JPH08198977A - Water-absorbing porous sheet - Google Patents
Water-absorbing porous sheetInfo
- Publication number
- JPH08198977A JPH08198977A JP7008853A JP885395A JPH08198977A JP H08198977 A JPH08198977 A JP H08198977A JP 7008853 A JP7008853 A JP 7008853A JP 885395 A JP885395 A JP 885395A JP H08198977 A JPH08198977 A JP H08198977A
- Authority
- JP
- Japan
- Prior art keywords
- water
- porous sheet
- sheet
- adsorbent
- absorbing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、吸水性、力学的特性に
優れている上に、特に大気からの悪臭の吸着が少ないこ
とにより、臭気発生が少なく、調湿板、加湿器の保水
材、水蒸散板、結露防止板等として好適に利用できる吸
水性多孔シートに関するものである。INDUSTRIAL APPLICABILITY The present invention is excellent in water absorption and mechanical properties and, in particular, has a small amount of bad odors adsorbed from the atmosphere, so that a small amount of odor is generated and a moisture retaining material for humidity control plates and humidifiers. The present invention relates to a water-absorbing porous sheet that can be suitably used as a water evaporation plate, a condensation preventing plate, and the like.
【０００２】[0002]
【従来の技術】従来、調湿板、加湿器の保水材、水蒸散
板、結露防止板等としては、ポリエステル繊維等の有機
合成繊維あるいはガラス繊維等の無機繊維よりなる基材
に、シリカゲル、アルミナゲル、あるいは珪酸系、アル
ミナ系等の活性土壌等の吸着剤を付着して一体化させ、
親水性を高めた多孔性シートが用いられている。例え
ば、特開平１−２８３１２９号公報には、繊維とバイン
ダー樹脂とから得られる複合シートに特定の微粒子を添
着することによって得られる親水性、力学的特性に優れ
た多孔性複合シート及びその製造法が開示されている。2. Description of the Related Art Conventionally, as a humidity control plate, a water retaining material for a humidifier, a water evaporation plate, a condensation prevention plate, etc., silica gel is used as a base material made of organic synthetic fibers such as polyester fibers or inorganic fibers such as glass fibers. Alumina gel or adsorbent such as silicic acid-based or alumina-based activated soil is attached and integrated,
A porous sheet with increased hydrophilicity is used. For example, in JP-A-1-283129, a porous composite sheet excellent in hydrophilicity and mechanical properties obtained by attaching specific fine particles to a composite sheet obtained from fibers and a binder resin, and a method for producing the same Is disclosed.
【０００３】しかしながら、上記のような広く普及して
いる多孔性シートは、基材により形体保持をさせ、吸着
剤により吸水性を保有させているものであり、付着する
臭気物質にまで着目して、吸着剤の付着量を考慮したも
のはなかった。さらには、最近では調湿板、加湿器の保
水材、水蒸散板、結露防止板等から発生する臭いが問題
とされ、その原因は吸着剤の付着量に起因するものと考
えられる。本発明者らは、調湿板、加湿器の保水材、水
蒸散板、結露防止板等における悪臭のメカニズムを以下
のごとく考察している。However, the widely used porous sheet as described above has a shape held by a base material and water absorption by an adsorbent, and attention is paid to odorous substances attached thereto. There was no consideration of the amount of adsorbent attached. Furthermore, recently, the odor generated from the humidity control plate, the water retaining material of the humidifier, the water evaporation plate, the dew condensation prevention plate, etc. has become a problem, and the cause thereof is considered to be due to the adhering amount of the adsorbent. The present inventors have considered the mechanism of bad odor in the humidity control plate, the water retaining material of the humidifier, the water evaporation plate, the dew condensation prevention plate, etc. as follows.
【０００４】すなわち、調湿板、加湿器の保水材、水蒸
散板、結露防止板等の吸水性多孔シートに用いられてい
る吸着剤としてはシリカゲル、アルミナゲル、あるいは
珪酸系またはアルミナ系等の活性土壌等であり、これら
は、いずれも比表面積の高い多孔質物質で、表面は水酸
基等の活性基で覆われている。これに水が水素結合によ
り強い親和力で吸着する。一方、例えば煙草臭、トイレ
タリー臭等の悪臭物質は比較的弱いファンデルワールス
力により吸着する。しかるに大気中の悪臭成分を取り込
んだ多孔性シートに水が供給されると水の方が悪臭物質
よりも親和性が強いため、悪臭物質が多孔性シートから
脱着してしまい、雰囲気下に悪臭が飛散して不快に感ず
るようになる。That is, as the adsorbent used for the water-absorbing porous sheet such as the humidity control plate, the water retaining material of the humidifier, the water evaporation plate, the dew condensation preventing plate, silica gel, alumina gel, silicic acid type or alumina type etc. Activated soil and the like, all of which are porous substances having a high specific surface area, the surface of which is covered with active groups such as hydroxyl groups. Water is adsorbed to this with a strong affinity by hydrogen bonding. On the other hand, malodorous substances such as cigarette odor and toiletry odor are adsorbed by a relatively weak Van der Waals force. However, when water is supplied to the porous sheet that has taken in the malodorous components in the air, water has a stronger affinity than the malodorous substance, so the malodorous substance is desorbed from the porous sheet, and the malodorous substance is generated in the atmosphere. Scatter and start to feel uncomfortable.
【０００５】[0005]
【発明が解決しようとする課題】そこで、本発明の課題
は、吸水性、力学的特性に優れている上に、特に大気か
らの悪臭の吸着が少なく、臭気発生の問題を解決するこ
とができて、調湿板、加湿器の保水材、水蒸散板、結露
防止板等として好適に利用できる吸水性多孔シートの提
供にある。SUMMARY OF THE INVENTION The object of the present invention is to solve the problem of odor generation because it is excellent in water absorption and mechanical properties and, in particular, it absorbs less bad odors from the atmosphere. Thus, the present invention provides a water-absorbing porous sheet that can be suitably used as a humidity control plate, a water retaining material for a humidifier, a water evaporation plate, a dew condensation preventing plate, and the like.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、このよう
な課題を解決するめに鋭意研究の結果、吸水性多孔シー
トの吸水性を持たせている吸着剤の付着量を比表面積
（ｍ2 ／ｇ）と付着量（ｇ／ｍ3 ）の積が２．５×１０
6 （ｍ2 ／ｍ3 ）以下となるように調節することによ
り、上記問題を解決することができるという事実を見出
し、本発明に到達した。Means for Solving the Problems As a result of intensive research aimed at solving such problems, the present inventors have found that the amount of adsorbent adhering to the water-absorbing porous sheet has a specific surface area (m). The product of 2 / g) and the adhered amount (g / m 3 ) is 2.5 × 10.
The present invention has been accomplished by finding the fact that the above problems can be solved by adjusting the amount to be 6 (m 2 / m 3 ) or less.
【０００７】すなわち、本発明の要旨は、多孔性基材に
吸着剤が付着してなる吸水性多孔シートであって、この
吸水性多孔シートの一方の面から他の面に貫通する連続
気孔を有していて、さらに気孔率が４０〜９０％、吸水
率が４０％以上、水滴吸収性が３秒以内、曲げ強度が３
０ｋｇ／ｃｍ2 以上であり、吸着剤の付着量は吸着剤の
比表面積（ｍ2 ／ｇ）と付着量（ｇ／ｍ3 ）との積が
２．５×１０6 （ｍ2 ／ｍ3 ）以下であることを特徴と
する吸水性多孔シートである。That is, the gist of the present invention is a water-absorbing porous sheet having an adsorbent adhered to a porous substrate, wherein continuous pores penetrating from one surface of this water-absorbing porous sheet to the other surface are formed. It has a porosity of 40 to 90%, a water absorption rate of 40% or more, a water drop absorbency within 3 seconds, and a bending strength of 3
0 kg / cm 2 or more, the deposition amount of the adsorbent specific surface area of the adsorbent (m 2 / g) and coating weight (g / m 3) product of the 2.5 × 10 6 (m 2 / m 3 ) It is a water-absorbing porous sheet characterized by the following.
【０００８】以下、本発明を詳細に説明する。本発明の
吸水性多孔シートとは、調湿板、加湿器の保水材、水蒸
散板、結露防止板等に使用される吸水媒体のことであ
り、吸水性多孔シートは、外部からの水の供給や大気中
の水蒸気等の接触により水を保持し、自然放置や熱風の
供給により気化するという、乾湿が繰り返し行えるもの
である。The present invention will be described in detail below. The water-absorbent porous sheet of the present invention is a humidity control plate, a water-retaining material for a humidifier, a water evaporation plate, a water-absorption medium used for a dew condensation preventing plate, etc. Water can be retained by supply or contact with water vapor in the atmosphere, and can be left to stand or vaporized by supplying hot air.
【０００９】また、本発明の吸水性多孔シートは、一方
の面から他の面に貫通する多数の連続気孔を有してお
り、また、気孔率が４０〜９０％である。気孔率が４０
％未満であると、十分な吸水量を得ることができない。
また、気孔率が９０％以上であるとシートの腰がなくな
り、曲げ強度等の十分な力学的特性が得られない。本発
明における気孔率は全容積に対する非貫通性あるいは貫
通性の気孔の容積比率を百分率で表したものであり、か
かる気孔率は具体的には次のようにして測定される。す
なわち、まずシートの乾燥重量Ｗ（ｇ）と体積Ｖ（ｃｍ
3 ）を測定する。次にシートを粉末状にしてシートの真
密度ρ（ｇ／ｃｍ3 ）を測定し、気孔率を次式により算
出する。The water-absorbent porous sheet of the present invention has a large number of continuous pores penetrating from one surface to the other surface and has a porosity of 40 to 90%. Porosity is 40
If it is less than%, a sufficient amount of water absorption cannot be obtained.
Further, if the porosity is 90% or more, the rigidity of the sheet is lost and sufficient mechanical properties such as bending strength cannot be obtained. The porosity in the present invention represents the volume ratio of non-penetrating or penetrating pores with respect to the total volume as a percentage, and the porosity is specifically measured as follows. That is, first, the dry weight W (g) of the sheet and the volume V (cm
3 ) Measure. Next, the sheet is made into a powder and the true density ρ (g / cm 3 ) of the sheet is measured, and the porosity is calculated by the following formula.
【００１０】[0010]
【数１】 [Equation 1]
【００１１】また、本発明の吸水性多孔シートは、構成
素材の間隙に形成された通常の非貫通性の気孔を多数に
含有するが、それ以外にシートの一方の面から他方の面
に貫通する連続気孔も多数有する。かかる連続気孔はシ
ートを構成する繊維の空隙をぬって折れ曲がり、一方の
面から他方の面に貫通しているもの、一方の面から他方
の面に直線的に貫通しているもの等多様な形態のものが
挙げられる。本発明において連続気孔の存在の有無は便
宜上次のようにして判断する。まずシートから直径１０
ｍｍの円板を切り抜き、この円板に１Ｎｌ／ｍｉｎの割
合で空気を流した場合に圧力損失が１０００ｍｍＨ2 Ｏ
／ｍｍ以下の場合に連続気孔を有すると判断する。但
し、圧力損失の単位：ｍｍＨ2 Ｏ／ｍｍの分母のｍｍは
シートの厚さである。上記圧力損失はシートの貫通性の
程度を表すものである。本発明のシートにおいては、特
に上記圧力損失が５００ｍｍＨ2 Ｏ／ｍｍ以下であるこ
とが好ましい。Further, the water-absorbing porous sheet of the present invention contains a large number of ordinary non-penetrating pores formed in the gaps of the constituent materials, but in addition to that, it penetrates from one surface of the sheet to the other surface. It also has a large number of continuous pores. Such continuous pores have various forms such as bending through the voids of the fibers constituting the sheet, penetrating from one surface to the other surface, linearly penetrating from one surface to the other surface, etc. The following are listed. In the present invention, the presence or absence of continuous pores is determined as follows for convenience. First from the sheet, the diameter 10
mm disk was cut out and the pressure loss was 1000 mmH 2 O when air was flown through this disk at a rate of 1 Nl / min.
If it is less than or equal to / mm, it is determined to have continuous pores. However, mm in the denominator of the unit of pressure loss: mmH 2 O / mm is the thickness of the sheet. The pressure loss indicates the degree of sheet penetrability. In the sheet of the present invention, the pressure loss is preferably 500 mmH 2 O / mm or less.
【００１２】また、本発明の吸水性多孔シートは、その
用途が調湿板、加湿器の保水材、水蒸散板、結露防止板
等であるため、吸水率が４０％以上であり、水滴吸収性
が３秒以内、曲げ強度が３０ｋｇ／ｃｍ2 以上でなくて
はならない。吸水率が４０％未満では水の保持量が少な
すぎて問題であり、水滴吸収性が３秒を超えるようでは
水の吸水力が劣り問題であり、曲げ強度が３０ｋｇ／ｃ
ｍ2 未満では吸水性多孔シートの形態維持性に問題が生
じる。さらに、吸水率の好ましい範囲は６０〜９０％で
あり、より好ましくは６５〜８０％である。曲げ強度は
３０ｋ／ｃｍ2以上必要であり、強度は高いほど良い。Further, since the water-absorbing porous sheet of the present invention is used as a humidity control plate, a water retaining material for a humidifier, a water evaporation plate, a dew condensation preventing plate, etc., it has a water absorption rate of 40% or more and absorbs water droplets. The property must be within 3 seconds and the bending strength must be 30 kg / cm 2 or more. If the water absorption rate is less than 40%, the amount of retained water is too small, which is a problem. If the water drop absorption exceeds 3 seconds, the water absorption capacity is poor, and the bending strength is 30 kg / c.
If it is less than m 2 , there is a problem in the shape retention of the water absorbent porous sheet. Furthermore, the preferable range of the water absorption is 60 to 90%, and more preferably 65 to 80%. Bending strength is required to be 30 k / cm 2 or more, and the higher the strength, the better.
【００１３】本発明の吸水性多孔シートは多孔性基材に
吸着剤が付着してなるものであって、多孔性基材として
は、従来公知の有機繊維、無機繊維あるいは有機繊維と
無機繊維との複合繊維を主材として構成されている。有
機合成繊維としては、ポリエステル繊維、ポリアミド繊
維、ポリオレフィン繊維等が挙げられ、中でもポリエス
テル繊維が好ましく用いられる。無機繊維としては、ガ
ラス繊維等が挙げられる。これらの形態は長繊維または
短繊維からなる不織布、織物、編み物等シート状であれ
ばいずれの形態でもよい。また、前記繊維体の繊維密
度、繊維径すなわち繊度は特に限定することなく、いず
れのものでもよい。The water-absorbent porous sheet of the present invention comprises an adsorbent adhered to a porous substrate, and as the porous substrate, there are known organic fibers, inorganic fibers or organic fibers and inorganic fibers. The main material is the composite fiber. Examples of the organic synthetic fiber include polyester fiber, polyamide fiber, polyolefin fiber and the like, and among them, polyester fiber is preferably used. Examples of the inorganic fiber include glass fiber and the like. Any of these forms may be used as long as it is a non-woven fabric made of long fibers or short fibers, a woven fabric, a knitted fabric, or the like. The fiber density, fiber diameter, or fineness of the fibrous body is not particularly limited and may be any one.
【００１４】本発明における多孔性基材は、特にシート
の剛性、耐久性等を重視する用途の場合には、シートを
強化するための強化用の樹脂として、熱硬化性樹脂や熱
可塑性樹脂を使用することが好ましい。熱硬化性樹脂と
しては、フェノール樹脂、メラミン樹脂、ユリア樹脂等
が挙げられ、特に、１５０℃以下の温度で熱流動性を示
すフェノール樹脂が挙げられ、かかる熱流動性のフェノ
ール樹脂とはＪＩＳ−Ｋ−６９１１〔成形材料（円板式
流れ）〕に基づく伸びが３〜１５ｃｍのものをいう。熱
流動性を有するフェノール樹脂の使用形態は粉粒体状で
あるものが好ましく、かかるフェノール樹脂としてはフ
ェノール類とアルデヒド類とを反応させて得られる熱硬
化性のフェノール・アルデヒド樹脂、フェノール類とア
ルデヒド類と含窒素化合物とを反応させて得られる熱硬
化性の含窒素フェノール・アルデヒド樹脂等が挙げられ
る。また、熱可塑性樹脂としては、ポリエチレン樹脂、
ポリスチレン樹脂、ポリ塩化ビニル樹脂、ポリアミド樹
脂等が挙げられる。The porous base material in the present invention is a thermosetting resin or a thermoplastic resin as a reinforcing resin for strengthening the sheet, particularly in applications where importance is attached to the rigidity and durability of the sheet. Preference is given to using. Examples of the thermosetting resin include a phenol resin, a melamine resin, a urea resin, and the like. In particular, a phenol resin that exhibits heat fluidity at a temperature of 150 ° C. or lower is included, and such a heat fluid phenol resin is JIS- Elongation based on K-6911 [molding material (disc flow)] is 3 to 15 cm. The use form of the phenol resin having heat fluidity is preferably in the form of powder or granules. As such a phenol resin, a thermosetting phenol / aldehyde resin obtained by reacting phenols and aldehydes, and phenols are used. Examples thereof include thermosetting nitrogen-containing phenol / aldehyde resins obtained by reacting aldehydes with a nitrogen-containing compound. Further, as the thermoplastic resin, polyethylene resin,
Examples thereof include polystyrene resin, polyvinyl chloride resin, and polyamide resin.
【００１５】本発明に用いられる吸着剤としてはシリカ
ゲル、アルミナゲル、あるいは珪酸系またはアルミナ系
等の活性土壌等が挙げられ、８〜２０Åのミクロポア、
２０〜５００Åのメソポア、５００Å以上であるマクロ
ポアを有する多孔性物質であり、かつ、吸着性に優れる
ものである。これらは天然品、人工品のどちらであって
もよい。シリカゲルとは珪酸のゲルでＳｉＯ2 ・ｎＨ2
Ｏ（ｎは水和物量を示す。）の構造式で示される。アル
ミナゲルとは酸化アルミニウムのゲルでＡｌ2 Ｏ3 ・ｎ
Ｈ2 Ｏ（ｎは水和物量を示す。）の構造式で示される。
珪酸系、アルミナ系等の活性土壌としては一般的に粘土
鉱物とされるものであり、珪素、アルミニウム、カリウ
ム、ナトリウム、マグネシウム、カルシウム等で構成さ
れ、水和物を含み、主成分として酸化珪素を含む物質
で、例えばアロフェン、カオリナイト、モンモリロナイ
ト、ハロイサイト、セピオライト、パリゴルスカイト、
ベーマイト等が挙げられ、天然に産出される天然品の
他、合成ゼオライト等のように人工品であるものも含ま
れる。Examples of adsorbents used in the present invention include silica gel, alumina gel, silicic acid-based or alumina-based activated soil, and the like. Micropores of 8 to 20 Å,
It is a porous substance having mesopores of 20 to 500 Å and macropores of 500 Å or more, and is excellent in adsorptivity. These may be natural products or artificial products. Silica gel is a silica gel, SiO 2 · nH 2
It is represented by the structural formula of O (n represents the amount of hydrate). Alumina gel is a gel of aluminum oxide, Al 2 O 3 · n
It is represented by the structural formula of H 2 O (n represents the amount of hydrate).
Clay minerals, such as silicic acid-based and alumina-based active soils, are generally made of clay minerals, and are composed of silicon, aluminum, potassium, sodium, magnesium, calcium, etc., containing hydrates, and silicon oxide as the main component. A substance containing, for example, allophane, kaolinite, montmorillonite, halloysite, sepiolite, palygorskite,
Examples thereof include boehmite and the like, and include natural products produced naturally and artificial products such as synthetic zeolite.
【００１６】また、これら吸着剤の形状は球状、多面体
状等で特に限定されない。形態も破砕品、成形品、球状
品等特に限定されない。さらに、粒径としては１００μ
ｍ以下のもの、好ましくは５μｍ以下のもの、さらに好
ましくは０．５μｍ以下のものを用いる。粒径が１００
μｍより大きいと、吸着剤が多孔性基材表面（孔内も含
む）に均一に付着することができない。すなわち、吸着
剤が基材表面に点在することとなり、しかる場合には、
多孔性基材に吸水しない部分が生じる。これを確認する
には例えば次のようにして確認できる。The shape of these adsorbents is not particularly limited and may be spherical, polyhedral or the like. The form is also not particularly limited, such as a crushed product, a molded product, and a spherical product. Furthermore, the particle size is 100μ
m or less, preferably 5 μm or less, and more preferably 0.5 μm or less. Particle size is 100
If it is larger than μm, the adsorbent cannot uniformly adhere to the surface of the porous substrate (including the inside of the pores). That is, the adsorbent is scattered on the surface of the base material, and in that case,
A part which does not absorb water is generated in the porous substrate. This can be confirmed, for example, as follows.
【００１７】すなわち、吸水性多孔シート上の１０箇所
を適当に選び、１００ｍｍ上方から水を０．５μｌ滴下
し、水が完全に吸水するまでの時間を測定し、これを水
滴吸収性とし、１０箇所の水滴吸収性の最小値と最大値
の差が５秒以上をもってシートに吸水しない部分がある
と判断する方法、あるいは、吸水性多孔シート表面にカ
ーボンを厚さ１０ｎｍ程度となるように真空蒸着させ、
日本電子社製ＪＸＡ−８６２１形ＷＤ／ＥＤコンバイン
マイクロアナライザ−にて珪素元素あるいはアルミニウ
ム元素の面分析（元素マッピング）を実施すれば、繊維
表面に珪素あるいはアルミニウムの付着状態、すなわち
吸着剤の付着状態が確認され、繊維表面で珪素あるいは
アルミニウムが検出されない部分があれば付着ムラがあ
り、シート全体に吸着剤が行き渡っていないと判断する
方法等である。That is, 10 points on the water-absorbent porous sheet were appropriately selected, 0.5 μl of water was dropped from 100 mm above, and the time until the water completely absorbed water was measured. A method of determining that there is a part that does not absorb water in the sheet when the difference between the minimum value and the maximum value of the water drop absorbability of a portion is 5 seconds or more, or vacuum deposition of carbon on the surface of the water absorbent porous sheet to a thickness of about 10 nm Let
If the surface analysis (elemental mapping) of silicon element or aluminum element is performed by JEOL JXA-8621 WD / ED combine microanalyzer, the adhered state of silicon or aluminum on the fiber surface, that is, the adsorbed state of adsorbent If there is a portion where silicon or aluminum is not detected on the fiber surface, there is uneven adhesion and it is judged that the adsorbent has not spread all over the sheet.
【００１８】吸着剤の付着量としては、吸着剤の比表面
積（ｍ2 ／ｇ）と付着量（ｇ／ｍ３）の積が２．５×１
０６ （ｍ2 ／ｍ3 ）以下となるように調節する。この
際１．１×１０6 （ｍ2 ／ｍ3 ）以下が好ましく、さら
に好ましくは０．３５×１０6（ｍ2 ／ｍ3 ）以下、よ
りさらに好ましくは０．１８×１０6 （ｍ2 ／ｍ3 ）以
下である。比表面積と付着量の積が２．５×１０6 （ｍ
2 ／ｍ3 ）より大きくなると臭気物質の取り込み量が多
くなり、目的とする吸水性多孔シートの臭気の抑制がな
されない。吸着剤の比表面積は特に制限されるものでな
く、上述の吸着剤の比表面積と付着量の積が２．５×１
０6 （ｍ2 ／ｍ3 ）以下を満足する値であればよい。比
表面積と付着量の積があまり小さい場合には付着量が少
なくなって水の取り込み量が少なくなるので、付着量は
少なくとも０．１×１０3 （ｇ／ｃｍ3 ）であることが
好ましい。The amount of adsorbent adhered is 2.5 × 1 as the product of the specific surface area (m 2 / g) and the amount (g / m 3 ) of adsorbent.
Adjust so that it is not more than 0 6 (m 2 / m 3 ). At this time, it is preferably 1.1 × 10 6 (m 2 / m 3 ) or less, more preferably 0.35 × 10 6 (m 2 / m 3 ) or less, still more preferably 0.18 × 10 6 (m 2). / M 3 ) or less. The product of the specific surface area and the adhesion amount is 2.5 × 10 6 (m
When it is larger than 2 / m 3 ), the amount of the odorous substance taken in increases, and the desired odor of the water-absorbing porous sheet is not suppressed. The specific surface area of the adsorbent is not particularly limited, and the product of the specific surface area of the adsorbent and the adhesion amount is 2.5 × 1.
Any value that satisfies 0 6 (m 2 / m 3 ) or less may be used. When the product of the specific surface area and the adhesion amount is too small, the adhesion amount decreases and the amount of water taken in decreases, so the adhesion amount is preferably at least 0.1 × 10 3 (g / cm 3 ).
【００１９】本発明の吸水性多孔シートを製造する方法
としては、有機繊維及び／又は無機繊維と吸着剤を一括
して乾式あるいは湿式にて抄造する方法、あるいは、あ
らかじめ有機繊維及び／又は無機繊維と強化用の樹脂か
ら多孔性基材を作製しておいて、これに吸着剤を含浸あ
るいはコーティングする方法等があげられる。以上のよ
うにして、臭気発生が少なく、吸水性、力学的特性に優
れた吸水性多孔シートを得ることができる。The method for producing the water-absorbing porous sheet of the present invention includes a method in which the organic fiber and / or the inorganic fiber and the adsorbent are batch-processed in a dry or wet manner, or the organic fiber and / or the inorganic fiber is previously prepared. And a method of impregnating or coating an adsorbent on a porous base material prepared from a reinforcing resin. As described above, it is possible to obtain a water-absorbing porous sheet that has little odor generation and is excellent in water absorption and mechanical properties.
【００２０】なお、本発明における特性値は次のように
して求めた。 （１）吸水率：吸水性多孔シートの乾燥重量Ｗ1 （ｇ）
を測定し、次に、シートを水に十分に浸漬した後、水中
から引き上げて雫を切り、濡れた状態における重量Ｗ2
（ｇ）を測定し、次式により求めた。The characteristic values in the present invention were obtained as follows. (1) Water absorption rate: Dry weight W 1 (g) of the water absorbent porous sheet
Then, after the sheet is sufficiently immersed in water, the sheet is pulled up from the water to remove the drops, and the weight W 2 in a wet state is measured.
(G) was measured and determined by the following formula.
【００２１】[0021]
【数２】 [Equation 2]
【００２２】（２）水滴吸収性：シートの吸水所要時間
を表す値であり、具体的にはマイクロピペットで水５０
μｌを計り取り、１００ｍｍ上方からシートに水を滴下
させて、水がシートに完全に吸収されるのに要する時間
を測定し、この操作をシートの１０点について実施し、
この平均値をいう。この値が小さい程吸水性が良好であ
る。 （３）曲げ強度：ＪＩＳ−Ｋ−７２０３〔硬質プラスチ
ックの曲げ試験方法〕に基づいて測定した。(2) Water drop absorbency: A value showing the time required for water absorption of the sheet, and specifically, it is 50
We measured μl and dropped water onto the sheet from above 100 mm to measure the time required for the water to be completely absorbed by the sheet. This operation was carried out for 10 points of the sheet,
This is the average value. The smaller this value, the better the water absorption. (3) Bending strength: measured according to JIS-K-7203 [bending test method for hard plastics].
【００２３】[0023]
【実施例】以下実施例により本発明を具体的に説明す
る。なお、臭気の評価は次のようにして行った。 臭気の評価：３００ｍ3 の室内中で１日約１００本の喫
煙を実施し、吸水性多孔シートの暴露放置を７日間行っ
た。その後、悪臭の全く感じられない空間に置いてシー
ト上に水約１ｍｌを滴下し、水滴下部から発せられる臭
気を臭覚に障害のない１０人をモニターに選び官能検査
を実施した。官能検査の判定基準は、１；臭いを感じな
い、２；やや臭う、３；臭う、４；臭いがきつい、５；
極めて臭いがきつい、として１０人の平均値をとった。
この評価結果は評価２以下であると概ね使用するにさし
つかえない数値である。The present invention will be described in detail with reference to the following examples. The odor was evaluated as follows. Odor evaluation: About 100 cigarettes were smoked in a room of 300 m 3 per day, and the water-absorbent porous sheet was left exposed for 7 days. Then, about 1 ml of water was dropped on the sheet in a space where no bad odor was felt, and 10 people with no odor sensation were selected as the odors emitted from the water dropping part for sensory tests. The sensory test criteria are: 1; no odor, 2; slightly odor, 3; odor, 4; odor is strong, 5;
It was extremely odorous, and the average value of 10 people was taken.
This evaluation result is a numerical value that can be generally used when the evaluation is 2 or less.
【００２４】実施例１ 繊度１０デニール、繊維長５１ｍｍのポリエチレンテレ
フタレート短繊維８０重量部、繊度４デニール、繊維長
５１ｍｍのポリエチレンテレフタレート／イソフタレー
ト共重合体短繊維２０重量部からなる混繊不織布（目付
７００ｇ／ｍ2）を、加熱プレス成形機にて１８０℃、
１ｋｇ／ｃｍ2 で５分間加熱加圧し、厚さ２ｍｍの部分
融着した短繊維不織布２０×２０ｃｍ2 （シートＡ）を
調製した。他方、粒径０．１μｍ、比表面積２５０ｍ2
／ｇのシリカゲル微粒子２００ｇを水１リットル中に分
散させて分散液Ａを調製し、これをシートＡに含浸し
て、絞りローラで分散液Ａを絞った後、６０℃乾燥機中
で１２時間乾燥して、吸水性多孔シートＡを得た。この
吸水性多孔シートＡのシリカゲルの付着量は１．５×１
０3 ｇ／ｍ3 であった。Example 1 80 parts by weight of polyethylene terephthalate short fibers having a fineness of 10 denier and a fiber length of 51 mm, and 20 parts by weight of polyethylene terephthalate / isophthalate copolymer short fibers having a fineness of 4 denier and a fiber length of 51 mm were used as a mixed fiber nonwoven fabric. 700 g / m 2 ) at 180 ° C. with a hot press molding machine,
It was heated and pressed at 1 kg / cm 2 for 5 minutes to prepare a partially fused short fiber nonwoven fabric 20 × 20 cm 2 (sheet A) having a thickness of 2 mm. On the other hand, particle size 0.1 μm, specific surface area 250 m 2
/ G of silica gel fine particles is dispersed in 1 liter of water to prepare a dispersion liquid A, which is impregnated in a sheet A, and the dispersion liquid A is squeezed with a squeezing roller, and then in a dryer at 60 ° C for 12 hours. After drying, a water absorbent porous sheet A was obtained. The amount of silica gel attached to the water absorbent porous sheet A is 1.5 × 1.
It was 0 3 g / m 3 .
【００２５】実施例２ 繊度１０デニール、繊維長５１ｍｍのポリエチレンテレ
フタレート短繊維よりなる不織布（目付５００ｇ／
ｍ2 ）２０×２０ｃｍ2 に、フェノール樹脂（ユニチカ
社製ユニベックス樹脂ＵＡ−３０、平均粒径２５μｍ、
熱流動性５０ｍｍ）の水分散液（２００ｇ／ｌ）を含浸
し、絞りローラでこの分散液を絞った後、１００℃で２
０分間乾燥し、未硬化のフェノール樹脂が付着している
ポリエチレンテレフタレート不織布を得た。この際のフ
ェノール樹脂の付着量は４０重量％であった。これを１
８０℃に余熱したプレス成形機を用いて１ｋｇ／ｃｍ2
で５分間加熱加圧して、フェノール樹脂を硬化させて厚
さ２ｍｍのシートＢを得た。さらに、シートＢに実施例
１で調製した分散液Ａを含浸し、絞りローラで分散液Ａ
を絞った後、６０℃乾燥機中で１２時間乾燥し吸水性多
孔シートＢを得た。この吸水性多孔シートＢのシリカゲ
ルの付着量は１．５×１０3 ｇ／ｍ3 であった。Example 2 A non-woven fabric made of polyethylene terephthalate short fibers having a fineness of 10 denier and a fiber length of 51 mm (Basis weight: 500 g /
in m 2) 20 × 20cm 2, phenol resin (manufactured by Unitika Ltd. Yunibekkusu resin UA-30, average particle size 25 [mu] m,
It is impregnated with a water dispersion (200 g / l) having a heat fluidity of 50 mm, squeezed the dispersion with a squeezing roller, and then at 100 ° C. for 2 hours.
After drying for 0 minutes, a polyethylene terephthalate nonwoven fabric having an uncured phenol resin attached thereto was obtained. At this time, the amount of the phenol resin attached was 40% by weight. This one
1 kg / cm 2 using a press molding machine preheated to 80 ° C
Was heated and pressed for 5 minutes to harden the phenolic resin to obtain a sheet B having a thickness of 2 mm. Further, the sheet B was impregnated with the dispersion A prepared in Example 1, and the dispersion A was squeezed with a squeezing roller.
Was squeezed, and then dried in a dryer at 60 ° C. for 12 hours to obtain a water-absorbent porous sheet B. The amount of silica gel attached to the water absorbent porous sheet B was 1.5 × 10 3 g / m 3 .
【００２６】実施例３ 実施例２と同様にしてシリカゲルの付着量が５×１０3
ｇ／ｍ3 である吸水性多孔シートＣを得た。Example 3 As in Example 2, the amount of silica gel adhered was 5 × 10 3.
A water-absorbent porous sheet C having g / m 3 was obtained.
【００２７】実施例４ 実施例２と同様にしてシリカゲルの付着量が０．６５×
１０3 ｇ／ｍ3 である吸水性多孔シートＤを得た。Example 4 As in Example 2, the amount of silica gel adhered was 0.65 ×.
A water-absorbent porous sheet D having a weight of 10 3 g / m 3 was obtained.
【００２８】実施例５ 実施例２で得たシートＢに粒径０．２μｍ、比表面積２
４０ｍ2 ／ｇのアルミナ微粒子を水中に分散させた分散
液Ｂ（２００ｇ／ｌ）を含浸し、絞りローラで分散液Ｂ
を絞った後、６０℃乾燥機中で１２時間乾燥した。この
際のアルミナのシートＢへの付着量は１．５×１０3 ｇ
／ｍ3 であった。こうして吸水性多孔シートＥを得た。Example 5 The sheet B obtained in Example 2 has a particle size of 0.2 μm and a specific surface area of 2
Disperse liquid B (200 g / l) in which 40 m 2 / g of alumina fine particles are dispersed in water and impregnate it with a squeezing roller.
Was squeezed and dried in a dryer at 60 ° C. for 12 hours. At this time, the amount of alumina adhered to the sheet B was 1.5 × 10 3 g
/ M 3 . Thus, a water absorbent porous sheet E was obtained.
【００２９】実施例６ 実施例２で得たシートＢに粒径０．０５μｍ、比表面積
２５０ｍ2 ／ｇのシリカゲル微粒子を水中に分散させた
分散液Ｃ（２００ｇ／ｌ）を含浸し、絞りローラで分散
液Ｃを絞った後、６０℃乾燥機中で１２時間乾燥して、
吸水性多孔シートＦを得た。この吸水性多孔シートＦの
シリカゲルの付着量は０．２５×１０3ｇ／ｍ3 であっ
た。Example 6 The sheet B obtained in Example 2 was impregnated with a dispersion C (200 g / l) prepared by dispersing silica gel fine particles having a particle size of 0.05 μm and a specific surface area of 250 m 2 / g in water, and squeezing rollers. After squeezing the dispersion C with, dried in a dryer at 60 ° C. for 12 hours,
A water absorbent porous sheet F was obtained. The amount of silica gel attached to the water absorbent porous sheet F was 0.25 × 10 3 g / m 3 .
【００３０】実施例７ 実施例２で得たシートＢに粒径１０μｍ、比表面積２５
ｍ2 ／ｇのカオリナイト微粒子を水中に分散させた分散
液Ｄ（２００ｇ／ｌ）を含浸し、絞りローラで分散液Ｄ
を絞った後、６０℃乾燥機中で１２時間乾燥して吸水性
多孔シートＧを得た。この吸水性多孔シートＧのカオリ
ナイトの付着量は１５×１０3 ｇ／ｍ3であった。Example 7 The sheet B obtained in Example 2 has a particle size of 10 μm and a specific surface area of 25.
Disperse liquid D (200 g / l) in which m 2 / g of kaolinite particles are dispersed in water, and disperse liquid D with a squeezing roller.
Was squeezed and then dried in a dryer at 60 ° C. for 12 hours to obtain a water absorbent porous sheet G. The amount of kaolinite deposited on the water absorbent porous sheet G was 15 × 10 3 g / m 3 .
【００３１】実施例８ 実施例７と同様にしてカオリナイトの付着量が５０×１
０3 ｇ／ｍ3 である吸水性多孔シートＨを得た。Example 8 Similar to Example 7, the amount of kaolinite deposited was 50 × 1.
A water-absorbent porous sheet H having an amount of 0 3 g / m 3 was obtained.
【００３２】比較例１ 実施例２と同様にしてシリカゲルの付着量が１２．５×
１０3 ｇ／ｍ3 である吸水性多孔シートＩを得た。Comparative Example 1 As in Example 2, the amount of silica gel adhered was 12.5 ×.
A water-absorbent porous sheet I having a weight of 10 3 g / m 3 was obtained.
【００３３】比較例２ 実施例２で使用した未硬化のフェノール樹脂が付着した
ポリエチレンテレフタレート不織布を１８０℃に余熱し
たプレス成形機を用いて、１０ｋｇ／ｃｍ2 で５分間加
熱加圧して、フェノール樹脂を硬化させて厚さ０．８ｍ
ｍ、気孔率３５％のシートＪを得た。さらにはシートＪ
に分散液Ａを含浸し、絞りローラで分散液Ａを絞った
後、６０℃乾燥機中で１２時間乾燥した。この際のシリ
カゲルのシートＪへの付着量は１．５×１０3 ｇ／ｍ3
であった。こうして吸水性多孔シートＪを得た。Comparative Example 2 The polyethylene terephthalate nonwoven fabric to which the uncured phenol resin used in Example 2 was attached was heated and pressurized at 10 kg / cm 2 for 5 minutes using a press molding machine preheated to 180 ° C. Cured to a thickness of 0.8 m
A sheet J having m and porosity of 35% was obtained. Further sheet J
The dispersion A was impregnated in the above, the dispersion A was squeezed with a squeezing roller, and then dried in a dryer at 60 ° C. for 12 hours. At this time, the amount of silica gel adhered to the sheet J was 1.5 × 10 3 g / m 3
Met. Thus, a water absorbent porous sheet J was obtained.
【００３４】比較例３ 実施例２で使用した未硬化のフェノール樹脂が付着した
ポリエチレンテレフタレート不織布を１８０℃に余熱し
たプレス成形機を用いて、０．２ｋｇ／ｃｍ2で５分間
加熱加圧して、フェノール樹脂を硬化させて厚さ５．０
ｍｍ、気孔率９３％のシートＫを得た。さらにはシート
Ｋに分散液Ａを含浸し、絞りローラで分散液Ａを絞った
後、６０℃乾燥機中で１２時間乾燥して吸水性多孔シー
トＫを得た。この吸水性多孔シートＫのシリカゲルの付
着量は１．５×１０3 ｇ／ｍ3 であった。Comparative Example 3 The polyethylene terephthalate nonwoven fabric to which the uncured phenol resin used in Example 2 was attached was heated and pressurized at 0.2 kg / cm 2 for 5 minutes using a press molding machine preheated to 180 ° C. Phenolic resin is cured to a thickness of 5.0
A sheet K having a size of mm and a porosity of 93% was obtained. Further, the sheet K was impregnated with the dispersion liquid A, the dispersion liquid A was squeezed with a squeezing roller, and then dried in a dryer at 60 ° C. for 12 hours to obtain a water absorbent porous sheet K. The amount of silica gel attached to the water absorbent porous sheet K was 1.5 × 10 3 g / m 3 .
【００３５】比較例４ 実施例２で得たシートＢに粒径１２０μｍ、比表面積２
４０ｍ2 ／ｇのシリカゲル微粒子を水中に分散させた分
散液Ｅ（２００ｇ／ｌ）を含浸し、絞りローラで分散液
Ｅを絞った後、６０℃乾燥機中で１２時間乾燥した。こ
の際のシリカゲルのシートＢへの付着量は５×１０3 ｇ
／ｍ3 であった。こうして吸水性多孔シートＬを得た。Comparative Example 4 The sheet B obtained in Example 2 had a particle size of 120 μm and a specific surface area of 2
A dispersion E (200 g / l) in which 40 m 2 / g of silica gel particles were dispersed in water was impregnated, the dispersion E was squeezed with a squeezing roller, and then dried in a dryer at 60 ° C. for 12 hours. At this time, the amount of silica gel adhered to the sheet B is 5 × 10 3 g
/ M 3 . Thus, a water absorbent porous sheet L was obtained.
【００３６】比較例５ 比較例５と同様にして粒径１２０μｍ、比表面積２４０
ｍ2 ／ｇのシリカゲルの付着量が１５×１０3 ｇ／ｍ3
である吸水性多孔シートＭを得た。上記実施例１〜８及
び比較例１〜５にて得られた吸水性多孔シートＡ〜Ｍに
ついて吸水率、水滴吸収性、曲げ強度及び臭気を測定し
た。その結果を表１にまとめて示す。Comparative Example 5 As in Comparative Example 5, the particle size was 120 μm and the specific surface area was 240.
Adhesion amount of silica gel of m 2 / g is 15 × 10 3 g / m 3
A water-absorbent porous sheet M having With respect to the water-absorbing porous sheets A to M obtained in Examples 1 to 8 and Comparative Examples 1 to 5, the water absorption rate, water drop absorbency, bending strength and odor were measured. The results are summarized in Table 1.
【００３７】[0037]
【表１】 [Table 1]
【００３８】表１から明らかなように、粒径０．１μ
ｍ、比表面積２５０ｍ2 ／ｇのシリカゲルを吸着剤とし
た吸水性多孔シートＢ、Ｉに着目すると比表面積と付着
量の積が３．１３×１０6 ｍ2 ／ｍ3 である吸水性多孔
シートＩは水滴吸収性、曲げ強度においては優れるが、
臭気の点で問題がある。また、吸水性多孔シートＢと同
一のシリカゲルを使用した吸水性多孔シートＪにおいて
は気孔率が３５％であり、曲げ強度と臭気においては優
れるものの、水滴吸収性すなわち吸水性に問題がある。
また、同様に吸水性多孔シートＫにおいては気孔率が９
３％であり、水滴吸収性と臭気には優れるものの、曲げ
強度が低く、力学的特性に問題がある。さらには粒径１
２０μｍ、比表面積２５０ｍ2 ／ｇのシリカゲルを吸着
剤とした吸水性多孔シートＬはシリカゲルの付着量は５
×１０3 ｇ／ｍ3 であり、臭気の点では問題ないが、水
滴吸収性で問題がある。また、Ｌと同様のシリカゲルを
使用して付着量が１５×１０3 ｇ／ｍ3 である吸水性多
孔シートＭにおいては水滴吸収性では問題ないが、臭気
においては問題である。それに対して実施例の吸水性多
孔シートＡ、Ｂ、Ｃ、Ｄ、Ｅ、Ｆ、Ｇ、Ｈはいずれも上
記したような吸水性、力学的特性、及び臭気に関して問
題はなく、優れた吸水性多孔シートとしての特性を備え
ていることが明らかである。As is clear from Table 1, the particle size is 0.1 μm.
m, a water-absorbing porous sheet B using silica gel having a specific surface area of 250 m 2 / g as an adsorbent, and focusing on I, the product of the specific surface area and the adhered amount is 3.13 × 10 6 m 2 / m 3 I is excellent in water drop absorbency and bending strength,
There is a problem in terms of odor. In addition, the water-absorbing porous sheet J using the same silica gel as the water-absorbing porous sheet B has a porosity of 35% and is excellent in bending strength and odor, but has a problem in water droplet absorbability, that is, water absorption.
Similarly, in the water absorbent porous sheet K, the porosity is 9
Although it is 3%, the water drop absorbency and the odor are excellent, but the bending strength is low and there is a problem in mechanical properties. Furthermore, particle size 1
The water-absorbing porous sheet L using 20 μm and a specific surface area of 250 m 2 / g of silica gel as an adsorbent has a silica gel adhesion amount of 5
It is × 10 3 g / m 3 , and there is no problem in terms of odor, but there is a problem in water droplet absorption. Further, in the water-absorbing porous sheet M having the adhesion amount of 15 × 10 3 g / m 3 using the same silica gel as L, there is no problem with the water droplet absorbability, but there is a problem with odor. On the other hand, the water-absorbing porous sheets A, B, C, D, E, F, G, and H of the examples all have no problem with respect to water absorption, mechanical characteristics, and odor as described above, and have excellent water absorption. It is clear that it has the properties of a porous sheet.
【００３９】[0039]
【発明の効果】以上のように構成されているので、本発
明の吸水性多孔シートは、臭気発生が少なく、吸水性、
力学的特性に優れているので、調湿板、加湿器の保水
材、水蒸散板、結露防止板等として好適に利用できる。As described above, the water-absorbing porous sheet of the present invention has a small amount of odor generation, water-absorbing property, and
Since it has excellent mechanical properties, it can be suitably used as a humidity control plate, a water retaining material for a humidifier, a water evaporation plate, a dew condensation preventing plate, and the like.
Claims (3)
性多孔シートであって、この吸水性多孔シートの一方の
面から他の面に貫通する連続気孔を有していて、さらに
気孔率が４０〜９０％、吸水率が４０％以上、水滴吸収
性が３秒以内、曲げ強度が３０ｋｇ／ｃｍ2 以上であ
り、吸着剤の付着量は吸着剤の比表面積（ｍ2 ／ｇ）と
付着量（ｇ／ｍ3 ）との積が２．５×１０6 （ｍ2 ／ｍ
3 ）以下であることを特徴とする吸水性多孔シート。1. A water-absorbing porous sheet having an adsorbent adhered to a porous substrate, which has continuous pores penetrating from one surface of the water-absorbing porous sheet to the other surface thereof. Porosity is 40 to 90%, water absorption is 40% or more, water drop absorbency is within 3 seconds, bending strength is 30 kg / cm 2 or more, and the adsorbent adhesion amount is the specific surface area of the adsorbent (m 2 / g ) And the adhesion amount (g / m 3 ) are 2.5 × 10 6 (m 2 / m
3 ) A water-absorbing porous sheet characterized by having the following:
求項１記載の吸水性多孔シート。2. The water-absorbing porous sheet according to claim 1, wherein the porous substrate is composed of fibers.
成されている請求項１記載の吸水性多孔シート。3. The water-absorbing porous sheet according to claim 1, wherein the porous substrate is composed of fibers and a reinforcing resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7008853A JP3059352B2 (en) | 1995-01-24 | 1995-01-24 | Water-absorbing porous sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7008853A JP3059352B2 (en) | 1995-01-24 | 1995-01-24 | Water-absorbing porous sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08198977A true JPH08198977A (en) | 1996-08-06 |
| JP3059352B2 JP3059352B2 (en) | 2000-07-04 |
Family
ID=11704300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7008853A Expired - Lifetime JP3059352B2 (en) | 1995-01-24 | 1995-01-24 | Water-absorbing porous sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3059352B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002249612A (en) * | 2001-02-23 | 2002-09-06 | Sanwa Kako Co Ltd | Resin foam having vibration-camping property and containing tourmaline ore, and method for producing the same |
| JP2002249613A (en) * | 2001-02-23 | 2002-09-06 | Sanwa Kako Co Ltd | Resin open-cell foam having vibration-damping property and containing tourmaline ore, and method for producing the same |
| KR100535969B1 (en) * | 1999-08-19 | 2005-12-09 | 니찌아스 카부시키카이샤 | Humidification element for vaporizing humidifier |
-
1995
- 1995-01-24 JP JP7008853A patent/JP3059352B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100535969B1 (en) * | 1999-08-19 | 2005-12-09 | 니찌아스 카부시키카이샤 | Humidification element for vaporizing humidifier |
| JP2002249612A (en) * | 2001-02-23 | 2002-09-06 | Sanwa Kako Co Ltd | Resin foam having vibration-camping property and containing tourmaline ore, and method for producing the same |
| JP2002249613A (en) * | 2001-02-23 | 2002-09-06 | Sanwa Kako Co Ltd | Resin open-cell foam having vibration-damping property and containing tourmaline ore, and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3059352B2 (en) | 2000-07-04 |
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