to claim 1, wherein the hygroscopic agent is at least one of CaO, BaO, and SrO. 吸湿剤として、比表面積10m/g以上の粉末が用いられている請求項1記載の吸湿性成形体。 The hygroscopic molded article according to claim 1, wherein a powder having a specific surface area of 10 m 2 / g or more is used as the hygroscopic agent. 吸湿剤として、比表面積40m/g以上の粉末が用いられている請求項1記載の吸湿性成形体。 The hygroscopic molded article according to claim 1, wherein a powder having a specific surface area of 40 m 2 / g or more is used as the hygroscopic agent. 吸湿剤が吸湿性成形体中30〜95重量%含有されている請求項1記載の吸湿性成形体。 The hygroscopic molded article according to claim 1, wherein the hygroscopic agent is contained in the hygroscopic molded article in an amount of 30 to 95% by weight. 樹脂成分が、フッ素系、ポリオレフィン系、ポリアクリル系、ポリアクリロニトリル系、ポリアミド系、ポリエステル系及びエポキシ系の少なくとも1種の高分子材料である請求項1記載の吸湿性成形体。 The hygroscopic molded article according to claim 1, wherein the resin component is at least one polymer material of fluorine, polyolefin, polyacryl, polyacrylonitrile, polyamide, polyester, and epoxy. さらにガス吸着剤を含有する請求項1記載の吸湿性成形体。 Furthermore, the hygroscopic molded object of Claim 1 containing a gas adsorbent. ガス吸着剤が、無機多孔質材料からなる請求項8記載の吸湿性成形体。 The hygroscopic molded article according to claim 8, wherein the gas adsorbent is made of an inorganic porous material. 吸湿性成形体表面の一部又は全部に樹脂被覆層が形成されている請求項1記載の吸湿性成形体。 The hygroscopic molded article according to claim 1, wherein a resin coating layer is formed on a part or all of the surface of the hygroscopic molded article. 樹脂成分がフィブリル化されている請求項1記載の吸湿性成形体。 The hygroscopic molded article according to claim 1, wherein the resin component is fibrillated. 吸湿剤としてCaO、BaO及びSrOの少なくとも1種であって比表面積10m/g以上の粉末が用いられ、かつ、樹脂成分としてフッ素系樹脂が用いられてなる請求項1記載の吸湿性成形体。 The hygroscopic molded article according to claim 1, wherein a powder having at least one of CaO, BaO and SrO and having a specific surface area of 10 m 2 / g or more is used as a hygroscopic agent, and a fluororesin is used as a resin component. . フッ素系樹脂がフィブリル化されている請求項12記載の吸湿性成形体。 The hygroscopic molded article according to claim 12, wherein the fluororesin is fibrillated. 請求項1記載の電子デバイス用吸湿性成形体。 The hygroscopic molded object for electronic devices according to claim 1.
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