JP4599592B2 - Anti-condensation agent - Google Patents
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Description
本発明は、調湿剤、及び結露防止剤として有用な多孔質材料、その調製方法、及びその用途に関するものであり、更に詳しくは、ナノメートルオーダーの金属、金属酸化物、金属含水酸化物等よりなる微粒子を、その粒子間の空隙を損なうことなく充填、集積させた構造体からなり、該微粒子間に、細孔半径が１ｎｍから１０ｎｍのナノメートルサイズの空孔を有し、所定の相対湿度域において優れた吸放湿特性を有する新規多孔質材料、その調製方法、及びその用途に関するものである。従来、一般に、材料自体が多孔質な材料を使用して調湿材料が製造されていた調湿材料の技術分野において、本発明は、ナノメートルオーダーの微粒子の粒子間に形成されるナノメートルサイズの空孔の多孔質構造を有する新しい多孔質材料を提供すること、及びナノメートルオーダーの微粒子の粒子間に形成された特定の多孔質構造の、ナノメートルサイズの空孔の有する吸放湿機能を利用した新しい調湿材、及び結露防止剤を提供すること、を特徴とするものである。 The present invention relates to a porous material useful as a humidity control agent and an anti-condensation agent, a method for preparing the same, and a use thereof, and more specifically, nanometer order metals, metal oxides, metal hydrated oxides, etc. And a nanometer-sized pore having a pore radius of 1 nm to 10 nm between the fine particles, and having a predetermined relative relationship. The present invention relates to a novel porous material having excellent moisture absorption / release characteristics in a humidity range, a method for preparing the same, and a use thereof. Conventionally, in general, in the technical field of a humidity control material in which the humidity control material is manufactured using a porous material, the present invention has a nanometer size formed between fine particles of nanometer order. Providing a new porous material having a porous structure of pores, and a moisture absorbing / releasing function of pores of a nanometer size with a specific porous structure formed between fine particles of nanometer order The present invention is characterized by providing a new humidity-controlling material and a dew condensation preventing agent.
一般に、我国の住宅建築様式においては、例えば、床下は、周囲をコンクリート側壁等で覆って、一辺が肩幅程度の矩形の出入口を空けただけのものが多く、風通しが不良なために多湿になりがちであり、そのことが、木材腐朽菌の繁殖や湿気を好む白アリによる被害の原因となっている。そのため、従来から建築物床下の腐蝕を防止したり、生活の快適化、及び衛生化を図るために適した湿度環境を提供する試みが種々行なわれてきた。例えば、木炭、及び天然軽石等の調湿剤を床下地盤に直接撒いて、床下空間の湿度を低減する方法が古くから行なわれていた。しかし、この種の方法では、これらの材料の吸湿能力には限界があり、その効果も充分ではなかった。 In general, in home building styles in Japan, for example, the floor under the floor is often covered with concrete side walls, etc., and only a rectangular entrance with a width of about one shoulder is opened, resulting in high humidity due to poor ventilation. It tends to cause damage by white ants who prefer the growth of wood decay fungi and moisture. For this reason, various attempts have been made in the past to provide a humidity environment suitable for preventing corrosion under the floor of a building, and for making life comfortable and sanitary. For example, a method of reducing humidity in the under-floor space by applying a humidity control agent such as charcoal and natural pumice directly to the floor base plate has been practiced for a long time. However, in this type of method, the moisture absorption capacity of these materials is limited, and the effect is not sufficient.
また、最近では、調湿材料として、珪藻土、アロフェン、セピオライト、及び鹿沼土等の無機系の粘土鉱物や、炭、及びシリカゲル等が一般に使われている。しかしながら、無機系の粘土鉱物を調湿材料とした場合、一般に、吸湿能力はあるが、放湿能力が劣っているため、長期間の使用に対して充分な調湿能力を持ち合わせておらず、更に、得られる調湿材料の産地により水蒸気の吸着量も大きく異なる。また、調湿材料が水蒸気を急激に吸着及び脱着する湿度範囲もその産地により異なり、所望の湿度範囲で吸放湿する材料の選定が困難である。調湿材料を、特に、床下の調湿に用いようとする場合、高湿度下での吸放湿が重要であるが、天然鉱物や炭等は、吸湿・放湿曲線の立上がりが相対湿度５０％から６０％にあり、床下調湿に適した相対湿度７５％から９３％、特に好ましい相対湿度８０％付近では、常に飽和している状態となり、必ずしも最適な調湿材料と言えるものではない。 Recently, inorganic clay minerals such as diatomaceous earth, allophane, sepiolite, and Kanuma earth, charcoal, and silica gel are generally used as humidity control materials. However, when an inorganic clay mineral is used as a humidity control material, in general, it has a moisture absorption capacity, but has a poor moisture release capacity, so it does not have sufficient humidity control capacity for long-term use. Furthermore, the amount of water vapor adsorbed varies greatly depending on the production area of the resulting humidity control material. Moreover, the humidity range in which the humidity control material rapidly adsorbs and desorbs water vapor varies depending on the production area, and it is difficult to select a material that absorbs and releases moisture within a desired humidity range. When using humidity-controlling materials, especially for humidity control under the floor, it is important to absorb and release moisture under high humidity. However, for natural minerals and charcoal, the rise of the moisture-absorption curve is 50% relative humidity. When the relative humidity is 75% to 93% suitable for under-floor humidity control, particularly in the vicinity of a particularly preferable relative humidity of 80%, it is always saturated, and is not necessarily an optimal humidity control material.
また、シリカゲルは、一度吸湿すると、加熱しない限り水分を放出しないので、床下の調湿材料としては不適当である。また、木材の腐れの原因となる腐朽菌の育成条件は、相対湿度８０％以上であるため、床下調湿材としては、相対湿度８０％付近において充分な吸湿力を求められる。一方、調湿能力を長期間維持するためには、相対湿度が低下した時、好ましくは相対湿度６０％前後の時に、水蒸気を放出し、調湿能力が回復するものでなければならない。 Silica gel is not suitable as a humidity control material under the floor because once it absorbs moisture, it does not release moisture unless it is heated. Moreover, since the growth condition of the decaying fungi that causes the rotting of wood is 80% or higher relative humidity, a sufficient moisture-absorbing capacity is required as an underfloor humidity control material in the vicinity of 80% relative humidity. On the other hand, in order to maintain the humidity control capability for a long period of time, it is necessary to release water vapor and restore the humidity control capability when the relative humidity decreases, preferably around 60% relative humidity.
また、近年では、省エネ性を高めるために、住宅の高気密・高断熱化が進み、押入等の換気が不十分な場所においては、結露が生じやすく、その対策のために、塩化カルシウム等の乾燥剤が使用されることが多い。しかし、これらの潮解性を有する塩類は、繰り返し利用が困難であり、そのために、相対湿度が低下した時、好ましくは相対湿度６０％前後の時に、水蒸気を放出し、調湿能力が回復する材料が、押入等の結露防止用にも求められていた。このような調湿機能を有する天然材料として、稚内層珪質頁岩が報告されており（非特許文献１参照）、床下調湿材として市販されているが、産出地が限られており、安定供給の面で難点がある。 Also, in recent years, in order to improve energy saving, the house has become highly airtight and highly insulated, and in places where ventilation such as intrusion is insufficient, condensation tends to occur. A desiccant is often used. However, these deliquescent salts are difficult to repeatedly use, and therefore, when relative humidity is lowered, preferably when the relative humidity is around 60%, a material that releases moisture and recovers humidity conditioning ability. However, it has also been required to prevent condensation such as intrusion. Wakkanai layer siliceous shale has been reported as a natural material having such a humidity control function (see Non-Patent Document 1) and is commercially available as an underfloor humidity control material. There are difficulties in terms of supply.
モンスーン気候帯に属し、比較的湿潤な環境である我が国においては、上述のような住環境に限らず、結露対策は、重要な課題である。例えば、各種機械設備を設置する機械室や工場棟等では、空調管理が必ずしも充分でない場合、制御盤内等で結露が発生し、腐食、漏電等のトラブルの要因となったりもするので、結露対策が必要である。 In Japan, which belongs to the monsoon climatic zone and has a relatively humid environment, countermeasures for condensation are an important issue, not limited to the living environment as described above. For example, in a machine room or factory building where various mechanical equipment is installed, if air conditioning management is not always sufficient, condensation may occur in the control panel, etc., which may cause troubles such as corrosion and leakage. Countermeasures are necessary.
相対湿度８０％付近で充分な調湿能力が期待できる多孔質材料の製造技術として、例えば、γ―アルミナ多孔体の製造方法がある（特許文献１参照）。この種の方法によれば、通常、２ｎｍから４ｎｍ付近に細孔径の揃った鋭いピークを示し、１０ｎｍから数十ｎｍ付近にもピークを示し、平均孔径は３ｎｍから６ｎｍ程度のγ−アルミナ多孔体を得ることができる。しかし、この種の材料は、高湿度域である相対湿度９０％から９５％において毛管凝縮により水蒸気を吸収することが期待される半径４ｎｍから１０ｎｍの細孔が少ないため、結露防止材料としては好ましくない。また、上述の製造方法において、γ―アルミナ微粒子を連結している非晶質シリカを完全に溶解してしまうと、細孔構造が崩壊してしまうため、結露防止材料としての多孔質材料の製造方法としては難点がある。 As a technique for producing a porous material that can be expected to have sufficient humidity control ability at a relative humidity of around 80%, for example, there is a production method of a γ-alumina porous body (see Patent Document 1). According to this type of method, a γ-alumina porous material usually shows a sharp peak with a uniform pore diameter in the vicinity of 2 nm to 4 nm, a peak in the vicinity of 10 nm to several tens of nm, and an average pore diameter of about 3 nm to 6 nm. Can be obtained. However, since this type of material has few pores with a radius of 4 nm to 10 nm that are expected to absorb water vapor by capillary condensation at a relative humidity of 90% to 95% in a high humidity region, it is preferable as a dew condensation prevention material. Absent. In addition, in the above-described manufacturing method, if the amorphous silica connecting the γ-alumina fine particles is completely dissolved, the pore structure collapses, so that the porous material as a dew condensation prevention material is manufactured. There are difficulties as a method.
一方、無機系以外の調湿材料としては、例えば、平均粒子径が２００μｍから１０００μｍの木粉原料を主成分として熱硬化性樹脂と熱可塑性樹脂を配合して、熱成形したもの（特許文献２参照）や、ポリオールと吸水性樹脂の分散体を、ポリイソシアネートと反応させて発泡ウレタン樹脂とした化粧材用調湿材（特許文献３参照）、等が報告されているが、この種の調湿剤では、製造コスト、調湿機能等の面で難点がある。 On the other hand, as a humidity control material other than inorganic materials, for example, a thermosetting resin and a thermoplastic resin are blended with a wood powder raw material having an average particle diameter of 200 μm to 1000 μm as a main component and thermoformed (Patent Document 2). For example), and a humidity control material for cosmetics (see Patent Document 3) obtained by reacting a dispersion of a polyol and a water-absorbing resin with a polyisocyanate to produce a foamed urethane resin. In the case of a moistening agent, there are difficulties in terms of manufacturing cost, humidity control function, and the like.
このように、従来、種々の調湿材料が知られているが、現状では、各々に問題点があって充分に満足いくものはなく、また、床下調湿に適した相対湿度域で充分に吸放湿し、手軽に調湿効果が長時間に亘って有効に発揮できる調湿材料として期待される稚内層珪質頁岩は、安定供給の面で難点があるため、当技術分野においては、従来材のような問題点のない新たな調湿材料の開発が強く要望されていた。 As described above, various humidity control materials have been known in the past, but at present, there are problems with each of them and there are no satisfactory ones, and the relative humidity range suitable for underfloor humidity control is sufficient. Wakkanai layered siliceous shale, which is expected to be a moisture conditioning material that absorbs and releases moisture and can effectively exert its humidity conditioning effect over a long period of time, has difficulties in terms of stable supply. There has been a strong demand for the development of a new humidity control material that is free from the problems of conventional materials.
本発明者らは、以前、相対湿度５０％から７０％の環境を自律的に維持する材料として、γ−アルミナ系多孔質材料の研究を行った際、熱処理温度条件をムライトが生成する温度域にした場合、細孔半径１ｎｍから１０ｎｍのブロードな細孔分布を有する多孔質材料が得られる可能性を見出した。その後、更に、床下調湿や押入等の結露防止に適した相対湿度６０％から９０％、特に好ましい相対湿度８０％付近で吸湿能力を有し、住宅の床下や押入等を適度な湿度に長期間に亘って保つことができる結露防止剤について鋭意研究を重ねた。 In the past, the inventors of the present invention have studied the γ-alumina porous material as a material that autonomously maintains an environment with a relative humidity of 50% to 70%. In this case, the inventors have found that a porous material having a broad pore distribution with a pore radius of 1 nm to 10 nm can be obtained. After that, it has a moisture absorption capacity at a relative humidity of 60% to 90% suitable for prevention of condensation such as underfloor humidity control and indentation, and particularly preferred near relative humidity of 80%. We conducted extensive research on anti-condensation agents that can be maintained over a period of time.
その結果、カオリン系鉱物を加熱して、ムライト相と非晶質シリカとに相分離された熱処理物を調製し、次いで、得られた熱処理物をアルカリ又はフッ酸にて処理して非晶質シリカを溶出させることにより得られる多孔質材料が、ある限られた温度領域で処理した場合においてのみ、細孔半径１ｎｍから１０ｎｍ付近のブロードな細孔分布を有し、相対湿度変動に応じて吸放湿を繰り返すことで、調湿能力が長期間持続する結露防止剤として使用できることを見出した（特許文献４参照）。 As a result, the kaolin-based mineral is heated to prepare a heat-treated product that is phase-separated into a mullite phase and amorphous silica, and then the resulting heat-treated product is treated with an alkali or hydrofluoric acid to be amorphous. The porous material obtained by elution of silica has a broad pore distribution with a pore radius of 1 nm to 10 nm only when treated in a limited temperature range, and absorbs in accordance with relative humidity fluctuations. It has been found that by repeating moisture release, it can be used as an anti-condensation agent that maintains the humidity control ability for a long period of time (see Patent Document 4).
このような状況の中で、本発明者らは、上記従来技術に鑑みて、上記従来技術の諸問題を抜本的に解決することが可能な新しい調湿材料を開発することを目標として鋭意研究を重ねた結果、ケルビンの毛管凝縮理論に基づく調湿現象を発現し得る、細孔半径１ｎｍから１０ｎｍの範囲にブロードな細孔分布を有する多孔質構造を形成するためには、材料自体が多孔質でなくとも、材料粒子間の空隙に適切な孔径の空孔を形成できれば、材料に調湿機能を付与できること、また、ナノメートルオーダーの金属、金属酸化物あるいは金属含水酸化物等の微粒子を、その粒子間の空隙を損なうことなく充填、集積させることにより、ナノメートルサイズの空孔を形成することができること、更に、これを熱処理することにより容易に除湿能力を回復させることができ、更に、再利用が可能な結露防止剤を調製することができること、を見出し、更に研究を重ねて本発明を完成させるに至った。 Under such circumstances, the present inventors have conducted intensive research with the goal of developing a new humidity control material capable of drastically solving the problems of the above-described conventional technology in view of the above-described conventional technology. As a result, in order to form a porous structure having a broad pore distribution in the pore radius range of 1 nm to 10 nm that can express the humidity control phenomenon based on the Kelvin capillary condensation theory, the material itself is porous. If the pores of the appropriate pore size can be formed in the voids between the material particles, the material can be provided with a humidity control function, and fine particles such as nanometer order metals, metal oxides or metal hydrated oxides can be added. In addition, by filling and accumulating without interfering with the voids between the particles, it is possible to form nanometer sized pores, and furthermore, heat treatment can easily recover the dehumidifying ability. So that it is further to be able to prepare a condensation inhibitor reusable, find, and completed the present invention by further investigations.
本発明は、ナノメートルオーダーの微粒子の微粒子間にナノメートルサイズの空孔を形成した多孔質材料を提供することを目的とするものである。また、本発明は、上記多孔質材料の優れた吸放湿機能を利用した、床下の調湿や押入等の結露防止に適した相対湿度７５％から９３％、特に好ましい相対湿度８０％付近で吸湿力を有しながら、相対湿度６０％付近においては放湿し、住宅の床下や押入等を適度な湿度に長期間に亘って保つことができる新しい調湿剤、及び結露防止剤を提供することを目的とするものである。 An object of the present invention is to provide a porous material in which nanometer-sized pores are formed between fine particles of nanometer order. In addition, the present invention utilizes the excellent moisture absorption / release function of the porous material, and has a relative humidity of 75% to 93%, particularly preferably around 80% relative humidity, which is suitable for prevention of dew condensation such as humidity adjustment and intrusion under the floor. Provided are a new humidity control agent and an anti-condensation agent that can absorb moisture at a relative humidity of about 60% while maintaining moisture absorption, and can keep the underfloor and indentation of a house at an appropriate humidity over a long period of time. It is for the purpose.
また、本発明は、ケルビンの毛管凝縮理論に基づき、相対湿度７５％から９３％の領域で水蒸気吸着量の増加を示す細孔半径１ｎｍから１０ｎｍ付近の細孔分布を有する上記多孔質材料の用途を提供することを目的とするものである。更に、本発明は、上記多孔質材料を有効成分として含有する材料を熱処理することにより容易に調湿性能を回復させることができ、再利用が可能な新しい調湿材、及び結露防止剤を提供することを目的とするものである Further, the present invention is based on Kelvin's capillary condensation theory, and uses of the porous material having a pore distribution in the vicinity of a pore radius of 1 nm to 10 nm showing an increase in the amount of water vapor adsorption in the range of 75% to 93% relative humidity. Is intended to provide. Furthermore, the present invention provides a new humidity conditioning material and a dew condensation prevention agent that can easily recover the humidity conditioning performance by heat-treating a material containing the porous material as an active ingredient, and can be reused. Is intended to
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）ナノメートルオーダーの微粒子を、その粒子間の空隙を損なうことなく充填、集積させることで、該微粒子間に、ナノメートルサイズの空孔を有する多孔質構造を形成させてなる多孔質材料であって、
ナノメートルオーダーの微粒子が、平均粒径１ｎｍから３０ｎｍの微粒子であり、粒子間の空孔が、細孔半径１ｎｍから１０ｎｍの範囲に細孔分布を有し、ナノメートルオーダーの微粒子が、アルミニウム酸化物、又はアルミニウム含水酸化物よりなり、上記多孔質材料が、相対湿度７５％から９３％の範囲で水蒸気吸着量の増加を示し、相対湿度７５％から９３％の範囲で吸湿した水蒸気を相対湿度７０％において放湿する水蒸気吸着・脱着等温線を示すことを特徴とする多孔質材料。
（２）３００℃前後の熱処理に対して、耐熱性を有する上記（１）に記載の多孔質材料。
（３）上記（１）又は（２）に記載の多孔質材料からなることを特徴とする調湿剤。
（４）上記（１）又は（２）に記載の多孔質材料からなることを特徴とする結露防止剤。
（５）上記（３）に記載の調湿剤を用いて、床下又は室内を調湿することを特徴とする床下又は室内の調湿方法。
（６）上記（４）に記載の結露防止剤を用いて、床下又は室内の結露を防止することを特徴とする床下又は室内の結露防止方法。
（７）ナノメートルオーダーの微粒子を、その粒子間の空隙を損なうことなく充填、集積させることにより、該微粒子間に、ナノメートルサイズの空孔を有する多孔質構造を形成することからなる多孔質材料の調製方法であって、
ナノメートルオーダーの微粒子の平均粒径が、１ｎｍから３０ｎｍであり、粒子間の空孔が、細孔半径１ｎｍから１０ｎｍの範囲に細孔分布を有し、ナノメートルオーダーの微粒子が、アルミニウム酸化物、又はアルミニウム含水酸化物であり、上記多孔質材料が、相対湿度７５％から９３％の範囲で水蒸気吸着量の増加を示し、相対湿度７５％から９３％の範囲で吸湿した水蒸気を相対湿度７０％において放湿する水蒸気吸着・脱着等温線を示すことを特徴とする多孔質材料の調製方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) fine particles of nanometer order, filling without compromising the voids between the particles, by integration, among microparticles, comprising to form a porous structure having pores of nanometer-sized multi-porous Material ,
The nanometer-order fine particles are fine particles having an average particle diameter of 1 nm to 30 nm, the pores between the particles have a pore distribution in the pore radius range of 1 nm to 10 nm, and the nanometer-order fine particles are oxidized by aluminum. The porous material exhibits an increase in the amount of water vapor adsorbed in the range of 75% to 93% relative humidity, and the moisture absorbed in the range of 75% to 93% relative humidity. A porous material having a water vapor adsorption / desorption isotherm that releases moisture at 70%.
( 2 ) The porous material according to (1), which has heat resistance against heat treatment at around 300 ° C.
( 3 ) A humidity conditioner comprising the porous material according to (1) or (2 ) above.
( 4 ) An anti-condensation agent comprising the porous material according to (1) or (2 ) above.
( 5 ) An underfloor or indoor humidity control method comprising adjusting the humidity under the floor or indoors using the humidity control agent according to ( 3 ) above.
( 6 ) An underfloor or indoor dew condensation prevention method characterized by using the dew condensation preventing agent according to ( 4 ) above to prevent underfloor or indoor dew condensation.
(7) nanometer order fine particles, filler without impairing the voids between the particles, by integration, between the fine particles, Ru Tona forming a porous structure having pores of nanometer size A method for preparing a porous material, comprising :
The average particle size of the nanometer order fine particles is 1 nm to 30 nm, the pores between the particles have a pore distribution in the range of the pore radius 1 nm to 10 nm, and the nanometer order fine particles are aluminum oxide Or an aluminum hydrate oxide, and the porous material exhibits an increase in the amount of water vapor adsorbed in the range of 75% to 93% relative humidity, and the moisture absorbed in the range of 75% to 93% relative humidity is 70% relative humidity. % Is a water vapor adsorption / desorption isotherm that dehumidifies in%.
次に、本発明について更に詳細に説明する。
本発明は、ナノメートルオーダーの微粒子、例えば、金属、金属酸化物、又は金属含水酸化物よりなる微粒子を、その粒子間の空隙を損なうことなく充填、集積させることにより、該微粒子間に、細孔半径１ｎｍから１０ｎｍの範囲にブロードな細孔分布を有する空孔を形成した特定の多孔質構造を持つ多孔質材料を製造し、提供する点、及び上記多孔質材料からなる調湿剤、及び結露防止剤を提供する点に特徴を有するものである。本発明の多孔質材料は、材料自体が多孔質である必要はなく、ナノメートルオーダーの材料粒子間の空隙にナノメートルサイズの空孔を形成して材料粒子間に特定の多孔質構造を構築した点に特徴を有するものである。
Next, the present invention will be described in more detail.
In the present invention, fine particles of nanometer order, for example, fine particles made of metal, metal oxide, or metal hydrated oxide are filled and accumulated without damaging the voids between the fine particles. Producing and providing a porous material having a specific porous structure in which pores having a broad pore distribution in a pore radius range of 1 nm to 10 nm are formed, and a humidity control agent comprising the porous material; and It is characterized by providing an anti-condensation agent. The porous material of the present invention does not need to be porous, and a specific porous structure is formed between the material particles by forming nanometer-sized pores in the voids between the material particles of the nanometer order. It has the characteristics in the point.
本発明の多孔質材料は、ナノメートルオーダーの微粒子が、平均粒径１ｎｍから３０ｎｍの範囲にブロードな細孔分布を有すること、及び粒子間の空孔が、細孔半径１ｎｍから１０ｎｍの範囲にブロードな細孔分布を有すること、を特徴としている。また、本発明の多孔質材料は、上記ナノメートルオーダーの微粒子が、金属、金属酸化物、又は金属含水酸化物よりなること、該金属酸化物、又は金属含水酸化物は、アルミニウム酸化物、又はアルミニウム含水酸化物であること、及び３００℃前後の熱処理に対して、耐熱性を有すること、を特徴としている。本発明の調湿剤は、上記多孔質材料を有効成分として含むことを特徴とするものである。また、本発明の結露防止剤は、上記多孔質材料を有効成分として含むことを特徴とするものである。 In the porous material of the present invention, fine particles on the order of nanometers have a broad pore distribution in an average particle size range of 1 nm to 30 nm, and pores between particles have a pore radius in a range of 1 nm to 10 nm. It has a broad pore distribution. In the porous material of the present invention, the nanometer-order fine particles are made of a metal, a metal oxide, or a metal hydrated oxide. The metal oxide or the metal hydrated oxide is an aluminum oxide, or It is characterized by being an aluminum hydrated oxide and having heat resistance against heat treatment at around 300 ° C. The humidity control agent of the present invention includes the above porous material as an active ingredient. In addition, the anti-condensation agent of the present invention is characterized by containing the porous material as an active ingredient.
本発明の多孔質材料の多孔質構造について説明すると、本発明の方法で形成される多孔質構造は、微粒子の集積体からなり、該集積体を構成する粒子サイズを適宜調整することにより、多孔質構造を任意に制御することが可能である。多孔質構造を形成する材料としては、その組成よりも粒子サイズが重要であり、粒子間の空隙が、細孔半径１ｎｍから１０ｎｍの範囲にブロードな細孔分布を有するためには、少なくとも数十ナノメートル以下、好適には、１ｎｍから３０ｎｍの粒径を有する粒子を用いることが必要とされる。 The porous structure of the porous material of the present invention will be described. The porous structure formed by the method of the present invention consists of an aggregate of fine particles, and by appropriately adjusting the size of the particles constituting the aggregate, It is possible to arbitrarily control the quality structure. As a material for forming a porous structure, the particle size is more important than the composition, and in order for the voids between the particles to have a broad pore distribution in the pore radius range of 1 nm to 10 nm, it is at least several tens. It is necessary to use particles having a particle size of nanometers or less, preferably 1 nm to 30 nm.
本発明において、微粒子間の空隙を損なうことなく微粒子を充填、集積して任意のナノメートルサイズの空孔を形成するには、具体的には、１ｎｍから３０ｎｍの粒径の微粒子を、その粒子間の空隙を損なうことがないよう、過度な圧力を掛けることなく堆積又は圧粉といった方法により充填することが好適である。本発明において、ナノメートルオーダーの微粒子を、その粒子間の空隙を損なうことなく充填、集積させるとは、上記粒子間に本来的に形成される空隙を略維持した状態で粒子を任意の手段で充填、集積させることを意味するものであり、具体的には、上記空隙が維持されるように、過度な圧力を掛けることなく堆積、圧粉する等の充填手段で充填し、集積させる方法が例示される。しかし、充填、集積の手段は、これらに制限されるものではなく、上記空隙を損なうことなく粒子を充填、集積させることができる手段及び方法であれば同様に使用することができる。 In the present invention, in order to form fine pores having an arbitrary nanometer size by filling and accumulating fine particles without impairing voids between the fine particles, specifically, fine particles having a particle size of 1 nm to 30 nm are used. In order not to damage the gaps between them, it is preferable to fill by a method such as deposition or compaction without applying excessive pressure. In the present invention, filling and accumulating fine particles of nanometer order without impairing the voids between the particles means that the particles are maintained by any means while maintaining the voids originally formed between the particles. Specifically, a method of filling and accumulating with a filling means such as depositing and compacting without applying excessive pressure so as to maintain the above-mentioned voids is meant. Illustrated. However, the means for filling and accumulating is not limited to these, and any means and method capable of filling and accumulating particles without impairing the voids can be used as well.
本発明では、平均粒径が１ｎｍから３０ｎｍ前後の微粒子を、その粒子間へ空隙を損なうことなく充填、集積させることにより、ナノサイズの空孔を形成した、多孔質構造を構築することが可能となる。このように処理した集積体の粒子間には、例えば、約１ｎｍから３０ｎｍ程度、好ましくは約１ｎｍから１０ｎｍを含む空孔が形成される。また、本発明では、集積体の粒子の粒径、製造条件、及び処理条件等を調整することにより空孔の孔径を任意にコントロールすることができる。空孔の孔径をコントロールするための具体的方法としては、好適には、例えば、粒子の粒径を適宜選択することで空孔の孔径を制御する方法、及び異なる粒径の粒子を配合することで、形成される空孔の孔径を制御する方法が例示されるが、これらに制限されるものではない。 In the present invention, it is possible to construct a porous structure in which nano-sized pores are formed by filling and accumulating fine particles having an average particle diameter of about 1 nm to about 30 nm without impairing voids between the particles. It becomes. For example, pores containing about 1 nm to 30 nm, preferably about 1 nm to 10 nm, are formed between the particles of the aggregate thus treated. In the present invention, the pore diameter of the pores can be arbitrarily controlled by adjusting the particle size, production conditions, processing conditions, and the like of the aggregate particles. As a specific method for controlling the pore diameter of the pores, preferably, for example, a method of controlling the pore diameter of the pores by appropriately selecting the particle diameter of the particles, and blending particles having different particle diameters Thus, methods for controlling the hole diameter of the formed holes are exemplified, but the method is not limited thereto.
本発明では、ナノメートルオーダーの微粒子として、好適には、例えば、金属酸化物、又は金属含水酸化物が使用されるが、具体的には、例えば、アルミニウム酸化物（アルミナ）、アルミニウム含水酸化物（ベーマイト、ギブサイト等）等が例示される。本発明では、好適には、ナノメートルオーダーの材料として、これらのアルミニウム酸化物系材料が好適な材料として使用されるが、これらに制限されるものではなく、これらと同等もしくは類似のものであれば、他の金属系酸化物等であっても同様に使用することができる。調湿現象は、基本的には、ケルビンの毛管凝縮理論に基づくものであるため、多孔質構造の形成に用いる材料の材質には基本的には依存しない。 In the present invention, for example, a metal oxide or a metal hydrated oxide is preferably used as the nanometer order fine particles. Specifically, for example, an aluminum oxide (alumina) or an aluminum hydrated oxide is used. (Boehmite, Gibbsite, etc.) In the present invention, these aluminum oxide materials are preferably used as materials on the order of nanometers. However, the present invention is not limited to these materials, and any equivalent or similar materials may be used. For example, other metal oxides can be used in the same manner. The humidity control phenomenon is basically based on Kelvin's capillary condensation theory, and therefore basically does not depend on the material used to form the porous structure.
そのため、本発明で用いられる材料は、水との相互作用によりその性状を変化させるもの、例えば、潮解、溶解等により形状が消失する可溶性の塩類微粒子、膨潤等により変形し得る高分子系微粒子、水と化学反応する金属あるいは金属酸化物系微粒子等でない限り、その種類及び組成が特に限定されるものではない。本発明においては、細孔半径１ｎｍから１０ｎｍの範囲にブロードな細孔分布を有する多孔質構造を持つ多孔質材料が、調湿剤、及び結露防止剤として利用可能な多孔質構造の多孔質材料として例示される。本発明では、多孔質材料の粒径をより精密に制御することにより、ケルビンの毛管凝縮理論に基づく調湿現象が生じる相対湿度条件を精密に調整することが可能である。 Therefore, the material used in the present invention is one that changes its properties by interaction with water, for example, soluble salt fine particles whose shape disappears due to deliquescence, dissolution, etc., polymeric fine particles that can be deformed by swelling, The type and composition are not particularly limited unless the metal or metal oxide fine particles chemically react with water. In the present invention, a porous material having a porous structure having a broad pore distribution in a pore radius range of 1 nm to 10 nm is used as a humidity control agent and a dew condensation preventing agent. It is illustrated as. In the present invention, by controlling the particle size of the porous material more precisely, it is possible to precisely adjust the relative humidity condition in which the humidity conditioning phenomenon based on the Kelvin capillary condensation theory occurs.
この場合、金属酸化物あるいは金属含水酸化物が熱的、化学的に安定な条件であれば、材料自体は変化することがなく、当然の結果として、材料粒子間に形成される空隙も影響を受けることはない。一般的に、結露防止剤は、吸湿により、その性能が徐々に低下し、吸湿飽和に至ると無力化するが、本発明では、材料が影響を受けない範囲での熱処理により、吸湿性能を容易に回復させることが可能である。例えば、本発明の結露防止剤を、５０℃から３００℃の温度で、熱処理することにより、吸湿飽和した吸湿能力を再生することができる。本発明においては、材料の金属酸化物あるいは金属含水酸化物が熱的、化学的に安定な条件で、材料を粒子間の空隙を損なうことなく充填、集積させるが、その具体的な方法としては、前述のように、空隙を損なうことがないよう、過度な圧力を掛けることなく堆積又は圧粉するといった方法が例示される。 In this case, if the metal oxide or the metal hydrated oxide is thermally and chemically stable, the material itself does not change, and as a result, the voids formed between the material particles are also affected. I will not receive it. In general, anti-condensation agents gradually lose their performance due to moisture absorption, and become neutral when moisture absorption is saturated.In the present invention, moisture absorption performance is easily achieved by heat treatment within a range that does not affect the material. It is possible to recover. For example, the moisture absorption capacity saturated with moisture absorption can be regenerated by heat-treating the dew condensation inhibitor of the present invention at a temperature of 50 ° C. to 300 ° C. In the present invention, the material metal oxide or metal hydrated oxide is filled and accumulated in a thermally and chemically stable condition without damaging the voids between the particles. As described above, there is exemplified a method of depositing or compacting without applying excessive pressure so as not to damage the air gap.
上記方法により、細孔半径１ｎｍから１０ｎｍの範囲にブロードな細孔分布を有する多孔質構造を有し、ケルビンの毛管凝縮理論に基づき、相対湿度７５％から９５％の領域で水蒸気吸着量の増加を示す多孔質材料を調製することができる。本発明では、平均粒径１ｎｍから３０ｎｍの微粒子を、その粒子間の空隙を損なうことなく充填、集積させることにより、細孔分布が精密に制御された、細孔半径１ｎｍから１０ｎｍの範囲にブロードな細孔分布を有する多孔質材料を調製することができる。 By the above method, it has a porous structure with a broad pore distribution in the pore radius range of 1 nm to 10 nm, and based on the Kelvin capillary condensation theory, the amount of water vapor adsorption is increased in the range of 75% to 95% relative humidity. Can be prepared. In the present invention, fine particles with an average particle diameter of 1 nm to 30 nm are filled and accumulated without impairing the voids between the particles, and the pore distribution is broadly controlled within a range of pore diameters of 1 nm to 10 nm. A porous material having a fine pore distribution can be prepared.
このように、本発明では、例えば、平均粒径１ｎｍから３０ｎｍの微粒子を、その粒子間の空隙を損なうことなく充填、集積させることにより、該空隙に、細孔半径１ｎｍから１０ｎｍの範囲にブロードな細孔分布の空孔を有する多孔質構造からなる多孔質材料を製造することが可能であり、また、これらの製造工程における処理条件を調節することにより、細孔分布が精密に制御された、所定の相対湿度の領域において優れた吸放湿特性を有する、調湿剤、及び結露防止剤として有用な多孔質材料を製造し、提供することができる。 Thus, in the present invention, for example, fine particles having an average particle diameter of 1 nm to 30 nm are filled and accumulated without impairing the voids between the particles, so that the voids are broadened in the range of pore diameters of 1 nm to 10 nm. It is possible to manufacture a porous material having a porous structure having pores with a fine pore distribution, and the pore distribution is precisely controlled by adjusting the processing conditions in these manufacturing processes. It is possible to produce and provide a porous material useful as a humidity control agent and an anti-condensation agent having excellent moisture absorption / release characteristics in a predetermined relative humidity region.
本発明の多孔質材料は、床下等の調湿には、例えば、そのまま散布して用いることが可能であり、また、押入等の結露防止には、例えば、通気性を有する容器等に充填して使用することが可能である。また、該多孔質材料を繊維等に漉き込み、紙製又は布製シート形状にて使用することも可能である。また、上記多孔質材料は、その調湿性能等を妨げないような適宜の工夫を付加することで、例えば、内装建材等の原材料として利用することができる。しかし、本発明の、多孔質材料の調湿剤及び／又は結露防止剤の使用形態は特に制限されるものではなく、それらの製品の形態については製品の種類及び大きさ等に応じて任意に設計することができる。 The porous material of the present invention can be used by, for example, spraying as it is for humidity adjustment under the floor, etc., and for preventing condensation such as intrusion, it is filled in, for example, a breathable container. Can be used. It is also possible to use the porous material in fibers or the like and use it in the form of paper or cloth. Moreover, the said porous material can be utilized as raw materials, such as an interior building material, by adding the appropriate device which does not disturb the humidity control performance etc., for example. However, the use form of the humidity control agent and / or anti-condensation agent of the porous material of the present invention is not particularly limited, and the form of those products is arbitrarily selected according to the type and size of the product. Can be designed.
従来材では、主に、粒子自体が多孔質性を有する材料が調湿剤として使用されていた。これに対して、本発明では、ナノメートルオーダーの微粒子が、その粒子間の空隙を損なうことなく充填、集積された構造体からなり、該微粒子間に、ナノメートルサイズの空孔を有する多孔質材料が使用される。本発明の多孔質材料は、細孔半径１ｎｍから１０ｎｍの範囲にブロードな細孔分布を有する多孔質構造を有し、ケルビンの毛管凝縮理論に基づき、相対湿度７５％から９３％の領域で水蒸気吸着量の増加を示す。該多孔質材料は、後記する実施例に示されるように、その吸着・脱着等温線からみて、吸着等温線の立ち上がりは約８０％付近であり、相対湿度７５％から９３％の範囲での吸湿量は、約１２ｍａｓｓ％であること、脱着等温線からは、相対湿度約７０％において、相対湿度７５％から９３％の範囲で吸着していた水蒸気は放湿され、結露防止能力が回復されること、等の特性を有する。 In the conventional material, a material in which the particles themselves have a porous property is mainly used as a humidity control agent. On the other hand, in the present invention, the fine particles of nanometer order are composed of a structure that is filled and integrated without impairing the voids between the particles, and the porous material has pores of nanometer size between the fine particles. Material is used. The porous material of the present invention has a porous structure having a broad pore distribution in a pore radius range of 1 nm to 10 nm, and is based on Kelvin's capillary condensation theory in a region where the relative humidity is 75% to 93%. An increase in the amount of adsorption is shown. The porous material has an adsorption isotherm rise of about 80% as seen from the adsorption / desorption isotherm, as shown in the examples described later, and absorbs moisture in the range of 75% to 93% relative humidity. The amount is about 12 mass%. From the desorption isotherm, water vapor adsorbed in the range of 75% to 93% relative humidity is released at a relative humidity of about 70%, and the dew condensation prevention ability is restored. And so on.
本発明により、１）ナノメートルオーダーの微粒子間に、細孔半径が１ｎｍから１０ｎｍの範囲にブロードな細孔分布を有する空孔を形成した特定の多孔質構造を有し、優れた吸放湿機能を有する多孔質材料を提供することができる、２）上記多孔質材料を利用することにより、ケルビンの毛管凝縮理論に基づき、相対湿度７５％から９３％の領域で水蒸気吸着量の増加を示す調湿剤又は結露防止剤を提供することができる、３）相対湿度７５％から９３％の領域で水蒸気吸着量の増加を示す上記多孔質材料を用いて所定の空間を調湿する該空間の調湿方法及び結露防止方法を提供することができる、４）該調湿剤及び結露防止剤は、３００℃、２時間の熱処理程度では調湿性能には殆ど影響を与えないため、吸湿によって調湿性能が低下した場合でも、熱処理するだけで、容易に、かつ短時間でその調湿性能を回復し得る再利用可能性を有する、５）住宅の床下又は室内を適度な湿度に保つ、調湿剤又は結露防止剤を提供することができる、という格別の効果が奏される。 According to the present invention, 1) a specific porous structure in which pores having a broad pore distribution in a pore radius range of 1 nm to 10 nm are formed between fine particles of nanometer order, and excellent moisture absorption and desorption It is possible to provide a porous material having a function. 2) Based on the Kelvin capillary condensation theory, by using the porous material, the water vapor adsorption amount is increased in the region of 75% to 93% relative humidity. A humidity control agent or an anti-condensation agent can be provided. 3) Using the above porous material exhibiting an increase in the amount of water vapor adsorption in the range of 75% to 93% relative humidity, A humidity control method and a dew condensation prevention method can be provided. 4) The humidity control agent and the dew condensation prevention agent have little effect on the humidity control performance after heat treatment at 300 ° C. for 2 hours. Wet performance is reduced Even if heat treatment, it has a reusability that can restore its humidity control performance easily and in a short time just by heat treatment. 5) Keeping the underfloor or interior of the house at a moderate humidity, humidity control or anti-condensation The special effect that an agent can be provided is produced.
次に、実施例及び比較例に基づいて本発明を具体的に説明するが、本発明は、以下の実施例及び比較例によって何ら限定されるものではない。 Next, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.
（１）アルミニウム含水酸化物による多孔質構造の構築
材料として、比表面積１２６ｍ２／ｇ、平均粒子サイズ３０ｎｍのアルミニウム含水酸化物（ベーマイト）を用意した。このベーマイト粒子を、過度な圧力を掛けることなく充填することにより、その粒子間の空隙を損なうことなく集積し、粒子間の接触により粒子間の空隙に、ブロードなナノメートルサイズの細孔分布を有する空孔を形成した特定の多孔質構造を構築した。
(1) Construction of porous structure with aluminum hydrated oxide As a material, an aluminum hydrated oxide (boehmite) having a specific surface area of 126 m 2 / g and an average particle size of 30 nm was prepared. By filling the boehmite particles without applying excessive pressure, the voids between the particles are accumulated without impairing, and the contact between the particles creates a broad nanometer-size pore distribution in the voids between the particles. A specific porous structure with pores was constructed.
（２）測定方法
比表面積は、１０５℃で加熱・真空脱気処理した試料を用いて、窒素ガスを用いたＢＥＴ法により、比表面積自動測定装置（Ｓｏｒｐｔｏｍａｔｉｃ １９００，Ｃａｌｒｏ Ｅｒｂａ社）で測定した。細孔径分布は、比表面積自動測定装置で測定した窒素吸着等温線をＤｏｌｌｉｍｏｒｅ−Ｈｅａｌ法により解析して求めた。水蒸気吸着量は、測定温度（２５℃）にて真空脱気処理した試料を用いて、吸着平衡測定装置（ＥＡＭ−０１，ＪＴトーシ（株））で、相対湿度１０％から９５％の範囲で測定した。
(2) Measuring method The specific surface area was measured with a specific surface area automatic measuring device (Sorptomatic 1900, Calro Erba) by a BET method using nitrogen gas using a sample heated and vacuum degassed at 105 ° C. The pore size distribution was determined by analyzing the nitrogen adsorption isotherm measured with a specific surface area automatic measuring device by the Dollimore-Heal method. The amount of water vapor adsorption can be measured in a range from 10% to 95% relative humidity using an adsorption equilibrium measuring device (EAM-01, JT Toshi Co., Ltd.) using a sample that has been vacuum degassed at the measurement temperature (25 ° C.). It was measured.
（３）結果
本実施例において、粒子間の空隙として形成され、調湿に寄与し得ると考えられる細孔容積は、０．４７ｍｌ／ｇであった。また、その細孔径分布を図１（実施例１）に示す。細孔半径１ｎｍから３０ｎｍの範囲にブロードな細孔分布を有することが判る。また、その吸着・脱着等温線を図２（実施例１）に示す。吸着等温線の立ち上がりは約８０％付近であった。相対湿度７５％から９３％の範囲での吸湿量に着目すると、約１２ｍａｓｓ％であった。脱着等温線からは相対湿度約７０％において、相対湿度７５％から９３％の範囲で吸着していた水蒸気は放湿され、結露防止能力が回復することが示された。
(3) Results In this example, the pore volume formed as voids between particles and considered to be able to contribute to humidity control was 0.47 ml / g. The pore size distribution is shown in FIG. 1 (Example 1). It can be seen that there is a broad pore distribution in the pore radius range of 1 nm to 30 nm. Further, the adsorption / desorption isotherm is shown in FIG. 2 (Example 1). The rise of the adsorption isotherm was about 80%. When paying attention to the moisture absorption in the range of 75% to 93% relative humidity, it was about 12 mass%. From the desorption isotherm, it was shown that the water vapor adsorbed in the range of 75% to 93% relative humidity was released at a relative humidity of about 70%, and the ability to prevent condensation was recovered.
比較例
（１）試料の調製
比較例として、実施例１と同組成であるが、比表面積１２ｍ２／ｇ、粒子サイズ２００ｎｍのアルミニウム含水酸化物（ベーマイト）を用意した。このベーマイト粒子を過度な圧力を掛けることなく充填することにより粒子間の接触による空隙を形成した。
Comparative Example (1) Preparation of Sample As a comparative example, an aluminum hydrated oxide (boehmite) having the same composition as in Example 1 but having a specific surface area of 12 m 2 / g and a particle size of 200 nm was prepared. By filling the boehmite particles without applying excessive pressure, voids due to contact between the particles were formed.
（２）測定方法
比表面積は、１０５℃で加熱・真空脱気処理した試料を用いて、窒素ガスを用いたＢＥＴ法により、比表面積自動測定装置（Ｓｏｒｐｔｏｍａｔｉｃ １９００，Ｃａｌｒｏ Ｅｒｂａ社）で測定した。細孔径分布は、比表面積自動測定装置で測定した窒素吸着等温線をＤｏｌｌｉｍｏｒｅ−Ｈｅａｌ法により解析して求めた。水蒸気吸着量は、測定温度（２５℃）にて真空脱気処理した試料を用いて、吸着平衡測定装置（ＥＡＭ−０１，ＪＴトーシ（株））で、相対湿度１０％から９５％の範囲で測定した。
(2) Measuring method The specific surface area was measured with a specific surface area automatic measuring device (Sorptomatic 1900, Calro Erba) by a BET method using nitrogen gas using a sample heated and vacuum degassed at 105 ° C. The pore size distribution was determined by analyzing the nitrogen adsorption isotherm measured with a specific surface area automatic measuring device by the Dollimore-Heal method. The amount of water vapor adsorption can be measured in a range from 10% to 95% relative humidity using an adsorption equilibrium measuring device (EAM-01, JT Toshi Co., Ltd.) using a sample that has been vacuum degassed at the measurement temperature (25 ° C.). It was measured.
（３）結果
本比較例において、粒子間の空隙として形成され、調湿に寄与し得ると考えられる細孔容積は、０．０７ｍｌ／ｇであった。また、その細孔径分布を図１（比較例）に示す。実施例１と比較して、細孔半径１ｎｍから３０ｎｍの範囲における細孔は殆ど認められないことが判る。また、その吸着・脱着等温線を図２（比較例）に示す。吸着等温線の立ち上がりは殆ど認められず、毛管凝縮現象に起因する調湿効果がないことが判る。
(3) Results In this comparative example, the pore volume formed as voids between the particles and considered to be able to contribute to humidity control was 0.07 ml / g. The pore size distribution is shown in FIG. 1 (comparative example). Compared to Example 1, it can be seen that almost no pores are observed in the pore radius range of 1 nm to 30 nm. The adsorption / desorption isotherm is shown in FIG. 2 (comparative example). The rise of the adsorption isotherm is hardly recognized, and it is understood that there is no humidity conditioning effect due to the capillary condensation phenomenon.
（１）アルミニウム含水酸化物による多孔質構造の熱処理による影響
材料として、比表面積１２６ｍ２／ｇ、粒子サイズ３０ｎｍのアルミニウム含水酸化物（ベーマイト）を３５０℃で２時間熱処理したものを用意した。このベーマイト粒子を、過度な圧力を掛けることなく充填することにより、その粒子間の空隙を損なうことなく集積し、粒子間の接触により粒子間の空隙を形成させた。
(1) Influence of heat treatment of porous structure with aluminum hydrated oxide A material prepared by heat treating aluminum hydrated oxide (boehmite) having a specific surface area of 126 m 2 / g and a particle size of 30 nm at 350 ° C. for 2 hours was prepared. By filling the boehmite particles without applying an excessive pressure, the voids between the particles were accumulated without impairing, and voids between the particles were formed by contact between the particles.
（２）測定方法
比表面積は、１０５℃で加熱・真空脱気処理した試料を用いて、窒素ガスを用いたＢＥＴ法により、比表面積自動測定装置（Ｓｏｒｐｔｏｍａｔｉｃ １９００，Ｃａｌｒｏ Ｅｒｂａ社）で測定した。細孔径分布は、比表面積自動測定装置で測定した窒素吸着等温線をＤｏｌｌｉｍｏｒｅ−Ｈｅａｌ法により解析して求めた。水蒸気吸着量は、測定温度（２５℃）にて真空脱気処理した試料を用いて、吸着平衡測定装置（ＥＡＭ−０１，ＪＴトーシ（株））で、相対湿度１０％から９５％の範囲で測定した。
(2) Measuring method The specific surface area was measured with a specific surface area automatic measuring device (Sorptomatic 1900, Calro Erba) by a BET method using nitrogen gas using a sample heated and vacuum degassed at 105 ° C. The pore size distribution was determined by analyzing the nitrogen adsorption isotherm measured with a specific surface area automatic measuring device by the Dollimore-Heal method. The amount of water vapor adsorption can be measured in a range from 10% to 95% relative humidity using an adsorption equilibrium measuring device (EAM-01, JT Toshi Co., Ltd.) using a sample that has been vacuum degassed at the measurement temperature (25 ° C.). It was measured.
（３）結果
本実施例において、粒子間の空隙に空孔として形成され、調湿に寄与し得ると考えられる細孔容積は、０．４２ｍｌ／ｇであった。また、その細孔径分布を図３に示す。細孔半径１ｎｍから３０ｎｍの範囲にブロードな細孔分布を有することが判る。また、その吸着・脱着等温線を図４に示す。吸着等温線の立ち上がりは約８０％付近であった。相対湿度７５％から９３％の範囲での吸湿量に着目すると、約１２ｍａｓｓ％であった。脱着等温線からは相対湿度約７０％において、相対湿度７５％から９３％の範囲で吸着していた水蒸気は放湿され、結露防止能力が回復することが示された。
(3) Results In this example, the pore volume that was formed as voids in the voids between the particles and could contribute to humidity control was 0.42 ml / g. The pore size distribution is shown in FIG. It can be seen that there is a broad pore distribution in the pore radius range of 1 nm to 30 nm. Further, the adsorption / desorption isotherm is shown in FIG. The rise of the adsorption isotherm was about 80%. When paying attention to the moisture absorption in the range of 75% to 93% relative humidity, it was about 12 mass%. From the desorption isotherm, it was shown that the water vapor adsorbed in the range of 75% to 93% relative humidity was released at a relative humidity of about 70%, and the ability to prevent condensation was recovered.
本実施例により、比表面積１２６ｍ２／ｇ、粒子サイズ３０ｎｍのアルミニウム含水酸化物（ベーマイト）は、３５０℃、２時間の熱処理程度では調湿性能には殆ど影響を受けないことが明らかであり、吸湿によって調湿性能が低下した場合でも、熱処理で容易に、かつ短時間で調湿性能を回復し得ることが確認された。 According to this example, it is clear that the aluminum hydrous oxide (boehmite) having a specific surface area of 126 m 2 / g and a particle size of 30 nm is hardly affected by the humidity control performance at about 350 ° C. for 2 hours, It was confirmed that even when the humidity control performance is reduced by moisture absorption, the humidity control performance can be easily recovered by heat treatment in a short time.
以上詳述したように、本発明は、調湿剤、及び結露防止剤に係るものであり、本発明により、ナノメートルオーダーの微粒子を、その粒子間の空隙を損なうことなく充填、集積させることにより、粒子間に、ブロードナ細孔分布を有するナノメートルサイズの空孔を形成した多孔質材料を調製し、提供することができる。本発明は、上記多孔質材料を利用した、床下調湿や押入等の結露防止に適した相対湿度７５％から９３％、特に好ましい相対湿度８０％付近で吸湿力を有しながら、相対湿度６０％付近においては放湿し、住宅の床下や押入等を適度な湿度に長期間に亘って保つことができる、調湿剤、及び結露防止剤を提供することができる。 As described above in detail, the present invention relates to a humidity control agent and an anti-condensation agent, and according to the present invention, fine particles of nanometer order are filled and accumulated without impairing voids between the particles. Thus, a porous material in which nanometer-sized pores having a broadner pore distribution are formed between particles can be prepared and provided. The present invention uses the porous material described above, and has a relative humidity of 75% to 93% suitable for prevention of condensation such as underfloor humidity control and intrusion, and a relative humidity of 60% while having a hygroscopicity near a particularly preferable relative humidity of 80%. It is possible to provide a humidity control agent and an anti-condensation agent that release moisture in the vicinity of%, and can keep the underfloor and indentation of the house at an appropriate humidity for a long period of time.
また、本発明は、ケルビンの毛管凝縮理論に基づき、相対湿度７５％から９３％の領域で水蒸気吸着量の増加を示す特定の多孔質構造を有する調湿剤、及び結露防止剤を提供することができる。また、本発明は、３００℃、２時間の熱処理程度では調湿性能には殆ど影響を与えず、吸湿によって調湿機能が低下した場合でも、熱処理することにより容易に除湿能力を回復させることができる、再利用可能な、調湿剤、及び結露防止剤を提供することができる。本発明は、ナノメートルサイズの粒子の粒子間に形成された多孔質構造である、ナノメートルサイズの空孔の有する吸放出機能を利用した新しいタイプの調湿剤、及び結露防止剤を提供するものであり、従来材にない多様な空孔構造とそれに基づく多様な吸放湿機能を有する所望の吸放湿製品を任意に設計し、提供することを可能とするものである。 The present invention also provides a humidity control agent having a specific porous structure and an anti-condensation agent exhibiting an increase in water vapor adsorption in the region of relative humidity of 75% to 93% based on Kelvin's capillary condensation theory. Can do. In addition, the present invention has almost no effect on the humidity control performance at 300 ° C. for 2 hours, and even if the humidity control function is reduced by moisture absorption, the dehumidifying ability can be easily recovered by heat treatment. And reusable humidity control and anti-condensation agents can be provided. The present invention provides a new type of humidity control agent and anti-condensation agent using the absorption / release function of nanometer-size pores, which are porous structures formed between nanometer-size particles. Thus, it is possible to arbitrarily design and provide a desired moisture absorbing / releasing product having various pore structures that are not present in conventional materials and various moisture absorbing / releasing functions based thereon.
Claims (7)
ナノメートルオーダーの微粒子が、平均粒径１ｎｍから３０ｎｍの微粒子であり、粒子間の空孔が、細孔半径１ｎｍから１０ｎｍの範囲に細孔分布を有し、ナノメートルオーダーの微粒子が、アルミニウム酸化物、又はアルミニウム含水酸化物よりなり、上記多孔質材料が、相対湿度７５％から９３％の範囲で水蒸気吸着量の増加を示し、相対湿度７５％から９３％の範囲で吸湿した水蒸気を相対湿度７０％において放湿する水蒸気吸着・脱着等温線を示すことを特徴とする多孔質材料。 Fine particles of nanometer order, filling without compromising the voids between the particles, by integration, among microparticles, met multi porous material made by forming a porous structure having pores of nanometer size And
The nanometer-order fine particles are fine particles having an average particle diameter of 1 nm to 30 nm, the pores between the particles have a pore distribution in the pore radius range of 1 nm to 10 nm, and the nanometer-order fine particles are oxidized by aluminum. The porous material exhibits an increase in the amount of water vapor adsorbed in the range of 75% to 93% relative humidity, and the water vapor absorbed in the range of 75% to 93% relative humidity. A porous material having a water vapor adsorption / desorption isotherm that releases moisture at 70%.
ナノメートルオーダーの微粒子の平均粒径が、１ｎｍから３０ｎｍであり、粒子間の空孔が、細孔半径１ｎｍから１０ｎｍの範囲に細孔分布を有し、ナノメートルオーダーの微粒子が、アルミニウム酸化物、又はアルミニウム含水酸化物であり、上記多孔質材料が、相対湿度７５％から９３％の範囲で水蒸気吸着量の増加を示し、相対湿度７５％から９３％の範囲で吸湿した水蒸気を相対湿度７０％において放湿する水蒸気吸着・脱着等温線を示すことを特徴とする多孔質材料の調製方法。 Fine particles of nanometer order, filling without compromising the voids between the particles, by integration, among microparticles, Tona Ru porous material to form a porous structure having pores of nanometer size A preparation method of
The average particle size of the nanometer order fine particles is 1 nm to 30 nm, the pores between the particles have a pore distribution in the range of the pore radius 1 nm to 10 nm, and the nanometer order fine particles are aluminum oxide Or an aluminum hydrated oxide, wherein the porous material exhibits an increase in water vapor adsorption in the range of 75% to 93% relative humidity, and the moisture absorbed in the range of 75% to 93% relative humidity is 70% relative humidity. % Is a water vapor adsorption / desorption isotherm that dehumidifies in%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015056285A1 (en) | 2013-10-15 | 2015-04-23 | 株式会社Ｎａｔｏｍｉｃｓ | Method of preserving heat exchange surface and method of cooling moist air |
| JP2016194406A (en) * | 2016-05-17 | 2016-11-17 | 株式会社Ｎａｔｏｍｉｃｓ | Carrier for suppressing frost formation or defrosting, and heat exchanger having carrier |
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|---|---|---|---|---|
| CN101765753B (en) * | 2007-07-27 | 2011-12-28 | 三菱电机株式会社 | Heat exchanger, method of producing the heat exchanger |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000176276A (en) * | 1998-12-18 | 2000-06-27 | Agency Of Ind Science & Technol | Gas adsorbing and desorbing material and its production |
| JP2000189744A (en) * | 1999-01-05 | 2000-07-11 | Agency Of Ind Science & Technol | Production of moisture regulating material |
| JP2001170500A (en) * | 1999-01-12 | 2001-06-26 | Toyota Central Res & Dev Lab Inc | Porous body, method of producing the same and exhaust gas purification catalyst using the porous body |
| JP2002004193A (en) * | 2000-06-15 | 2002-01-09 | Ykk Corp | Conditioning paper and method for producing the same |
| JP2004010423A (en) * | 2002-06-06 | 2004-01-15 | Matsushita Electric Ind Co Ltd | Solid heat insulating material and its manufacturing method |
| JP2004345890A (en) * | 2003-05-21 | 2004-12-09 | Toyota Motor Corp | Porous composite oxide and its production method |
| WO2004113251A1 (en) * | 2003-06-20 | 2004-12-29 | Matsushita Electric Industrial Co., Ltd. | Porous body and method for producing same |
| JP2005081495A (en) * | 2003-09-09 | 2005-03-31 | Makio Naito | Porous body coated particle, precursor for heat insulating material containing the porous body coated particle and heat insulating material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01208376A (en) * | 1987-10-09 | 1989-08-22 | Matsushita Electric Works Ltd | Production of fine cellular body |
| JPH04108677A (en) * | 1990-08-28 | 1992-04-09 | Matsushita Electric Works Ltd | Production of microporous body |
| JP3633641B2 (en) * | 1994-02-25 | 2005-03-30 | 東京瓦斯株式会社 | Porous porous body and method for producing the same |
-
2005
- 2005-05-24 JP JP2005151695A patent/JP4599592B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000176276A (en) * | 1998-12-18 | 2000-06-27 | Agency Of Ind Science & Technol | Gas adsorbing and desorbing material and its production |
| JP2000189744A (en) * | 1999-01-05 | 2000-07-11 | Agency Of Ind Science & Technol | Production of moisture regulating material |
| JP2001170500A (en) * | 1999-01-12 | 2001-06-26 | Toyota Central Res & Dev Lab Inc | Porous body, method of producing the same and exhaust gas purification catalyst using the porous body |
| JP2002004193A (en) * | 2000-06-15 | 2002-01-09 | Ykk Corp | Conditioning paper and method for producing the same |
| JP2004010423A (en) * | 2002-06-06 | 2004-01-15 | Matsushita Electric Ind Co Ltd | Solid heat insulating material and its manufacturing method |
| JP2004345890A (en) * | 2003-05-21 | 2004-12-09 | Toyota Motor Corp | Porous composite oxide and its production method |
| WO2004113251A1 (en) * | 2003-06-20 | 2004-12-29 | Matsushita Electric Industrial Co., Ltd. | Porous body and method for producing same |
| JP2005081495A (en) * | 2003-09-09 | 2005-03-31 | Makio Naito | Porous body coated particle, precursor for heat insulating material containing the porous body coated particle and heat insulating material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015056285A1 (en) | 2013-10-15 | 2015-04-23 | 株式会社Ｎａｔｏｍｉｃｓ | Method of preserving heat exchange surface and method of cooling moist air |
| KR20160070134A (en) | 2013-10-15 | 2016-06-17 | 가부시키가이샤 나토믹스 | Method of preserving heat exchange surface and method of cooling moist air |
| US10371466B2 (en) | 2013-10-15 | 2019-08-06 | Natomics Co., Ltd. | Method of preserving heat exchange surface and method of cooling moist air |
| JP2016194406A (en) * | 2016-05-17 | 2016-11-17 | 株式会社Ｎａｔｏｍｉｃｓ | Carrier for suppressing frost formation or defrosting, and heat exchanger having carrier |
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