JPH0196558A - Blood agglutinating and coagulating agent - Google Patents

Blood agglutinating and coagulating agent

Info

Publication number
JPH0196558A
JPH0196558A JP62252430A JP25243087A JPH0196558A JP H0196558 A JPH0196558 A JP H0196558A JP 62252430 A JP62252430 A JP 62252430A JP 25243087 A JP25243087 A JP 25243087A JP H0196558 A JPH0196558 A JP H0196558A
Authority
JP
Japan
Prior art keywords
zinc
blood
silicate
coagulating agent
amorphous silica
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
Application number
JP62252430A
Other languages
Japanese (ja)
Other versions
JP2532515B2 (en
Inventor
Masahide Ogawa
小川 政英
Teiji Sato
悌治 佐藤
Masanori Tanaka
正範 田中
Kazuo Enomoto
一雄 榎本
Takayuki Ishizuki
石附 隆之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mizusawa Industrial Chemicals Ltd
Original Assignee
Mizusawa Industrial Chemicals Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mizusawa Industrial Chemicals Ltd filed Critical Mizusawa Industrial Chemicals Ltd
Priority to JP62252430A priority Critical patent/JP2532515B2/en
Publication of JPH0196558A publication Critical patent/JPH0196558A/en
Application granted granted Critical
Publication of JP2532515B2 publication Critical patent/JP2532515B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Investigating Or Analysing Biological Materials (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

PURPOSE:To obtain a coagulating agent having excellent coagulation power and high surface activity and liquid absorptivity by preparing a compsn. contg. zinc silicate, zinc aminosilicate or these zincs and amorphous silica or nonamorphous silica alumina at prescribed ratios. CONSTITUTION:The coagulating agent is prepd. from the compsn. of the zinc silicate, zinc aminosilicate or these zincs and amorphous silica or the nonamorphous silica alumina which has 0.1-100mum median diameter, 30-1,000m<2>/g BET specific surface area and 30-200ml/100g oil absorption and contains ZnO at 5-70wt.% in the entire part. The coagulation effect tends to degrade if the concn. of the ZnO in the entire part is below said range. Conversely, the agent having the high activity and the high liquid absorptivity is hardly obtainable if the concn. exceeds the above-mentioned range. The coagulation effect of serum and the liquid absorptivity tend to degrade if the median diameter is larger than the above-mentioned range. Conversely, the coagulation effect degrades or the yield of adhesion to a base body such as paper is low if the median diameter is smaller than the above-mentioned range.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は血液凝集凝固剤に関するもので、人又は動物の
血液に対して迅速な凝集性及び凝固性を示し、特に病院
における血液廃棄処理並び食肉センターや水酸加工場に
おける立木処理に有用であり、また絆創膏、包帯、生理
用品等における血液漏れ防止に有用である血液凝集凝固
剤に関する。
Detailed Description of the Invention (Industrial Application Field) The present invention relates to a blood coagulant and coagulant, which exhibits rapid agglutination and coagulation properties for human or animal blood, and is particularly useful in blood waste treatment and treatment in hospitals. The present invention relates to a blood aggregation coagulant that is useful for processing standing trees in meat centers and hydrochloric acid processing plants, and is also useful for preventing blood leakage in adhesive plasters, bandages, sanitary products, etc.

(従来の技術) 水酸加工場では、多量の面木が発生しているが、この面
木は汚濁度が非常に高いため、通常の排水処理設備では
処理できず、別途の処理が必要とされている。立木は凝
集処理の最も困難な汚水の一つであり、汚水中に含まれ
る血液分を完全に捕集し、凝集させて、汚水を清澄化さ
せることは、従来の排水処理技術では不可能に近かった
(Conventional technology) A large amount of mengi is generated in hydrochloric acid processing plants, but because the pollution level of this menki is extremely high, it cannot be treated with ordinary wastewater treatment equipment, and separate treatment is required. has been done. Standing trees are one of the most difficult types of wastewater to coagulate, and it is impossible with conventional wastewater treatment technology to completely collect the blood contained in wastewater, coagulate it, and clarify the wastewater. It was close.

例えば、青森県水酸加工研報告59年度第144〜14
6頁には、ポリアクリル酸ソーダ系高分子凝集剤を使用
したマイワシ面木の凝集処理試験の結果が報告されてい
るが、蛋白質として約60〜80%程度の凝集率が得ら
れているにすぎない。
For example, Aomori Prefecture Hydroxic Acid Processing Research Institute Report No. 144-14
Page 6 reports the results of a flocculation treatment test of sardine sardines using a sodium polyacrylate polymer flocculant, and it was found that a flocculation rate of about 60 to 80% was obtained for protein. Only.

また、生理用品における血液漏れ防止には、架橋ポリア
クリル酸塩の如ぎ高吸水性樹脂が広く使用されているが
、これらの高吸水性樹脂は比較的大きな吸液性を示すと
しても、血液を凝集凝固させるという能力には未だ欠け
ており、血液漏れを完全に防止するという能力には未だ
欠けている。
In addition, super absorbent resins such as cross-linked polyacrylates are widely used to prevent blood leakage in sanitary products, but even though these super absorbent resins exhibit relatively high liquid absorption, they do not absorb blood easily. It still lacks the ability to coagulate and coagulate blood, and it still lacks the ability to completely prevent blood leakage.

(発明が解決しようとする問題点) 血液と接触するだけで血液を凝集、凝固させることがで
きる無機粉体が得られれば、このものが血液廃棄処理、
良木処理及び生理用品や外用衛生材の血液漏れ防止に極
めて有用な血液凝集凝固剤となり得ることが期待される
(Problem to be solved by the invention) If an inorganic powder that can coagulate and coagulate blood simply by coming into contact with blood can be obtained, this powder can be used for blood waste treatment,
It is expected that it will be an extremely useful blood coagulant and coagulant for wood treatment and prevention of blood leakage in sanitary products and external sanitary products.

本発明者等は、以下に詳述する特定の物性を有するケイ
酸亜鉛、アルミノケイ酸亜鉛またはこれらと非晶質シリ
カ或いは非晶質シリカアルミナとの組成物は、優れた血
液凝集凝固作用を有することを見出した。
The present inventors have discovered that zinc silicate, zinc aluminosilicate, or a composition of these and amorphous silica or amorphous silica alumina, which have specific physical properties detailed below, have excellent blood coagulation and coagulation effects. I discovered that.

(問題点を解決するための手段) 本発明によれば、0.1乃至100μmのメジアン径、
30乃至1000m’/gのBET比表面積及び30乃
至200m7!/10Qgの吸油量(JISK 510
1)を有し且つ全体当りのZnOとしての含有量が5乃
至70重量%のケイ酸亜鉛、アルミノケイ酸亜鉛または
これらと非晶質シリカ或いは非晶質シリカアルミナとの
組成物から成ることを特徴とする血液凝集凝固剤が提供
される。
(Means for solving the problem) According to the present invention, the median diameter of 0.1 to 100 μm,
BET specific surface area of 30 to 1000 m'/g and 30 to 200 m7! /10Qg oil absorption (JISK 510
1) and a composition of zinc silicate, zinc aluminosilicate, or amorphous silica or amorphous silica alumina with a total ZnO content of 5 to 70% by weight. A blood coagulant and coagulant is provided.

(作用) 従来、亜鉛華、亜鉛華デンプン、チンク油、硫酸亜鉛は
、止血作用のある収しン薬として知られている。本発明
の血液凝集凝固剤における血液凝固作用も亜鉛成分の存
在によるものと認められるが、亜鉛成分を、微細粒径及
び高吸油性を有する活性のケイ酸塩、アルミノケイ酸塩
またはこれらの塩と非晶質シリカ或いは非晶質シリカア
ルミナとの組成物の形で用いることが本発明の特徴であ
る。
(Action) Zinc white, zinc white starch, tink oil, and zinc sulfate have been known as astringents with hemostatic effects. It is recognized that the blood coagulation effect of the blood coagulant and coagulant of the present invention is also due to the presence of the zinc component, but the zinc component is replaced with an active silicate, aluminosilicate, or a salt thereof having a fine particle size and high oil absorption. A feature of the present invention is that it is used in the form of a composition with amorphous silica or amorphous silica alumina.

亜鉛華は、亜鉛成分の含有量が最も高い化合物ではある
が、その比表面積は粒径の最も小さいものでも1 ff
127Hのオーダーと低く、表面活性が著しく小さく、
また吸液性も著しく小さい。事実、木材バルブ中に19
.8重量%の微粒子酸化亜鉛を内填し、これを坪量15
0 g/m2の紙に抄紙したものに、屠殺直後の牛の新
鮮な血液を滴下すると、滴下面積とほぼ同様の面積で裏
抜を生ずることが認められた。これに対して、本発明に
従い、ケイ酸亜鉛、アルミノケイ酸亜鉛或いはこれらと
非晶質シリカ乃至非晶質シリカアルミナとの組成物(以
下単にくアルミノ)ケイ酸亜鉛等と呼ぶことがある)を
、上記と同様な条件で内填し、抄紙したものに対して、
血液を滴下すると、裏抜けは殆んど乃至全く生じないこ
とが認められた。これは、本発明で用いる(アルミノ)
ケイ酸亜鉛等が血液を吸液乃至凝集させ且つその場で凝
固させる能力に優れていることを示している。
Zinc white is a compound with the highest zinc content, but its specific surface area is 1 ff even for the smallest particle size.
It has a low surface activity of the order of 127H, and its surface activity is extremely low.
In addition, the liquid absorption property is also extremely low. In fact, 19 in the wood valve
.. Filled with 8% by weight of fine particle zinc oxide, which has a basis weight of 15%.
When fresh blood from a cow immediately after slaughter was dripped onto 0 g/m2 paper, it was observed that bleed-out occurred in approximately the same area as the dripping area. In contrast, according to the present invention, zinc silicate, zinc aluminosilicate, or a composition of these with amorphous silica or amorphous silica alumina (hereinafter sometimes simply referred to as zinc aluminosilicate, etc.) is used. , for paper filled and made under the same conditions as above,
Little to no bleed-through was observed when blood was applied. This is used in the present invention (alumino)
This shows that zinc silicate and the like have excellent ability to absorb and coagulate blood and coagulate it on the spot.

この理由は、本発明に用いる(アルミノ)ケイ酸亜鉛等
においては、シリカ或いはシリカ−アルミナのマトリッ
クス中に亜鉛成分がイオン或いは層の形で組込まれてい
て、高い表面活性と吸液性とを有すること、及びこの活
性表面に亜鉛成分が有効な状態で存在すること及びこの
(アルミノ)ケイ酸亜鉛粒子の表面は負に帯電しており
、内因性経路と呼ばれる反応による凝固作用の寄与もあ
ることによると思われる。
The reason for this is that in the zinc (alumino)silicate used in the present invention, the zinc component is incorporated in the form of ions or layers in the silica or silica-alumina matrix, and has high surface activity and liquid absorbency. The zinc component exists in an effective state on the active surface, and the surface of the zinc (alumino)silicate particles is negatively charged, contributing to the coagulation effect through a reaction called the intrinsic pathway. I think it depends.

本発明に用いる(アルミノ)ケイ酸亜鉛等において、全
体当りのZnOが5乃至70重量%、特に10乃至50
重量%の濃度で存在することも重要であり、この濃度が
上記範囲を下廻ると、凝固作用が低下する傾向があり、
上記濃度範囲を上廻ると、高活性及び高吸液性のものが
得難くなる。この(アルミノ)ケイ酸亜鉛等が0.1乃
至100μmのメジアン径(本明細書におけるメジアン
径とはコールタ−カウンター法により測定したメジアン
径を意味する)、特に0.5乃至10μmのメジアン径
を有することも重要であり、上記範囲よりも大きい場合
には、血液の凝固作用や吸液性が低下する傾向があり、
また上記範囲よりも小さい場合には、凝集作用が低下し
たり、或いは紙等の基体への付着歩留り等が低下する傾
向が認められる。また、この(アルミノ)ケイ酸亜鉛等
は表面活性の点で30乃至10001112/g、特に
200乃至700 m’/gの比表面積を有するべきで
あり、吸液性の見地からは40乃至300 mp/10
0 g 。
In the zinc (alumino)silicate etc. used in the present invention, the ZnO content per total is 5 to 70% by weight, particularly 10 to 50% by weight.
It is also important that it is present in a concentration of % by weight; if this concentration falls below the above range, the coagulation effect tends to decrease;
If the concentration exceeds the above range, it becomes difficult to obtain a product with high activity and high liquid absorption. This (alumino)zinc silicate etc. has a median diameter of 0.1 to 100 μm (the median diameter in this specification means the median diameter measured by the Coulter counter method), especially a median diameter of 0.5 to 10 μm. It is also important to have the above range, and if it is larger than the above range, the blood coagulation effect and liquid absorption properties tend to decrease.
If the amount is smaller than the above range, there is a tendency for the aggregation effect to decrease or for the adhesion yield to substrates such as paper to decrease. In addition, this zinc (alumino)silicate etc. should have a specific surface area of 30 to 10001112/g, especially 200 to 700 m'/g in terms of surface activity, and should have a specific surface area of 40 to 300 m'/g in terms of liquid absorption. /10
0g.

特に70乃至200 mp/100 gの吸液性を有す
るべきである。
In particular, it should have a liquid absorption of 70 to 200 mp/100 g.

(発明の好適態様) (アルミソ ケイ 亜鉛 本発明の第一の態様では、層状ケイ酸亜鉛又は層状アル
ミノケイ酸亜鉛を用いる。このタイプの(アルミノ)ケ
イ酸亜鉛は、シリカまたはシリカ−アルミナの四面体層
と、ZnO,またはZnO6−Ap o6の八面体層と
が二層又は三層に積層されたものを基本骨格とし、この
基本骨格が場合によりc!1ilb方向に積層された構
造を有する。
(Preferred Embodiment of the Invention) (Aluminosilicate Zinc) In the first embodiment of the present invention, layered zinc silicate or layered zinc aluminosilicate is used. The basic skeleton is composed of two or three layers of octahedral layers of ZnO or ZnO6-Apo6, and this basic skeleton is laminated in the c!ilb direction depending on the case.

層状ケイ酸亜鉛の適当な例はソーコナイト型フィロケイ
酸亜鉛であり、その構造、物性及び製造方法は、特開昭
61−10019号公報に記載されている。層状アルミ
ノケイ酸亜鉛の適当な例は、フライポンタイト型含アル
ミニウムフィロケイ酸亜鉛であり、その構造、物性及び
製造方法は特開昭61−10021号、51−2751
28号、及び61−275127号公報に記載されてい
る。
A suitable example of layered zinc silicate is sauconite type zinc phyllosilicate, whose structure, physical properties and manufacturing method are described in JP-A-61-10019. A suitable example of the layered zinc aluminosilicate is flypontite type aluminum-containing zinc phyllosilicate, whose structure, physical properties, and manufacturing method are described in JP-A-61-10021, 51-2751.
No. 28, and No. 61-275127.

本発明の第二の態様では、亜鉛交換合成ゼオライトを使
用する。この亜鉛交換合成ゼオライトは、一般に酸化物
重量基準で、 Zn0   5〜50%、 特に 10〜35%、 Na0  0.1〜20%、 特に 0.5〜5%、 510、   35〜70%、 特に 40〜60%、 AJ!zOs  1 5〜35%、 特に 20〜30%、 H2O0〜25%、 特に  0〜10% で表わされる化学組成と、ゼオライトに特有のX−線回
折像とを有する。この亜鉛交換ゼオライトは、それ自体
公知のX型、Y型、A型、モルデナイト、P型等のNa
型ゼオライトを、塩化亜鉛、硫酸亜鉛等の亜鉛塩水溶液
と接触させ、イオン交換を行わせることにより製造され
る。この亜鉛交換に際して、ゼオライトの結晶構造が破
壊されても、血液凝集凝固剤としての作用に悪影響はな
い。
A second embodiment of the invention uses zinc-exchanged synthetic zeolites. This zinc-exchanged synthetic zeolite generally contains, on an oxide weight basis, Zn0 5-50%, especially 10-35%, Na0 0.1-20%, especially 0.5-5%, 510, 35-70%, especially 40-60%, AJ! It has a chemical composition expressed as zOs 15-35%, especially 20-30%, H2O 0-25%, especially 0-10%, and an X-ray diffraction pattern characteristic of zeolites. This zinc-exchanged zeolite is a Na
It is produced by contacting type zeolite with an aqueous zinc salt solution such as zinc chloride or zinc sulfate to perform ion exchange. Even if the crystal structure of the zeolite is destroyed during this zinc exchange, there is no adverse effect on its action as a blood coagulant and coagulant.

本発明において、上述した各種の(アルミノ)ケイ酸亜
鉛は、単独或いは2fffi以上の組合せで使用し得る
他に、非晶質シリカ或いは非晶質シリカアルミナとの組
成物の形で使用することができる。例えば、(アルミノ
)ケイ酸亜鉛の合成を、非晶質シリカ或いはシリカアル
ミナのゾルの存在下に行なうことにより、結晶の生長を
抑制し、これによりBET比表面積及び吸油量の増大し
た血液凝集凝固剤とすることができる。
In the present invention, the above-mentioned various zinc (alumino)silicates can be used alone or in a combination of 2fffi or more, and can also be used in the form of a composition with amorphous silica or amorphous silica alumina. can. For example, by synthesizing zinc (alumino)silicate in the presence of amorphous silica or silica-alumina sol, crystal growth is suppressed, thereby increasing blood coagulation and coagulation with increased BET specific surface area and oil absorption. It can be used as an agent.

このタイプの複合物の適当な例は、非晶質で多孔質のシ
リカ又はシリカアルミナとその一次粒子表面に形成され
た含アルミニウムフィロケイ酸塩層とから成り、3成分
組成比で5i025乃至80モル%、Zn05乃至65
モル%、及びAj!1031乃至60モル%の化学組成
を有し、X線回折で面間隔dx8.40〜6.40人に
実質上ピークを有していなく、面間隔dx2.71〜2
.56人と面間隔dx1.56〜1.52人にピークを
有し、比表面積が200 m’/g以上で細孔径10乃
至300人における細孔容積が0.25cc/g以上で
ある複合フィロケイ酸塩であり、このものは、シリカ又
はシリカアルミナのゾル乃至ゲル分散体を含有する水性
媒体に水溶性ケイ酸塩、水溶性亜鉛塩、並びに水溶性ア
ルミニウム塩及び/又はアルミン酸塩を、全体について
の3成分組成比が5i025乃至80モル%、Zn05
乃至65モル%及びAp、0.1乃至60モル%の化学
組成となるように添加し、添加された塩類をシリカ又は
シリカアルミナの存在下に反応させることにより得られ
る。
A suitable example of this type of composite is composed of amorphous porous silica or silica alumina and an aluminum-containing phyllosilicate layer formed on the surface of its primary particles, with a three-component composition ratio of 5i025 to 80 Mol%, Zn05 to 65
Mol%, and Aj! It has a chemical composition of 1031 to 60 mol%, has virtually no peak in the lattice spacing dx 8.40 to 6.40 in X-ray diffraction, and has a lattice spacing dx 2.71 to 2.
.. Composite phyllocarbonate having a peak at a surface spacing dx of 56 people and 1.56 to 1.52 people, a specific surface area of 200 m'/g or more, and a pore volume of 0.25 cc/g or more at a pore diameter of 10 to 300 people. Acid salts, which contain water-soluble silicates, water-soluble zinc salts, and water-soluble aluminum salts and/or aluminates as a whole in an aqueous medium containing a sol or gel dispersion of silica or silica-alumina. The three component composition ratio is 5i025 to 80 mol%, Zn05
It is obtained by adding the salts so as to have a chemical composition of 65 mol % to 65 mol % and 0.1 to 60 mol % Ap, and reacting the added salts in the presence of silica or silica alumina.

進 本発明の血液凝集凝固剤は、それ自体公知の剤型、例え
ば粉末、粒状物、水性スラリー、各種ベースト、樹脂溶
液分散体、樹脂ラテックス分散体等の形で種々の用途に
供し得る。
The blood aggregation and coagulation agent of the present invention can be used for various purposes in the form of known dosage forms such as powder, granules, aqueous slurry, various types of bases, resin solution dispersions, resin latex dispersions, and the like.

例えば水産加工場や食肉センターで生ずる良木処理や、
病院における血液廃棄処理に際しては、処理すべき廃水
等に対して、(アルミノ)ケイ酸亜鉛等の粉末或いは水
性分散体を添加し、攪拌を行うことにより、血液成分の
殆んど全てを凝集凝固させることができる。(アルミノ
)ケイ酸亜鉛等の添加量は、処理すべき廃水中に含まれ
る血液の濃度によっても相違するが、一般に0.Ol乃
至20重量%、特に0.1乃至5重量%の範囲から最適
添加量を選ぶのがよい。
For example, processing good quality wood produced at seafood processing plants and meat centers,
When disposing of blood in hospitals, almost all of the blood components are coagulated and coagulated by adding powder or aqueous dispersion of zinc (alumino)silicate, etc. to the wastewater to be treated and stirring. can be done. The amount of zinc (alumino)silicate, etc. added varies depending on the concentration of blood contained in the wastewater to be treated, but is generally 0. The optimum amount to be added is preferably selected from the range of 0.1 to 20% by weight, particularly 0.1 to 5% by weight.

また、絆創膏、包帯、血止めガーゼ、生理用品等の用途
に用いる場合には、紙、不織布、編織物等の内部に(ア
ルミノ)ケイ酸亜鉛等を粉末の形で内填乃至含浸せしめ
るか、或いは表面に(アルミノ)ケイ酸亜鉛を樹脂バイ
ンダー等と共に塗布するのがよい。これらの用途におい
ては、(アルミノ)ケイ酸亜鉛の面積当りの塗布乃至含
浸量は一般に1乃至200 g/m”、特に3乃至70
 g/m2の範囲内にあるのいがよい0本発明において
は、(アルミノ)ケイ酸亜鉛等と、架橋ポリアクリル酸
塩、アクリル酸グラフト澱粉、アクリル酸グラフトポリ
ビニルアルコール等の高吸水性樹脂を組成物の形で用い
ることもでき、このような組成物の使用により、血液漏
れを一層有効に防止することができる。両者の配合比は
、広範囲に変化させ得るが、一般に(アルミノ)ケイ酸
亜鉛と高吸水性樹脂とを1:99乃至90:10の重量
比で用いることができる。この組成物は、一般に粒径が
0.5μm乃至1mmの粒状物の形で用いることもでき
る。
In addition, when used for adhesive plasters, bandages, blood-stopping gauze, sanitary products, etc., zinc (alumino)silicate or the like is injected or impregnated into paper, nonwoven fabric, knitted fabric, etc. in powder form, or It is preferable to apply zinc (alumino)silicate to the surface together with a resin binder or the like. In these applications, the applied or impregnated amount of zinc (alumino)silicate per area is generally 1 to 200 g/m", in particular 3 to 70 g/m".
In the present invention, zinc (alumino)silicate, etc., and super absorbent resin such as crosslinked polyacrylate, acrylic acid grafted starch, acrylic acid grafted polyvinyl alcohol, etc. It can also be used in the form of a composition, and by using such a composition, blood leakage can be more effectively prevented. The blending ratio of both can be varied over a wide range, but generally zinc (alumino)silicate and super absorbent resin can be used in a weight ratio of 1:99 to 90:10. The composition can also be used in the form of granules, generally having a particle size of 0.5 μm to 1 mm.

本発明の血液凝集凝固剤は、人又は動物の血液から、血
液中の血球及び1aia素原を凝集させ、血清を分離す
るための凝集凝固剤としても使用することができる。こ
の場合、(アルミノ)ケイ酸亜鉛等は血液当り0.1乃
至5重量%、特に0.3乃至2重量%の量で使用するの
がよく、血液中に上記(アルミノ)ケイ酸亜鉛を添加し
、よく振盪させた後、遠心分離或いは遠心沈降等により
分離すればよい。この方法は血液中の血清の試験や、血
液製剤の製法に広く使用できる。
The blood aggregation and coagulation agent of the present invention can also be used as an agglutination and coagulation agent for aggregating blood cells and 1aia elements in human or animal blood and separating serum. In this case, the zinc (alumino)silicate etc. is preferably used in an amount of 0.1 to 5% by weight, especially 0.3 to 2% by weight based on the blood, and the above zinc (alumino)silicate is added to the blood. After shaking well, the mixture may be separated by centrifugation or centrifugal sedimentation. This method can be widely used for testing serum in blood and for manufacturing blood products.

(発明の効果) 本発明によれば、特定の物性を有するケイ酸亜鉛、アル
ミノケイ酸亜鉛或いはこれらと非晶質シリカ或いは非晶
質シリカアルミナとの組成物を、血液凝集凝固剤として
用いることにより、優れた凝集凝固作用が得られた。
(Effect of the invention) According to the present invention, by using zinc silicate, zinc aluminosilicate, or a composition of these and amorphous silica or amorphous silica alumina, which have specific physical properties, as a blood coagulation coagulant. , an excellent coagulation and coagulation effect was obtained.

(実施例) 参考例 1 血液 固剤含有紙葉(シート)の製法 TAPPI型標準紙葉調製機(東洋精機製作新製)を用
い、製紙用KPバルブと実施例、比較例に記載する粉末
を任意の割合で混合抄紙し、坪量130〜150g、粉
末含有率18〜20重量%、水分10%以下となるよう
に紙葉を調製した。
(Example) Reference Example 1 Blood Manufacturing method of paper sheets (sheets) containing solidifying agent Using a TAPPI type standard paper sheet preparation machine (newly manufactured by Toyo Seiki Seisakusho), the KP valve for paper manufacturing and the powder described in Examples and Comparative Examples were prepared. Paper sheets were prepared by mixing them in arbitrary ratios to have a basis weight of 130 to 150 g, a powder content of 18 to 20% by weight, and a moisture content of 10% or less.

実施例 1 3号ケイ酸ソーダ(Si(h : 22.0%、 Na
2O: 7.0%)330gと35%塩酸約80gを用
いて1)H2〜4の酸性条件下で中和反応させて調製し
たシリカゾルを加熱によりゲル化させ、水洗し、シリカ
ヒドロゲルを得た。得られたヒドロゲルを水とともに家
庭用ミキサーにて解砕し、非晶質シリカスラリー液(S
in、分=4.8%)を得た(第1工程)。
Example 1 No. 3 sodium silicate (Si (h: 22.0%, Na
Using 330 g of 2O: 7.0%) and about 80 g of 35% hydrochloric acid, a silica sol prepared by neutralization reaction under acidic conditions of 1) H2-4 was gelled by heating and washed with water to obtain a silica hydrogel. . The obtained hydrogel was crushed with water in a household mixer, and an amorphous silica slurry liquid (S
in, min=4.8%) (first step).

3号ケイ酸ソーダ205gと水酸化ナトリウム221 
g (Na08分:5.5モル)を水に溶かして全量を
12とし、これをA液(Sin2分: 0.75モル)
とする。一方、塩化亜鉛(無水塩)180gと塩化アル
ミニウム(6水塩)241gを水に溶かして全量を11
とし、これをB液(Zn0分:1.2モル、  Aj!
2(h分;0.6そル)とする。第一工程にて得たシリ
カスラリー液1.5にg (SITJh分:1.2モル
)を52ビーカーにとり、攪拌下、液温を40℃に保ち
ながらA液とB液をそれぞれ25cc/分の速度で同時
に注加した。注下終了後この反応液のpHは約7.2で
あった。さらに攪拌を続け、1時間熟成した。反応液を
吸引が過水洗し、11’O℃で乾燥した。得られたケー
キをサンプルミルにて粉砕し、複合フィロアルミノケイ
酸亜鉛の白色微粉末を得た。(第2工程) 上記第2工程にて得た粉末を用いて、参考例1と全く同
様の方法で坪!14/g、複合フィロアルミソケイ酸亜
鉛含有率!9.7%、水分9.8%の紙葉を得た。(第
3工程) 実施例 2 新潟県中条町産・酸性白土を粗砕したのち線状に成型(
直径:3mm)シたもの250gに、該粘土に含有され
ているアルミニウム、マグネシウム、カルシウム、鉄、
ナトリウム、カリウム、チタニウム等の塩基性金属成分
の全ダラム当量数(1,14グラム当量7100 g乾
燥物)の3.5倍グラム当量数に相当する硫酸、すなわ
ち34%硫酸700mpを加え、85℃の水浴で15時
間加熱し、酸処理を行なった。濾過により水洗し、ケー
キを得た。該ケーキの少量を110℃で乾燥し、粉砕し
、定量分析するとSio2分は92.7%(110℃乾
燥物基準)であった。得られたケーキをボットミルに入
れ、水を加えて朝鮮ボールとともに湿式粉砕し、5i0
2分を15%含むスラリーを得た。
205g of No. 3 sodium silicate and 221g of sodium hydroxide
Dissolve g (Na08 min: 5.5 mol) in water to make a total volume of 12, and make this solution A (Sin 2 min: 0.75 mol)
shall be. On the other hand, dissolve 180 g of zinc chloride (anhydrous salt) and 241 g of aluminum chloride (hexahydrate) in water and add 11 g of the total amount to 11 g.
This was used as solution B (Zn0 min: 1.2 mol, Aj!
2 (h minutes; 0.6 soru). Add 1.5 g of the silica slurry obtained in the first step (SITJh: 1.2 mol) to a 52 beaker, and add 25 cc/min each of A and B solutions while stirring and keeping the liquid temperature at 40°C. were added simultaneously at a rate of After the completion of pouring, the pH of this reaction solution was approximately 7.2. Stirring was continued and the mixture was aged for 1 hour. The reaction solution was washed with water under suction and dried at 11'O<0>C. The obtained cake was pulverized in a sample mill to obtain a fine white powder of composite zinc phylloaluminosilicate. (Second step) Using the powder obtained in the second step, the same method as in Reference Example 1 was carried out to obtain tsubo! 14/g, composite phylloalumisosilicate zinc content! A paper sheet with a moisture content of 9.7% and a moisture content of 9.8% was obtained. (Third step) Example 2 Acidic clay from Nakajo Town, Niigata Prefecture was roughly crushed and then formed into a linear shape (
Diameter: 3 mm) 250 g of clay contains aluminum, magnesium, calcium, iron,
Add sulfuric acid equivalent to 3.5 times the number of gram equivalents of the total Durham equivalent number (1.14 gram equivalent 7100 g dry matter) of basic metal components such as sodium, potassium, titanium, etc., that is, 700 mp of 34% sulfuric acid, and heat at 85°C. The mixture was heated in a water bath for 15 hours to perform acid treatment. A cake was obtained by filtration and washing with water. A small amount of the cake was dried at 110° C., pulverized, and quantitatively analyzed to find that the Sio2 content was 92.7% (based on dry matter at 110° C.). The resulting cake was placed in a bot mill, water was added, and it was wet-milled with Korean balls to form a 5i0
A slurry containing 15% of 2 min was obtained.

(第1工程) つぎに得られたスラリー2008 (Si02分:30
g)と酸化亜鉛(試薬−級)30gを12のオートクレ
ーブ容器にとり、更に水370gを加えて、500回転
/分の攪拌条件下で160℃で5時間水熱合成反応を行
なった。冷却後反応物をとりだし、?過により水を分離
したのち、130℃で乾燥した。乾燥品を卓上小型サン
プルミルにて粉砕し、ソーコナイト型ケイ酸亜鉛白色微
粉末を得た。(第2工程) 上記第2工程にて得た粉末を用いて、参考例1と全く同
様の方法で坪量13/g、ソーコナイト型ケイ酸亜鉛含
有率19.0%、水分92%の紙葉を得た。(第3工程
) 実施例 3 1iのビーカーに塩化アンモニウム16g(0,3モル
)をとり、水を加えて0.6 pの水溶液とする。ここ
へケイソウ±(クリストバライト型シリカ、昭和化学工
業■製) 12 g (Si02分:0.2モル)、酸
化亜鉛24g(0,3モル)およびベーマイトゲル14
 g (Al2O+分: 0.1モル)を加えて攪拌す
る。このスラリーをIIのオートクレーブ容器に入れ、
300回転/分の攪拌条件下180℃で6時間水熱合成
反応を行なった。冷却後、反応物を取り出して、吸引濾
過し、水洗し、110℃で乾燥した。得られた乾燥ケー
キをサンプルミルにより粉砕し、二層構造を有するフラ
イポンタイトの白色微粉末を得た。(第1工程) 上記第1工程にて得た粉末を用いて、参考例1と全く同
様の方法で坪量145g、フライボンタイト含有率18
.9%、水分9.5%の紙葉を得た。
(First step) Next, the obtained slurry 2008 (Si02 minutes: 30
g) and 30 g of zinc oxide (reagent grade) were placed in a No. 12 autoclave container, 370 g of water was further added, and a hydrothermal synthesis reaction was carried out at 160° C. for 5 hours under stirring conditions of 500 rpm. After cooling, take out the reactant and ? After separating water by filtration, it was dried at 130°C. The dried product was pulverized in a small tabletop sample mill to obtain white fine powder of sauconite zinc silicate. (Second step) Using the powder obtained in the second step above, a paper with a basis weight of 13/g, a sauconite type zinc silicate content of 19.0%, and a moisture content of 92% was prepared in exactly the same manner as in Reference Example 1. Got leaves. (Third Step) Example 3 Take 16 g (0.3 mol) of ammonium chloride in a 1i beaker and add water to make a 0.6 p aqueous solution. Here, diatom ± (cristobalite type silica, manufactured by Showa Kagaku Kogyo ■) 12 g (Si02 min: 0.2 mol), zinc oxide 24 g (0.3 mol), and boehmite gel 14
g (Al2O+min: 0.1 mol) and stir. Put this slurry into autoclave container II,
A hydrothermal synthesis reaction was carried out at 180° C. for 6 hours under stirring conditions of 300 revolutions/minute. After cooling, the reaction product was taken out, filtered with suction, washed with water, and dried at 110°C. The obtained dry cake was pulverized using a sample mill to obtain a white fine powder of flypontite having a two-layer structure. (First step) Using the powder obtained in the first step above, the same method as in Reference Example 1 was used to obtain powder with a basis weight of 145 g and a flybontite content of 18.
.. A paper sheet with a moisture content of 9.5% and a water content of 9.5% was obtained.

(第2工程) 実施例 4 市販4A型ゼオライト粉末500gを51!ビーカーに
とり、これに2M塩化亜鉛溶液3jを加え、攪拌下60
℃にて5時間保持した。かかるスラリーを吸引濾過によ
り固形分を分離した。濾過固形分を再び51ビーカーに
とり、これに再び2M塩化亜鉛溶液31を加え、攪拌下
60℃にて5時間保持した。
(Second step) Example 4 500g of commercially available 4A type zeolite powder was added to 51! Place in a beaker, add 3j of 2M zinc chloride solution, and stir for 60 minutes.
It was held at ℃ for 5 hours. The solid content of the slurry was separated by suction filtration. The filtered solid content was again taken in a beaker 51, and 2M zinc chloride solution 31 was added thereto again, and the mixture was kept at 60° C. for 5 hours while stirring.

かかるスラリーを吸引lp過により濾過水洗し、150
℃で乾燥した。得られたケーキを小型サンプルミルにて
粉砕し、亜鉛−A型ゼオライトの白色微粉末を得た。(
第1工程) 上記第1工程にて得た粉末を用いて、参考例1と全く同
様の方法で坪量139g、亜鉛A型ゼオライト含有率1
8.5%、水分8.5%の紙葉を得た。
The slurry was filtered and washed with water by suction lp filtration, and
Dry at °C. The resulting cake was pulverized in a small sample mill to obtain a fine white powder of zinc-A type zeolite. (
1st step) Using the powder obtained in the above 1st step, in exactly the same manner as in Reference Example 1, the basis weight was 139 g, and the zinc A-type zeolite content was 1.
A paper sheet having a moisture content of 8.5% and a moisture content of 8.5% was obtained.

(第2工程) 比較例 1 試薬−級酸化亜鉛を用いて、参考例1と全(同様の方法
で坪量150g、酸化亜鉛含有率19.996゜水分8
.1%の紙葉を得た。
(Second Step) Comparative Example 1 Using reagent-grade zinc oxide, the same method as in Reference Example 1 was carried out, with a basis weight of 150 g, a zinc oxide content of 19.996°, and a moisture content of 8.
.. A 1% paper sheet was obtained.

比較例 2 試薬化学用塩基性炭酸亜鉛を用いて、参考例1と全く同
様の方法で坪量14/g、塩基性炭酸亜鉛含有率19.
3%、水分8.2%の紙葉を得た。
Comparative Example 2 Using basic zinc carbonate for chemical reagents, a basis weight of 14/g and a basic zinc carbonate content of 19.
A paper sheet having a moisture content of 3% and a moisture content of 8.2% was obtained.

比較例 3 市葉微粉ケイ酸(水滓化学工業ミズカシルp−78)を
用いて、参考例1と全く同様の方法で坪1135g、微
粉ケイ酸含有率19.1%、水分9.5%の紙葉を得た
Comparative Example 3 Using Ichiha fine powder silicic acid (Suiko Kagaku Kogyo Mizukashiru p-78), in exactly the same manner as in Reference Example 1, 1135 g of tsubo, fine powder silicic acid content 19.1%, moisture 9.5% was prepared. I got a paper leaf.

応用例 1 実施例1.2の第3工程、実施例3.4の第2工程、比
較例1〜3で得た各粉末内添の紙葉を使って、層殺直後
のホルスタイン牛の血液、層殺直後の豚の血液、繊維濃
厚を除去した鳥肌繊維血液(日本バイオ研究新製)を0
.2a+j!を紙葉の表面に滴下した。紙葉への滴下は
採血後3分以内に終了するようにした。滴下30分後の
紙葉裏面への血液の裏穆り状態を次の記号で評価し、結
果を第1表に示した。
Application example 1 Using paper sheets containing each powder obtained in the third step of Example 1.2, the second step of Example 3.4, and Comparative Examples 1 to 3, blood of Holstein cows immediately after stratification was prepared. , Pig blood immediately after stratification, Goosebump fiber blood (manufactured by Nippon Bio Research New Co., Ltd.) from which concentrated fibers have been removed.
.. 2a+j! was dropped onto the surface of the paper sheet. The dripping onto the paper sheet was completed within 3 minutes after blood collection. Thirty minutes after dropping, the state of blood staining on the back side of the paper sheet was evaluated using the following symbols, and the results are shown in Table 1.

第1表 第1表の結果より本発明のケイ酸亜鉛およびアルミノケ
イ酸亜鉛が血液凝固に効果があることは明白である。
From the results shown in Table 1, it is clear that the zinc silicate and zinc aluminosilicate of the present invention are effective for blood coagulation.

応用例 2 実施例1.2の第2工程、実施例3.4の第1工程にて
得た粉末、及び比較例1〜3の粉末を20mA遠沈管に
0.3g採取し、これに層殺直後のホルスタイン牛の血
液、層殺直後の豚の血液、ia維素濃厚除去した鳥肌繊
維血液(日本バイオ研究新製) 15 miqを入れ、
手で10回激しくふりまぜ7分後の血液の凝固状態を観
察し、次の記号で評価し、結果を第2表に示した。
Application example 2 0.3 g of the powder obtained in the second step of Example 1.2, the first step of Example 3.4, and the powder of Comparative Examples 1 to 3 was collected in a 20 mA centrifuge tube, and a layer was added to the powder. Add Holstein cow blood immediately after slaughter, pig blood immediately after stratification, and Goosebump fiber blood from which the IA fibril has been removed (manufactured by Nippon Bio Research New Co., Ltd.) at 15 mi.
The blood coagulation state was observed after 7 minutes of vigorous shaking 10 times by hand and evaluated using the following symbols, and the results are shown in Table 2.

第2表 第2表の結果より本発明のケイ酸亜鉛およびアルミノケ
イ酸亜鉛が血液凝固に効果があることは明白である。
From the results shown in Table 2, it is clear that the zinc silicate and zinc aluminosilicate of the present invention are effective for blood coagulation.

Claims (1)

【特許請求の範囲】 (1)0.1乃至100μmのメジアン径、30乃至1
000m_2/gのBET比表面積及び30乃至200
ml/100gの吸油量(JIS K 5101)を有
し、且つ全体当りのZnOとしての含有量が5乃至70
重量%のケイ酸亜鉛、アルミノケイ酸亜鉛またはこれら
と非晶質シリカ或いは非晶質シリカアルミナとの組成物
から成ることを特徴とする血液凝集凝固剤。 (2)ケイ酸亜鉛又はアルミノケイ酸亜鉛が層状ケイ酸
亜鉛又は層状アルミノケイ酸亜鉛である特許請求の範囲
第1項記載の血液凝集凝固剤。 (3)ケイ酸亜鉛がソーコナイトである特許請求の範囲
第1項記載の血液凝集凝固剤。(4)アルミノケイ酸亜
鉛がフライポンタイトである特許請求の範囲第1項記載
の血液凝集凝固剤。 (5)アルミノケイ酸亜鉛が亜鉛交換合成ゼオライトで
ある特許請求の範囲第1項記載の血液凝集凝固剤。 (6)前記組成物が面間隔(dx)8.40乃至6.4
0Åに実質上ピークが存在しなく且つ面間隔(dx)2
.71乃至2.56Åと面間隔(dx)1.56乃至1
.52Åに弱い回折ピークを有する含アルミニウムフイ
ロケイ酸亜鉛を含有する特許請求の範囲第1項記載の血
液凝集凝固剤。
[Claims] (1) Median diameter of 0.1 to 100 μm, 30 to 1
BET specific surface area of 000 m_2/g and 30 to 200
It has an oil absorption amount (JIS K 5101) of ml/100g and a total ZnO content of 5 to 70
1. A blood coagulating coagulant comprising a composition of zinc silicate, zinc aluminosilicate, or amorphous silica or amorphous silica alumina in the amount by weight. (2) The blood coagulation coagulant according to claim 1, wherein the zinc silicate or zinc aluminosilicate is layered zinc silicate or layered zinc aluminosilicate. (3) The blood aggregating and coagulating agent according to claim 1, wherein the zinc silicate is sauconite. (4) The blood aggregating and coagulating agent according to claim 1, wherein the zinc aluminosilicate is flypontite. (5) The blood aggregating and coagulating agent according to claim 1, wherein the zinc aluminosilicate is a zinc-exchanged synthetic zeolite. (6) The composition has a lattice spacing (dx) of 8.40 to 6.4.
There is virtually no peak at 0 Å and the interplanar spacing (dx)2
.. 71 to 2.56 Å and spacing (dx) 1.56 to 1
.. The blood aggregating and coagulating agent according to claim 1, which contains aluminum-containing zinc phyllosilicate having a weak diffraction peak at 52 Å.
JP62252430A 1987-10-08 1987-10-08 Blood coagulant Expired - Lifetime JP2532515B2 (en)

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JP2532515B2 JP2532515B2 (en) 1996-09-11

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