JPH09176998A - Egg shell membrane fine powder-blended paper and various functional paper utilizing egg shell membrane fine powder - Google Patents

Egg shell membrane fine powder-blended paper and various functional paper utilizing egg shell membrane fine powder

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Publication number
JPH09176998A
JPH09176998A JP7350120A JP35012095A JPH09176998A JP H09176998 A JPH09176998 A JP H09176998A JP 7350120 A JP7350120 A JP 7350120A JP 35012095 A JP35012095 A JP 35012095A JP H09176998 A JPH09176998 A JP H09176998A
Authority
JP
Japan
Prior art keywords
paper
fine powder
eggshell membrane
membrane fine
egg shell
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
JP7350120A
Other languages
Japanese (ja)
Other versions
JP3567308B2 (en
Inventor
Yoshihiro Kawaguchi
芳広 川口
Hiroshi Yokota
博志 横田
Tetsunori Kunitake
哲則 国武
Akinori Murayama
明徳 村山
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.)
Ishihara Chemical Co Ltd
QP Corp
Kami Shoji Co Ltd
Original Assignee
Ishihara Chemical Co Ltd
QP Corp
Kami Shoji Co 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 Ishihara Chemical Co Ltd, QP Corp, Kami Shoji Co Ltd filed Critical Ishihara Chemical Co Ltd
Priority to JP35012095A priority Critical patent/JP3567308B2/en
Publication of JPH09176998A publication Critical patent/JPH09176998A/en
Application granted granted Critical
Publication of JP3567308B2 publication Critical patent/JP3567308B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To obtain blended paper of egg shell membrane fine powder having high practicality and effectively retained in properties of egg shell film without impairing the properties and provide the egg shell membrane fine powder blended paper as various kinds of functional paper having new uses such as humidity control, oil absorption and removal of sebum. SOLUTION: An egg shell membrane is immersed in water or an alcoholic solvent and subjected to at least either one of stone mill type rotation grinding and ball mill type grinding to prepare powder of egg shell membrane by a wet pulverizing method and fiber structure of the fine powder is entangled to produce the objective blended paper having sheet shape. Since the paper is blended paper due to self-adhesiveness between fibers of egg shell membrane fine powder, contact area with outside air is increased and a function which egg shell membrane has is smoothly developed. Then, the blended paper can be provided into a market as various kind of paper having new uses such as conditioned paper and oil-absorbing paper. Convenience of use is increased by processing the powder of the egg shell membrane into paper.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は卵殻膜微細粉末配合紙、
並びに卵殻膜微細粉末を利用した各種機能紙に関し、卵
殻膜の性状を損なわずに有効に保持した実用性の高い卵
殻膜微細粉末の配合紙を提供するとともに、この卵殻膜
微細粉末配合紙を調湿、吸油、皮脂除去などの新たな用
途を備えた各種機能紙として提供しようとするものであ
る。BACKGROUND OF THE INVENTION The present invention relates to a paper containing eggshell membrane fine powder,
Also, regarding various functional papers using eggshell membrane fine powder, we provide highly practical eggshell membrane fine powder blended paper that effectively retains the eggshell membrane fine properties and prepares this eggshell membrane fine powder blended paper. It is intended to be provided as various functional papers having new uses such as moisture, oil absorption, and removal of sebum.

【０００２】[0002]

【発明の背景】近年、地球環境や生態系の保護の観点か
ら、生物を含めた資源の省力化や有効利用が強く要請さ
れているが、鳥卵の卵殻膜(特に、鶏卵など)はタンパク
質を主成分とする天然素材であり、皮膚疾患の治療への
適用が従来から試みられている程度で、その多くが利用
されないまま廃棄されているのが現状である。BACKGROUND OF THE INVENTION In recent years, from the viewpoint of protection of the global environment and ecosystems, there has been a strong demand for labor saving and effective utilization of resources including living organisms. However, the eggshell membrane of avian eggs (especially chicken eggs) is a protein. It is a natural material whose main component is, and its application to the treatment of skin diseases has been tried so far, and most of it is currently discarded without being used.

【０００３】[0003]

【従来の技術】特開昭６３―３０９２７３号公報には、
卵殻膜を利用したシートが開示されている。即ち、生の
卵殻膜に加熱乾燥、或は凍結乾燥などを施し、ハンマー
ミル、スパイラルミル等で乾式粉砕して粉末化し、この
乾式粉砕処理方式の卵殻膜粉末を主材としてシートを製
造して、皮膚疾患や創傷の治療材、同補助材、或は化粧
品補助材に使用できることが述べられている。2. Description of the Related Art Japanese Patent Laid-Open No. 63-309273 discloses
A sheet using an eggshell membrane is disclosed. That is, the raw eggshell membrane is subjected to heat drying, freeze-drying, etc., and is dry pulverized with a hammer mill, a spiral mill or the like to be powdered, and a sheet is produced by using the eggshell membrane powder of this dry pulverization treatment method as a main material. It is described that it can be used as a therapeutic material for skin diseases and wounds, its auxiliary material, or cosmetic auxiliary material.

【０００４】[0004]

【発明が解決しようとする課題】上記従来技術では、概
略的な手抄き方式の卵殻膜シートの実施例などが記載さ
れているだけで(同公報第３頁左上欄参照)、シートの実
用性が強度などの点で必ずしも充分ではないうえ、シー
トの用途が生体適合性などを中心とした創傷治療的なも
のに限定されている。SUMMARY OF THE INVENTION In the above-mentioned prior art, only a rough example of a hand-made egg shell membrane sheet is described (see the same publication, page 3, upper left column), and the sheet is practically used. The property is not always sufficient in terms of strength and the like, and the use of the sheet is limited to those for wound treatment centering on biocompatibility.

【０００５】本発明は、卵殻膜の性状を損なわずにうま
く引き出した実用性の高い卵殻膜微細粉末の配合紙を開
発するとともに、この配合紙を従来からの創傷治療的な
使途以外の全く新しい用途を備えた各種機能紙として開
拓することにより、有機天然物資源である卵殻膜の効率
的な活用と資源の省力化を図ることを技術的課題とす
る。The present invention develops a highly practical compounded paper of eggshell membrane fine powder that has been successfully drawn out without impairing the properties of the eggshell membrane, and has a completely new purpose other than the conventional use for wound healing. By cultivating various functional papers that have various uses, the technical task is to efficiently utilize the eggshell membrane, which is an organic natural product resource, and to save resources.

【０００６】[0006]

【課題を解決するための手段】本発明者らは、卵殻膜並
びにその粉末化の技術を継続的に鋭意研究した結果、卵
殻膜を所定の湿式粉砕処理方式により粉末化すると、卵
殻膜を構成するタンパク質の性状を損なわずにその活性
をうまく引き出せること、並びに、この卵殻膜微細粉末
の配合紙が優れた吸湿、或は吸油機能などを発揮するこ
とを新たに発見して、調湿紙、吸油紙、皮脂除去紙など
の各種機能紙への利用を図った。Means for Solving the Problems As a result of continuous studies on the eggshell membrane and a technique for pulverizing the eggshell membrane, the inventors of the present invention constituted the eggshell membrane when the eggshell membrane was pulverized by a predetermined wet pulverization treatment method. It is possible to extract the activity of the protein without impairing the properties of the protein, and it has been newly discovered that the compound paper of this eggshell membrane fine powder exerts an excellent moisture absorption or oil absorption function. It was used for various functional papers such as oil-absorbent paper and oil-removal paper.

【０００７】即ち、本発明１は、卵殻膜を水及びアルコ
ール系溶媒の少なくともいずれかに浸漬し、石臼式回転
磨砕及びボールミル式粉砕の少なくともいずれかを施し
て卵殻膜の湿式粉砕粉末を製造し、この卵殻膜微細粉末
の繊維構造を絡み合わせてシート形態に加工することを
特徴とする卵殻膜微細粉末配合紙である。That is, in the present invention 1, an egg shell membrane is immersed in at least one of water and an alcoholic solvent, and at least one of stone mill type rotary grinding and ball mill type grinding is applied to produce a wet ground powder of the egg shell membrane. Then, the egg shell membrane fine powder-containing paper is characterized in that the fiber structure of this egg shell membrane fine powder is entangled and processed into a sheet form.

【０００８】本発明２は、上記本発明１において、４級
アンモニウム塩類などのカチオン系界面活性剤により卵
殻膜微細粉末と繊維組成物を水に分散させて紙料を調製
し、湿式抄紙することを特徴とする卵殻膜微細粉末配合
紙である。[0008] The present invention 2 is the same as the above Invention 1, in which the eggshell membrane fine powder and the fiber composition are dispersed in water with a cationic surfactant such as a quaternary ammonium salt to prepare a paper stock, and wet papermaking. The eggshell membrane fine powder blended paper characterized by the following.

【０００９】本発明３は、上記本発明１又は２の卵殻膜
微細粉末配合紙を湿度環境に接触させて、環境中の湿気
の吸収と放出により湿度調節可能にすることを特徴とす
る卵殻膜微細粉末を利用した調湿紙である。The present invention 3 is characterized in that the egg shell membrane fine powder-containing paper of the present invention 1 or 2 is brought into contact with a humidity environment, and the humidity can be controlled by absorbing and releasing moisture in the environment. It is a humidity control paper that uses fine powder.

【００１０】本発明４は、上記本発明１又は２に記載の
卵殻膜微細粉末配合紙を被処理物に接触させて、有効主
成分である卵殻膜により被処理物の油分を吸収除去可能
にすることを特徴とする卵殻膜微細粉末を利用した吸油
紙である。In the present invention 4, the egg shell membrane fine powder-containing paper according to the present invention 1 or 2 is brought into contact with an object to be treated, and the egg shell membrane as an effective main component makes it possible to absorb and remove the oil content of the object to be treated. It is an oil-absorbent paper using an egg shell membrane fine powder characterized in that

【００１１】本発明５は、上記本発明１又は２に記載の
卵殻膜微細粉末配合紙を被処理物に接触させて、被処理
物中の貴金属、重金属などの金属を吸着可能にすること
を特徴とする卵殻膜微細粉末を利用した金属捕集紙であ
る。A fifth aspect of the present invention is to bring the eggshell membrane fine powder-mixed paper according to the first or second aspect of the invention into contact with an object to be treated so that metals such as noble metals and heavy metals in the object can be adsorbed. It is a metal-collecting paper using the characteristic eggshell membrane fine powder.

【００１２】上記卵殻膜微細粉末は、卵殻膜を水及び／
又はアルコール系溶媒(即ち、水とアルコール系溶媒の混
合系か、アルコール系溶媒、或は水単独)の中で湿式粉
砕して製造する。当該粉砕処理は石臼式回転磨砕又はボ
ールミル式粉砕を夫々単独で施しても良いが、例えば、
卵殻膜に石臼式回転磨砕を施した後に、連続してボール
ミル式粉砕を施しても良く、この両方式の粉砕を複数回
繰り返しても差し支えない。因みに、上記卵殻膜微細粉
末は、生の卵殻膜を予備洗浄し、微粉砕化し、濾過洗浄
と乾燥処理で製造するのが好ましい。当該予備洗浄で
は、水洗してからアルコール系溶媒で洗浄し、卵殻膜に
付着する油脂分を溶解除去することもでき、卵殻膜を次
工程での湿式粉砕処理に適した浸漬物にする。The above-mentioned eggshell membrane fine powder is prepared by mixing the eggshell membrane with water and / or
Alternatively, it is produced by wet pulverization in an alcoholic solvent (that is, a mixed system of water and an alcoholic solvent, an alcoholic solvent, or water alone). The crushing treatment may be carried out individually by stone mill type rotary grinding or ball mill type crushing, for example,
The egg shell membrane may be subjected to stone mill rotary grinding and then continuously subjected to ball mill grinding, or both grinding may be repeated a plurality of times. Incidentally, it is preferable that the above-mentioned eggshell membrane fine powder is produced by prewashing a raw eggshell membrane, finely pulverizing it, and filtering and washing and drying it. In the preliminary washing, it is also possible to wash with water and then with an alcoholic solvent to dissolve and remove the oil and fat adhering to the eggshell membrane, and make the eggshell membrane an immersion product suitable for wet pulverization in the next step.

【００１３】上記アルコール洗浄を選択した場合の利点
は、水洗後の水分の残存を問題にせず、アルコールへの
完全置換を必要としない点にもある。このアルコール洗
浄から次の磨砕、粉砕までの一貫した工程におけるアル
コールの濃度は、０.０１〜９９.９９％とすることがで
きるが、実用上は、卵殻膜の殺菌消毒効果を同時に発揮
できる３０〜７０％のものが好ましい。使用するアルコ
ールは、飽和、不飽和の脂肪族及び芳香族のモノ、ジ、
そして多価アルコールなどの広範なものを使用できる
が、エタノール、イソプロパノールが好ましく、さらに
は、日本薬局方収載のものを７０％エタノール、３０
％、５０％イソプロパノールとして用いることができ
る。The advantage of selecting the above-mentioned alcohol cleaning is also that there is no problem of remaining water after the water cleaning, and complete replacement with alcohol is not required. The concentration of alcohol in the consistent steps from the alcohol cleaning to the next grinding and crushing can be 0.01 to 99.99%, but in practice, the bactericidal and disinfecting effect of the eggshell membrane can be exhibited at the same time. 30 to 70% is preferable. The alcohols used are saturated, unsaturated aliphatic and aromatic mono, di,
Although a wide range of polyhydric alcohols and the like can be used, ethanol and isopropanol are preferable, and those listed in the Japanese Pharmacopoeia are 70% ethanol and 30%.
%, 50% isopropanol can be used.

【００１４】上記微粉砕では、卵殻膜の前記アルコール
浸漬物(或は、水への浸漬物など)を石臼式回転磨砕とボ
ールミル式粉砕を繰り返して粉砕物懸濁液を得る。当該
石臼式磨砕機は上下２枚の特殊グラインダーによって構
成され、固定側の上部グラインダーと回転側の下部グラ
インダーの間に生じる衝撃、剪断、圧縮、ころがり摩擦
等の力により原料を粉砕するものである。用いるグライ
ンダーには、従来通りのものも使用できるが、最近開発
された無気孔で割れない特性を有するセラミックスのも
のが適している。投入する卵殻膜のアルコール浸漬物
(又は水への浸漬物など)は、その浸漬比率が１:０.５
(固体:分散媒(V/V))以上であれば良く、実際には１:１
から１:１０までの範囲の使用が好ましい。運転に際し
て、一度磨砕されたものを繰り返し磨砕機に投入する連
続磨砕処理も効果的である。さらに、連続磨砕処理の間
に分散媒を交換すると、洗浄効果を一層促進できる。In the above fine pulverization, the alcohol-immersed product of the eggshell membrane (or the immersed product in water) is repeatedly subjected to stone mill type rotary grinding and ball mill type grinding to obtain a ground product suspension. The stone mill type grinding machine is composed of upper and lower special grinders, and crushes the raw material by the force such as impact, shearing, compression, and rolling friction generated between the upper grinder on the fixed side and the lower grinder on the rotating side. . As the grinder to be used, a conventional one can be used, but a ceramic material which has been developed recently and has a characteristic that it does not crack without pores is suitable. Alcohol soaked egg shell membrane
(Or immersion product in water) has an immersion ratio of 1: 0.5
It should be above (solid: dispersion medium (V / V)), actually 1: 1
Use in the range from 1 to 1:10 is preferred. In operation, continuous grinding treatment in which the material that has been ground once is repeatedly fed into the grinder is also effective. Furthermore, the cleaning effect can be further promoted by exchanging the dispersion medium during the continuous grinding process.

【００１５】石臼式磨砕を終えた磨砕物は、そのままボ
ールミル式粉砕機に投入される。ボールミル式粉砕に
は、円筒の中に被粉砕物と粉砕媒体(例えば、ジルコニア
ボール)を入れて、円筒内の回転軸の動きにより回転粉
砕するか、円筒を振動させて粉砕する方法を利用するこ
とができる。本工程においても、被粉砕物である卵殻膜
粉末のアルコール浸漬比率は前の工程と同様のものとす
る。本工程からの粉砕物の分離回収には、粉砕媒体のボ
ールの直径より小さい枡目のふるいを通してボールを捕
捉しておき、下段に設けたマイクロフィルターで粉砕物
懸濁液を濾過することにより行う。ボールの洗浄と濾集
粉砕物は、アルコール又は他の揮発性有機溶媒により、
卵殻膜由来の残存油脂分を洗浄除去後、乾燥して卵殻膜
微細粉末(最小粒子径で数ミクロン程度)とされる。この
最終段階の洗浄では、元の卵殻膜の容積が小さくなって
おり、また逆に表面積が大きくなっているので、効果的
に油脂分を溶解除去できる。尚、洗浄溶媒は各々単用若
しくは併用できるが、アセトン、エーテルを使用するこ
とも可能である。The ground product that has been subjected to the stone mill type grinding is put into the ball mill type crusher as it is. In the ball mill type pulverization, a method in which an object to be pulverized and a pulverization medium (for example, zirconia balls) are put in a cylinder and pulverized by rotation by the movement of a rotating shaft in the cylinder or oscillating the cylinder to pulverize is used. be able to. Also in this step, the alcohol immersion ratio of the eggshell membrane powder to be crushed is the same as in the previous step. Separation and collection of the pulverized product from this step is performed by capturing the ball through a sieve having a mesh smaller than the diameter of the ball of the pulverizing medium, and filtering the pulverized product suspension with a microfilter provided in the lower stage. . The balls are washed and the filter cake is crushed with alcohol or other volatile organic solvent.
The residual oil and fat derived from the eggshell membrane is washed and removed, and then dried to obtain an eggshell membrane fine powder (minimum particle diameter of about several microns). In this final-stage washing, the volume of the original eggshell membrane is small and, conversely, the surface area is large, so that the fats and oils can be effectively dissolved and removed. The washing solvents can be used alone or in combination, but acetone or ether can also be used.

【００１６】上記卵殻膜微細粉末は、前述のように、水
及び／又はアルコール系溶媒中で石臼式回転磨砕又はボ
ールミル式粉砕を施す湿式粉砕粉末であり、卵殻膜微細
粉末の粒子径としては、ミクロン単位を中心とした種々
の大きさに調製するのが一般的であるが、数十μｍ〜数
μｍ程度に調製すると、卵殻膜が本来的に保有する有機
構造に由来する比較的マクロな繊維構造を保持できる。
また、上記卵殻膜微細粉末は、乳酸、尿素、チオグリコ
ール酸などで適宜処理しても良い。As described above, the egg shell membrane fine powder is a wet pulverized powder which is subjected to stone mill type rotary grinding or ball mill type pulverization in water and / or alcoholic solvent, and the egg shell membrane fine powder has a particle size of , It is generally prepared in various sizes centered on the micron unit, but when prepared to have a size of several tens of μm to several μm, a relatively macroscopic structure derived from the organic structure originally possessed by the eggshell membrane is obtained. Can retain the fiber structure.
Further, the eggshell membrane fine powder may be appropriately treated with lactic acid, urea, thioglycolic acid or the like.

【００１７】上記卵殻膜微細粉末配合紙は、卵殻膜微細
粉末の繊維構造が絡み合ったシート形態のものを意味
し、一般的には、卵殻膜微細粉末と繊維組成物を混合し
た分散スラリーを紙料として調製し、この紙料を湿式抄
紙した繊維間自己接着性による抄造紙を基本とするが、
次の(1)〜(3)の紙なども包含される。 (1)卵殻膜微細粉末のみをラテックスなどの結合剤の添
加、或は無添加の条件下で湿式抄紙した紙。卵殻膜微細
粉末は比較的マクロな繊維構造を有するため、他の繊維
組成物を配合しなくても、湿式抄紙できる。 (2)卵殻膜微細粉末の分散液を結合剤の添加、或は無添
加の条件下で基材上に均一に塗布して乾燥するキャステ
ィング方式などで製造した紙。 (3)紙の片面、又は両面に卵殻膜微細粉末の塗膜を上記
(2)の方式などで固着した積層紙。また、紙同士の間に
卵殻膜微細粉末の塗膜を介在させた積層紙など。The above eggshell membrane fine powder blended paper means a sheet form in which the fiber structure of the eggshell membrane fine powder is entangled, and generally, a dispersion slurry prepared by mixing the eggshell membrane fine powder and the fiber composition is made into a paper. It is prepared as a paper, and the paper is basically made by wet papermaking, which is based on the self-adhesiveness between fibers.
The following papers (1) to (3) are also included. (1) Paper obtained by wet papermaking using only eggshell membrane fine powder with or without addition of a binder such as latex. Since the eggshell membrane fine powder has a relatively macro fiber structure, wet papermaking can be performed without adding other fiber composition. (2) Paper produced by a casting method or the like in which a dispersion liquid of egg shell membrane fine powder is uniformly applied onto a base material with or without a binder added and dried. (3) On one or both sides of the paper, apply a coating of eggshell membrane fine powder to the above
Laminated paper fixed by the method of (2). In addition, laminated paper in which a coating film of eggshell membrane fine powder is interposed between papers.

【００１８】上記繊維組成物は、製紙用として普通に使
用できるＮＢＫＰ・ＬＢＫＰ等の木材パルプ、脱墨パル
プ(ＤＩＰ)のほか、リンターパルプ・麻・バガス・ケナフ・
エスパルト草・ワラなどの非木材繊維パルプでも良い。
また、ポリエチレン・ポリプロピレン・ポリビニルアルコ
ール・ポリエステル・ポリアクリルニトリル系等の合成繊
維、レーヨン・キュプラ・アセテート等の再生又は半合成
繊維、ロックウール・ガラス繊維・炭素繊維等の無機繊維
などでも差し支えない。さらに、アルギン酸(及びその
塩)は生体親和性が良いので、これを繊維化したアルギ
ン酸繊維を当該繊維組成物に選択又は併用することもで
きる。尚、上記繊維組成物は用途に応じて適宜配合率を
変化させれば良く、パルプは未晒パルプ、晒パルプ(染
色されたものでも可)を単用、或は併用することができ
る。The above-mentioned fiber composition is used for papermaking, such as wood pulp such as NBKP and LBKP, deinked pulp (DIP), linter pulp, hemp, bagasse, kenaf, etc.
Non-wood fiber pulp such as esparto grass and straw may be used.
In addition, synthetic fibers such as polyethylene, polypropylene, polyvinyl alcohol, polyester, polyacrylonitrile, etc., recycled or semi-synthetic fibers such as rayon, cupra, acetate, etc., inorganic fibers such as rock wool, glass fiber, carbon fiber, etc. may be used. Further, since alginic acid (and its salt) has good biocompatibility, alginic acid fibers obtained by fibrating the alginic acid can be selected or used in combination with the fiber composition. Incidentally, the above-mentioned fiber composition may be appropriately mixed depending on the application, and the pulp may be unbleached pulp, bleached pulp (dyed pulp may be used) alone or in combination.

【００１９】上記湿式抄紙の場合、機械漉き、手漉きを
問わないが、機械漉きでは、一般に、円網、短網、長
網、サクションホーマー等の抄紙機を使用する。例え
ば、本発明２では、分散スラリーは卵殻膜微細粉末の懸
濁液であるが、ＪＩＳ−Ｐ−８２０９等の方式に基づけ
ば、容易に抄紙できる。In the case of the above-mentioned wet papermaking, it does not matter whether it is machine-made or hand-made, but in the case of machine-making, generally, a paper machine such as a cylinder, a short-mesh, a fourdrinier, and a suction homer is used. For example, in the present invention 2, the dispersed slurry is a suspension of eggshell membrane fine powder, but paper can be easily made based on the method of JIS-P-8209 or the like.

【００２０】上記湿式抄紙における紙料の調製は、卵殻
膜微細粉末を水に分散した液と繊維組成物の分散液を別
々に整えてから混合処理する２液方式でも良いし、卵殻
膜微細粉末と繊維組成物を同時に分散する１液方式でも
差し支えないが、卵殻膜微細粉末と繊維組成物の配合割
合を容易に選択できる点で、２液混合方式が便利であ
る。The stock for the wet papermaking may be prepared by a two-liquid system in which a liquid obtained by dispersing eggshell membrane fine powder in water and a dispersion liquid of the fiber composition are separately prepared and then mixed, or the eggshell membrane fine powder is used. Although the one-liquid system in which the fiber composition and the fiber composition are simultaneously dispersed may be used, the two-liquid mixing system is convenient in that the mixing ratio of the eggshell membrane fine powder and the fiber composition can be easily selected.

【００２１】上記卵殻膜微細粉末は、例えば、同じケラ
チンタンパク質で構成される羽毛微細粉末(本出願人が
特開平４−３１２５３４号公報などで先に開示)に比べ
て表面疎水性は高くはないため(後述の試験例参照)、水
になじんで比較的分散し易いが、湿式抄紙に際しては、
通常、カチオン系、ノニオン系、或は両性などの各種界
面活性剤で水中に分散する。この場合、上記カチオン系
界面活性剤は、特に、卵殻膜微細粉末の分散能力に優れ
ており、具体的には、下記の〜などの４級アンモニ
ウム塩類が好適である。 脂肪族アンモニウム塩類 芳香族アンモニウム塩類 ピリジニウム塩系、イミダゾリニウム塩系等の複素環
アンモニウム塩類 セルロース系或は〜のポリオキシアルキレンの付
加物The above-mentioned egg shell membrane fine powder is not higher in surface hydrophobicity than, for example, feather fine powder composed of the same keratin protein (disclosed earlier by the present applicant in Japanese Patent Laid-Open No. 4-31534, etc.). For this reason (see Test Examples below), it is relatively easy to disperse in water, but during wet papermaking,
Usually, it is dispersed in water with various surfactants such as cationic type, nonionic type and amphoteric type. In this case, the above-mentioned cationic surfactant is particularly excellent in the dispersing ability of the eggshell membrane fine powder, and specifically, quaternary ammonium salts such as the following are preferable. Aliphatic ammonium salts, aromatic ammonium salts, pyridinium salt-based, imidazolinium salt-based, etc. heterocyclic ammonium salts Cellulose-based or polyoxyalkylene adducts of

【００２２】上記の脂肪族アンモニウム塩類として
は、モノアルキルトリメチル、或はジアルキルジメチル
アンモニウム塩類、脂肪族アミド・ポリアミン類などが
挙げられ、具体的には、ジアルキル・ジメチルアンモニ
ウムクロライド(アーカード2HT-75;ライオン製等)、ラ
ウリル・トリメチルアンモニウムクロライド(カチオーゲ
ンTML;第一工業薬品製等)、セチル・トリメチルアンモニ
ウムクロライド(カチオーゲンTMP;第一工業薬品製等)、
ステアリル・トリメチルアンモニウムクロライド(カチオ
ーゲンTMS;第一工業薬品製等)、ジステアリル・ジメチル
アンモニウムクロライドなどが挙げられる。上記の芳
香族アンモニウム塩類としては、ベンザルコニウム塩
類、ベンゼトニウム塩類などが挙げられ、具体的には、
塩化ベンザルコニウム(カチオンG-50及びカチオンM;三
洋化成製、ニッカノンBZ;日華化学製等、より具体的に
は、ステアリル・ジメチル・ベンジルアンモニウムクロラ
イド;スワノールCA-1485;日本サーファクタント製等)な
どが挙げられる。上記の複素環アンモニウム塩類とし
ては、セチル・ピリジニウムクロライドなどが挙げられ
る。Examples of the above-mentioned aliphatic ammonium salts include monoalkyltrimethyl or dialkyldimethylammonium salts and aliphatic amide / polyamines. Specifically, dialkyldimethylammonium chloride (ARCARD 2HT-75; Lion, etc.), lauryl trimethylammonium chloride (Cathiogen TML; manufactured by Daiichi Kogyo, etc.), cetyl trimethylammonium chloride (Cationogen TMP; manufactured by Daiichi Kogyo, etc.),
Stearyl / trimethylammonium chloride (Cationogen TMS; manufactured by Dai-ichi Kogyo Yakuhin, etc.), distearyl / dimethylammonium chloride and the like can be mentioned. Examples of the aromatic ammonium salts include benzalkonium salts and benzethonium salts, and specifically,
Benzalkonium chloride (Cation G-50 and Cation M; Sanyo Kasei, Nikkanon BZ; Nika Kagaku etc., more specifically, stearyl dimethyl benzyl ammonium chloride; Swanol CA-1485; Nippon Surfactant etc.) And so on. Examples of the above heterocyclic ammonium salts include cetyl pyridinium chloride.

【００２３】上記４級アンモニウム塩類は紙料に加えた
場合に泡立ちがないか、少ないため、その配合率は０.
０１〜０.０５重量％程度が一般的である。The above-mentioned quaternary ammonium salts have no or little foaming when added to the paper stock, so that the compounding ratio is 0.1.
Generally, it is about 01 to 0.05% by weight.

【００２４】また、上記抄紙工程においては、下記に示
すように、通常の湿式抄紙で使用する各種薬剤を始め、
種々の処理剤を配合できる。 (1)湿潤紙力増強剤としては、ポリアミドアミンエピク
ロルヒドリン系樹脂、ホルムアルデヒド縮合物やポリエ
チレンイミン等のカチオン系ポリマーがあり、アニオン
系ポリマーを併用するのが一般的である。当該アニオン
系ポリマーには、アニオン系ポリアクリルアミドなどが
挙げられる。但し、卵殻膜微細粉末の湿式抄紙では、各
種の繊維や填料に自己定着性がある両性イオンラテック
ス系のバインダーを用いると、送りや地合が円滑化され
て、抄紙に好適である。In the above papermaking process, as shown below, various chemicals used in ordinary wet papermaking,
Various treating agents can be blended. (1) As the wet paper strength enhancer, there are polyamidoamine epichlorohydrin resins, cationic polymers such as formaldehyde condensates and polyethyleneimine, and it is common to use anionic polymers together. Examples of the anionic polymer include anionic polyacrylamide. However, in the wet papermaking of the eggshell membrane fine powder, if a zwitterionic latex-based binder having self-fixing property for various fibers and fillers is used, feeding and forming are facilitated, which is suitable for papermaking.

【００２５】(2)乾燥紙力増強剤としては、澱粉、酸化
澱粉・カルボキシメチル澱粉・カチオン化澱粉などの変性
澱粉、グアーガム・キサンタンガムなどの植物ガム、ポ
リビニルアルコール(ＰＶＡ)、カルボキシメチルセルロ
ース(ＣＭＣ)、ポリアクリルアミド(アニオン性・カチオ
ン性・両性)などを配合でき、これらの添加により、卵殻
膜微細粉末の脱落を円滑に防止する。(2) Examples of the dry paper strength enhancer include starch, modified starch such as oxidized starch, carboxymethyl starch and cationized starch, plant gum such as guar gum and xanthan gum, polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC). , Polyacrylamide (anionic / cationic / amphoteric), etc. can be blended, and addition of these can smoothly prevent the eggshell membrane fine powder from falling off.

【００２６】(3)紙に柔軟性や平滑性を付与するため、
クレー、タルクなどの各種填料を使用できる。 (4)内部サイジングとして、ロジン系の酸性サイズ剤、
或は、アルキルケテンダイマー・アルケニル無水コハク
酸などの中性サイズ剤を使用できる。 (5)ポリエチレンオキシド(ＰＥＯ)などの粘剤などを添
加しても良い。(3) To impart flexibility and smoothness to the paper,
Various fillers such as clay and talc can be used. (4) As an internal sizing, a rosin-based acidic sizing agent,
Alternatively, a neutral sizing agent such as alkyl ketene dimer / alkenyl succinic anhydride can be used. (5) A sticking agent such as polyethylene oxide (PEO) may be added.

【００２７】(6)例えば、卵殻膜微細粉末配合紙を調湿
紙に供する場合、シリカゲル、アルミナゲル、(天然・合
成)ゼオライトなどの他の無機系の調湿剤を補填するこ
とを妨げない。また、塩化コバルトなどを漉き込んで、
吸湿・放湿に伴い、淡紅色と青色間で色変化させるな
ど、調湿紙に色変を起こすように工夫しても良い。(6) For example, when the eggshell membrane fine powder blended paper is used as a humidity control paper, it does not prevent supplementing with other inorganic humidity control agents such as silica gel, alumina gel, and (natural / synthetic) zeolite. . Also, add cobalt chloride etc.,
It is also possible to devise a color change on the humidity-controlled paper, such as changing the color between light pink and blue due to moisture absorption / release.

【００２８】上記配合紙では、繊維総重量に対する卵殻
膜微細粉末の配合比率は０.１〜１００重量％である
が、湿式抄造する場合、卵殻膜微細粉末による各種機能
の促進や、脱水・目詰まり防止などにより抄紙の円滑化
を図る見地から、卵殻膜微細粉末の配合率は２０〜８０
重量％が好ましく、より好ましくは５０〜７０重量％で
ある。上記卵殻膜微細粉末の粒子径は一般に３ｍｍ〜数
μｍ程度であり、実際的には数十μｍ程度のものが適当
である。また、当該配合紙は、紙厚としては薄紙から板
紙までを含む概念である。In the above-mentioned compounded paper, the mixing ratio of the eggshell membrane fine powder to the total fiber weight is 0.1 to 100% by weight. However, in the case of wet papermaking, the eggshell membrane fine powder promotes various functions, dehydration and eyes From the viewpoint of smoothing papermaking by preventing clogging, etc., the mixing ratio of the eggshell membrane fine powder is 20-80.
% By weight, more preferably 50 to 70% by weight. The particle size of the above eggshell membrane fine powder is generally about 3 mm to several μm, and in practice, a particle size of about several tens μm is suitable. Further, the compounded paper is a concept that includes thin paper to paperboard as the paper thickness.

【００２９】上記金属捕集紙による捕集方法としては、
金属捕集紙を積層した容器内に金属含有液を通す濾過方
式が一般的であるが、金属含有液の中に多数枚の金属捕
集紙を浸漬するなどして、金属含有液と接触させても差
し支えない。The collection method using the metal collecting paper is as follows.
A filtration method in which a metal-containing liquid is passed through a container in which metal collecting papers are stacked is generally used, but a large number of metal collecting papers are immersed in the metal-containing liquid to bring them into contact with the metal-containing liquid. It doesn't matter.

【００３０】[0030]

【作用】湿式粉砕処理した本卵殻膜微細粉末は比較的マ
クロな繊維構造を有しており、繊維間自己接着性がある
うえ、他の繊維組成物とも絡み易いため、湿式抄紙に適
している。因みに、実際に卵殻膜微細粉末配合紙を顕微
鏡で観察すると、図８に示すように、卵殻膜の繊維構造
が絡み合っている様子が確認できる。また、後述の試験
例にも示すように、卵殻膜微細粉末は羽毛微細粉末に比
べても表面疎水性は高くはなく、模式的には、親水性的
な殻で覆われた繊維状疎水物の性質を帯びるため、水に
分散し易く、この点でも湿式抄紙に有利である。そのう
え、卵殻膜微細粉末の懸濁水に４級アンモニウム塩類を
使用すると、卵殻膜微細粉末の分散性がより向上するた
め、抄造紙の地合が良くなる。[Function] The eggshell membrane fine powder subjected to wet pulverization has a relatively macro fiber structure, has self-adhesive properties between fibers, and is easily entangled with other fiber compositions, and is therefore suitable for wet papermaking. . Incidentally, when the eggshell membrane fine powder-mixed paper is actually observed with a microscope, it can be confirmed that the fiber structure of the eggshell membrane is intertwined, as shown in FIG. In addition, as shown in the test examples below, the egg shell membrane fine powder is not so high in surface hydrophobicity as compared with the feather fine powder, and is typically a fibrous hydrophobic substance covered with a hydrophilic shell. Since it has the property of (3), it is easily dispersed in water, which is also advantageous for wet papermaking. In addition, when a quaternary ammonium salt is used in the suspension water of the eggshell membrane fine powder, the dispersibility of the eggshell membrane fine powder is further improved, so that the texture of the papermaking paper is improved.

【００３１】この卵殻膜微細粉末配合紙は、従来の創傷
被覆的な機能とは別に、水分或は油分に対する鋭敏な活
性を示す。例えば、卵殻膜微細粉末は油分の吸着能力が
高く、食品などの油吸収、皮膚面の皮脂除去、制汗、或
は、創傷面の体液吸収などに好適である。また、卵殻膜
微細粉末は湿気を吸着するだけではなく、吸着後の放出
も可能であって、湿気を呼吸して吸湿と放湿を可逆的に
行うので、簡略な操作で湿度環境を調節できる。The eggshell membrane fine powder-blended paper shows a sensitive activity against moisture or oil, in addition to the conventional wound-covering function. For example, the eggshell membrane fine powder has a high ability to adsorb oil, and is suitable for absorbing oil such as foods, removing sebum on the skin surface, antiperspirant, or absorbing body fluid on the wound surface. In addition, the eggshell membrane fine powder not only adsorbs moisture, but can also release it after adsorption, and respires moisture to absorb and release moisture reversibly, so the humidity environment can be adjusted with simple operations. .

【００３２】また、卵殻膜微細粉末の繊維間自己接着性
を利用した配合紙、或は、卵殻膜微細粉末を他の繊維組
成物の繊維間に漉き込んだ配合紙は、図８に示すよう
に、卵殻膜の繊維構造が均質に広く分布して外気との接
触面積が増大するため、卵殻膜微細粉末の有する吸湿、
吸油などの上記活性作用を大きく展開できる。Further, a compounded paper utilizing the inter-fiber self-adhesiveness of eggshell membrane fine powder or a compounded paper in which eggshell membrane fine powder is squeezed between fibers of another fiber composition is as shown in FIG. In addition, since the fiber structure of the eggshell membrane is widely distributed uniformly and the contact area with the outside air increases, the moisture absorption that the eggshell membrane fine powder has,
The above-mentioned active action such as oil absorption can be greatly expanded.

【００３３】[0033]

【発明の効果】【The invention's effect】

(1)多くが廃棄処分にされている卵殻膜を微細化し、こ
の微細粉末を紙に加工するとともに、調湿紙、吸油紙な
どの新たな用途を備えた各種機能紙として広く活用でき
るため、廃材の有効利用と資源の省力化を同時に図れ
る。また、天然物の卵殻膜タンパクの特性を活かした微
粉末の配合紙であるため、その利用に際しても、環境汚
染の危険がなく、生体への影響もない安全なエコロジー
商品となる。(1) Since eggshell membranes that are mostly discarded are miniaturized and this fine powder is processed into paper, it can be widely used as various functional papers with new applications such as humidity control paper and oil absorbent paper. Effective use of waste materials and resource saving can be achieved at the same time. In addition, since it is a fine powder compound paper that takes advantage of the properties of the natural egg shell membrane protein, it is a safe ecological product that is free from the risk of environmental pollution and has no effect on the living body when used.

【００３４】(2)卵殻膜をアルコール系溶媒により石臼
式回転磨砕などの所定の方式で湿式粉砕処理した微粉末
なので、卵殻膜が有機天然物として本来的に備えていた
比較的マクロな繊維構造を損なうことがない。このた
め、本発明１及び２の卵殻膜配合紙は、図８に示すよう
に、卵殻膜の繊維同士が良好に絡み合った紙であり、冒
述の従来技術の卵殻膜シートなどとは異なり、強度など
の点で実用性が高い。また、卵殻膜微細粉末は羽毛微細
粉末に比べて表面疎水性が高くはないため、比較的水に
分散し易く、この点でも湿式抄紙に適している。(2) The eggshell membrane is a fine powder obtained by wet pulverizing it with an alcoholic solvent by a predetermined method such as stone mill type rotary grinding, so that the eggshell membrane is a relatively macro fiber originally provided as an organic natural product. It does not damage the structure. Therefore, the eggshell membrane-containing paper of the present invention 1 and 2 is a paper in which the fibers of the eggshell membrane are entangled well with each other, as shown in FIG. 8, which is different from the eggshell membrane sheet of the prior art mentioned above. It is highly practical in terms of strength. Further, the egg shell membrane fine powder is not so high in surface hydrophobicity as the feather fine powder, so that it is relatively easy to disperse in water, and this point is also suitable for wet papermaking.

【００３５】(3)卵殻膜微細粉末配合紙は、下述のよう
に、前記従来技術の創傷治療的な使途とは全く別の調湿
や吸油などの新たな機能に着目したものであり、調湿紙
や吸油紙などの新規な用途を備えた各種機能紙として市
場に提供できる。(3) The eggshell membrane fine powder-blended paper is, as described below, focused on new functions such as humidity control and oil absorption, which are completely different from the above-mentioned conventional uses for wound therapy. It can be provided to the market as various functional papers with new uses such as humidity control paper and oil absorbent paper.

【００３６】また、卵殻膜微細粉末を繊維間に漉き込ん
で紙に加工することで、卵殻膜の繊維構造が均質に広く
分布して外気との接触面積が増大するため、卵殻膜微細
粉末の有する上記機能を有効に引き出せる。そのうえ、
卵殻膜を微細粉末から紙に加工することで、被処理物へ
の接触、貼着、擦り付けなどが容易になり、使用の利便
性が高まる。When the eggshell membrane fine powder is processed into paper by squeezing it between the fibers, the fiber structure of the eggshell membrane is uniformly and widely distributed and the contact area with the outside air is increased. It is possible to effectively take out the above-mentioned function. Besides,
By processing the eggshell membrane from fine powder into paper, it becomes easy to contact, stick, rub, etc. with the object to be processed, and the convenience of use is enhanced.

【００３７】(4)卵殻膜微細粉末配合紙は卵殻膜微細粉
末を原材料とするため、暖かみのある独特の風合を保有
し、この点でも今までにない種類の紙を市場に提供でき
る。(4) Eggshell membrane fine powder-blended paper has a unique texture with warmth because it uses eggshell membrane fine powder as a raw material, and in this respect also, it is possible to provide the market with unprecedented types of paper.

【００３８】(5)卵殻膜微細粉末配合紙は、後述の試験
例にも示すように、湿気の吸着と吸着後の放出に優れ、
湿気を呼吸して吸湿と放湿を可逆的に行えるため、湿度
環境を有効に保全でき、湿度調節の機能紙、即ち、調湿紙
として優れている。特に、紙形態である調湿紙では、上
述のように、折り畳みや変形が容易で、使用の利便性が
高い。以下、本調湿紙の具体的用途を示す。(5) The eggshell membrane fine powder blended paper is excellent in the adsorption of moisture and the release after adsorption, as shown in the test examples described later.
Since it respires moisture to absorb and release moisture reversibly, it can effectively maintain the humidity environment and is excellent as a functional paper for humidity control, that is, a humidity control paper. In particular, the humidity control paper in the form of paper is easy to fold and deform as described above, and is highly convenient to use. The specific uses of the humidity-controlled paper are shown below.

【００３９】書籍類、美術品、工芸品などの収蔵や運
搬。この場合には、本棚や収蔵庫などの壁面に貼る。 空調用のハニカム濾紙用に用いて、結露防止を図る。 屋内の壁紙に用いて結露防止を図る。 野菜などを包装して冷蔵庫に保存する。特に、葉菜類
等が冷蔵庫内で乾燥してパサつくのを防止する。 タンスや押し入れの中敷き、或は、和服や毛皮などの
収納。包装紙として、単独、或は和紙などと混用する。
また、カーペットの下敷きなどに利用する。 エレクトロニクス製品、フィルムなどの湿気に敏感な
機器や物品の保全。 衣類、寝装具(例えば、枕カバーやシーツなど)の湿気
の除去に利用する。 テニスラケット、バット、ゴルフ用品等を始めとする
スポーツ用品などのグリップ部のテープに用いる。 研究用薬品類の保管。従来では、シリカゲルや塩化カ
ルシウムなどを入れたデシケータを保管容器としていた
が、これらの乾燥剤の代替品として用いる。Storage and transportation of books, arts, crafts, etc. In this case, attach it to the wall of a bookshelf or storage. Use for honeycomb filter paper for air conditioning to prevent dew condensation. Use as indoor wallpaper to prevent condensation. Wrap vegetables and store in the refrigerator. In particular, it prevents leafy vegetables from drying out in the refrigerator and becoming dry. Storage of closets, closets, or Japanese clothes and fur. As a wrapping paper, used alone or mixed with Japanese paper.
It is also used as an underlay for carpets. Conservation of moisture-sensitive devices and articles such as electronic products and films. Used to remove moisture from clothes and bedding (eg pillowcases and sheets). Used as a tape for the grip of sports equipment such as tennis rackets, bats and golf equipment. Storage of research chemicals. Conventionally, a desiccator containing silica gel or calcium chloride has been used as a storage container, but it is used as a substitute for these desiccants.

【００４０】(6)卵殻膜微細粉末配合紙は後述の試験例
に示すように吸油能力に優れ、吸油紙として好適であ
る。以下、本吸油紙の具体的用途を示す。 食品用の包材。全部包装、或は一部包装に用いる。例
えば、ケーキ、菓子などの下部を包むレースペーパー
や、フライや油揚げなどの揚げ物の敷紙に使用すると、
余剰の油分を吸い取れる。また、上記レースペーパーに
供すると、前述の水分調節機能により、ケーキなどの食
品の水分保持機能も発揮できる。さらに、本吸油紙をパ
ウンドケーキなどを焼く場合の焼き型の離型紙に適用す
ると、焼き上がったケーキを型からスムーズに抜き外せ
る。(6) The eggshell membrane fine powder blended paper is excellent in oil absorption capacity as shown in the test examples described later and is suitable as an oil absorption paper. Hereinafter, specific uses of the oil-absorbent paper will be shown. Packaging material for food. Used for all packaging or some packaging. For example, when used for lace paper that wraps the bottom of cakes, confectionery, etc.
Can absorb excess oil. Further, when it is used for the lace paper, it can also exert a moisture retaining function of food such as cake due to the moisture regulating function described above. Furthermore, when the oil-absorbent paper is applied to a baking paper release paper for baking pound cake, the baked cake can be smoothly removed from the mold.

【００４１】油捕集紙。 油汚染した機械類、家庭やレストランの食器、或は湯垢
の付いた湯舟などの汚染表面に紙を擦り付けると、油分
や湯垢を良好に除去して速やかに表面を清浄にできる。
また、工場廃油、河川や海洋の浮上油、或は流出油など
も当該捕集紙で速やかに吸収除去して、環境を良好に保
全できる。Oil collecting paper. If you rub the paper on a contaminated surface such as oil-contaminated machinery, tableware in homes and restaurants, or a bath with water stains, you can remove oil and water stains well and clean the surface quickly.
In addition, waste oil from factories, floating oil from rivers and oceans, or spilled oil can be quickly absorbed and removed by the collecting paper, and the environment can be well preserved.

【００４２】皮脂除去紙や制汗紙などの化粧用機能
紙。 この機能紙を皮膚面に接触させると、その吸油能力によ
り皮膚面の皮脂分や老廃物などを有効に除去できる。ま
た、脇の下や掌などに付着させると、速やかに制汗でき
る。さらには、施設の手摺やノブ、事務機器や机、或は
スポーツ用品等のグリップ部などの皮膚が触れる箇所に
この機能紙を張り付けると、接触部に指紋や皮脂が付か
ず、表面をサラッとした感触と美観に良好に保持でき
る。因みに、この化粧用機能紙を化粧パックに適用する
と、顔面などの皮脂を除去できるうえ、逆に、皮膚面に
卵殻膜タンパクなどの栄養分を補給することも期待でき
る。尚、上記調湿紙などとの境界に属すると思われる
が、ベビー或は老人のおむつ交換時の汗分除去用に本化
粧用機能紙を適用することもできる。Functional paper for makeup such as sebum removal paper and antiperspirant paper. When this functional paper is brought into contact with the skin surface, its oil absorption ability enables effective removal of sebum and waste products from the skin surface. Also, if you attach it to your armpit or palm, you can quickly stop sweating. In addition, if you stick this functional paper to a place where skin touches, such as facility handrails and knobs, office equipment and desks, or grips of sports equipment, etc., the contact surface will not get fingerprints or sebum and the surface will be smooth. It is possible to maintain good feeling and aesthetics. By the way, when this functional cosmetic paper is applied to a makeup pack, it can be expected to remove sebum from the face and the like, and, conversely, to supplement the skin surface with nutrients such as eggshell membrane proteins. Although it seems to belong to the boundary with the humidity control paper and the like, the present functional cosmetic paper can be applied to remove sweat when a baby or an old person changes diapers.

【００４３】医薬用機能紙。 卵殻膜微細粉末配合紙は、そのままの形態で創傷部など
の被覆に利用できる。当該配合紙を皮膚面の創傷部に被
覆すると、創傷部から浸出する体液や膿などを円滑に吸
収除去できるとともに、上記(5)に示す吸湿性により被
覆部のムレを防止できる。尚、卵殻膜微細粉末と繊維組
成物から湿式抄紙する場合、繊維組成物として通常のパ
ルプ等に替えて生体親和性が良い前記アルギン酸繊維を
(或は、アルギン酸繊維に加え、他の繊維組成物を併せて)
用いることもできる。Functional medical paper. The eggshell membrane fine powder-blended paper can be used as it is for covering wounds and the like. When the wound part on the skin surface is covered with the compounded paper, it is possible to smoothly absorb and remove body fluid, pus, etc. leaching from the wound part, and prevent the stuffiness of the covering part due to the hygroscopicity described in (5) above. In the case of wet papermaking from the eggshell membrane fine powder and the fiber composition, the alginic acid fiber having good biocompatibility is used as the fiber composition instead of ordinary pulp.
(Or, in addition to alginic acid fiber, combine other fiber composition)
It can also be used.

【００４４】(7)湿式抄紙の場合、卵殻膜微細粉末に４
級アンモニウム塩類などのカチオン系界面活性剤を併用
すると、卵殻膜微細粉末の分散性が向上するため、繊維
の粗密が解消されて均一化し、抄造紙の地合いが良くな
る。また、分散性が良い分、紙料を水で希釈して分散性
を高める必要がなくなるため、抄紙の際の節水効率が上
がる。(7) In the case of wet papermaking, the eggshell membrane fine powder is 4
When a cationic surfactant such as a quaternary ammonium salt is used in combination, the dispersibility of the eggshell membrane fine powder is improved, so that the coarseness and fineness of the fibers are eliminated and the fibers are made uniform, and the texture of the papermaking paper is improved. In addition, since the dispersibility is good, it is not necessary to dilute the paper material with water to improve the dispersibility, so that the water saving efficiency at the time of papermaking is increased.

【００４５】(8)卵殻膜微細粉末は、作用の項目でも述
べたように、卵殻膜を所定の湿式粉砕処理で調製した微
細粉末なので、粉末の表面に多くの吸着サイトが露出す
ると推定でき、この粉末の配合紙は、後述の試験例に示
すように、鉛、鉄、銅、亜鉛等の重金属を初めとして、
パラジウム、銀等を代表とする貴金属などを有効に吸着
できる。因みに、特開昭５８−１５０４３３号公報に
は、生の卵殻膜に加熱乾燥、或は凍結乾燥などを施し、
ハンマーミル、スパイラルミル等で粉砕して製造した乾
式粉砕処理方式の卵殻膜粉末が、鉛、銅、水銀などの有
害金属の除去に効果があることが記載されているが、本
発明の卵殻膜微細粉末配合紙は、紙形態で各種の重金属
を吸着できるだけではなく、パラジウムなどの貴金属を
吸着できる点で、当該公報の技術とは異なる。このた
め、卵殻膜微細粉末を配合した本金属捕集紙は、各種の
産業廃水や海水などから重金属、貴金属などを効率的に
回収するのに好適である。(8) The eggshell membrane fine powder is a fine powder prepared by subjecting the eggshell membrane to a predetermined wet pulverization treatment as described in the item of action, so it can be estimated that many adsorption sites are exposed on the surface of the powder, The powder-containing paper has lead, iron, copper, zinc, and other heavy metals, as shown in the test examples below.
It can effectively adsorb precious metals such as palladium and silver. Incidentally, in JP-A-58-150433, a raw eggshell membrane is subjected to heat drying, freeze drying, or the like,
It is described that the eggshell membrane powder of the dry pulverization method produced by pulverizing with a hammer mill, a spiral mill, etc. is effective in removing harmful metals such as lead, copper and mercury, but the eggshell membrane of the present invention The finely powdered paper is different from the technique of the publication in that it can adsorb various heavy metals in the form of paper as well as noble metals such as palladium. Therefore, the present metal collecting paper containing the eggshell membrane fine powder is suitable for efficiently recovering heavy metals, precious metals and the like from various industrial wastewaters, seawater and the like.

【００４６】[0046]

【実施例】以下、卵殻膜微細粉末(ESMP;Egg Shell Memb
rane Powder)の製造実施例、当該粉末の表面疎水性と分
散性の試験例、並びに卵殻膜微細粉末の配合紙の製造実
施例を述べるとともに、卵殻膜微細粉末とその配合紙の
各吸湿・放湿試験例、卵殻膜微細粉末配合紙の評価並び
に吸油試験例、卵殻膜微細粉末とその配合紙の各金属吸
着試験例などを順次説明する。但し、本発明は下記の実
施例に拘束されるものではない。[Examples] Egg shell membrane fine powder (ESMP)
rane Powder), a test example of surface hydrophobicity and dispersibility of the powder, and a production example of a blended paper of eggshell membrane fine powder, as well as moisture absorption / release of eggshell membrane fine powder and the blended paper. A wet test example, evaluation of eggshell membrane fine powder blended paper, oil absorption test example, metal adsorption test example of eggshell membrane fine powder and the blended paper, and the like will be sequentially described. However, the present invention is not limited to the following examples.

【００４７】《卵殻膜微細粉末の製造実施例》鶏卵から
得た生の卵殻膜を水洗し、水に浸漬した。そして、この
卵殻膜の浸漬物を石臼式磨砕機(マスコロイダーＭＫＺ
Ａ６―５;増幸産業製)により３回循環させて磨砕処理し
た後、濾過、水洗、再び濾過処理をして第一段磨砕物を
得た。この第一段磨砕物を乾燥して、繊維形状を保有し
た平均粒子径３０〜４０μｍ程度(実際には、粒子径に幅
がある)の卵殻膜微細粉末ＥＳＭＰ−Ａを得た。<< Production Example of Eggshell Membrane Fine Powder >> A raw eggshell membrane obtained from chicken eggs was washed with water and immersed in water. Then, the soaked product of the eggshell membrane is crushed by a stone mill (mass colloider MKZ
A6-5; manufactured by Masuyuki Sangyo Co., Ltd., was circulated three times for grinding treatment, then filtered, washed with water, and filtered again to obtain a first-stage ground material. This first-stage ground product was dried to obtain an egg shell membrane fine powder ESMP-A having a fiber shape and an average particle size of about 30 to 40 μm (actually, the particle size varies).

【００４８】一方、卵殻膜をより細かく微細化して、例
えば、繊維組成物の細孔に充填する場合には、前述した
ように、上記第一段磨砕処理に引き続いて、振動ボール
ミル粉砕機又は遊星ボールミル磨砕機を用いたボールミ
ル式粉砕処理を追加しても良い。この場合、上記第一段
磨砕物に分級処理を施して、粗粉末と微粉末を同時に調
製すると、異なる粒子径の卵殻膜微細粉末を配合した調
湿或は吸油などの様々な性状を備えた機能紙を簡便に作
り分けられる。即ち、分級処理で微粉末を調製する場合
には、先ず、第一段磨砕物の一部を解砕機(カレントジ
ェットＣＪ２５;日清エンジニアリング社製)で気流粉砕
したのち、分級機(ターボクラシファイヤーＴＣ−２５
Ｎ;日清エンジニアリング社製)にかけて空気分級し、繊
維形状を含む平均粒子径約３０〜４０μｍの粗砕画分と
ともに、１０μｍ以下の微砕画分を得るのである。この
場合、例えば、３ｋｇ／ｈｒの処理速度では、平均粒子
径６.０３μｍの微砕画分が１１.７％程度の収率で得ら
れる。On the other hand, when the eggshell membrane is made finer and finer, for example, to fill the pores of the fiber composition, as described above, following the first stage grinding treatment, a vibrating ball mill grinder or A ball mill type grinding process using a planetary ball mill grinder may be added. In this case, when the coarse powder and the fine powder were prepared at the same time by subjecting the above-mentioned first-stage ground product to a classification treatment, various properties such as humidity control or oil absorption were obtained by blending eggshell membrane fine powder with different particle diameters. You can easily create different types of functional paper. That is, in the case of preparing a fine powder by classification, first, a part of the first-stage ground product is crushed by airflow using a crusher (Current Jet CJ25; manufactured by Nisshin Engineering Co., Ltd.), and then a classifier (turbo classifier). TC-25
N; manufactured by Nisshin Engineering Co., Ltd.) and air-classified to obtain a finely pulverized fraction of 10 μm or less together with a coarsely pulverized fraction having an average particle diameter of about 30 to 40 μm including a fiber shape. In this case, for example, at a treatment rate of 3 kg / hr, a finely divided fraction having an average particle diameter of 6.03 μm can be obtained with a yield of about 11.7%.

【００４９】《卵殻膜微細粉末による吸湿・放湿試験
例》上記製造実施例で得られた卵殻膜微細粉末ＥＳＭＰ
−Ａについて、相対湿度を変化させた場合の吸湿経時曲
線、並びに吸湿後の放湿経時曲線を調べた。即ち、上記
卵殻膜微細粉末ＥＳＭＰ−Ａをデシケータに収容し、相
対湿度７９.３％、５２％及び２０％の異なる湿度環境
に夫々静置して、卵殻膜微細粉末の吸湿経時変化を測定
した。また、デシケータの底部に水を収容し、相対湿度
１００％の測定条件とした。次いで、上記吸着試験終了
後、湿度環境の異なる各試料を塩化カルシウムで脱湿し
た乾燥デシケータ内に移して湿気の放出経時変化を測定
した。<< Example of Moisture Absorption / Desorption Test Using Eggshell Membrane Fine Powder >> Eggshell membrane fine powder ESMP obtained in the above-mentioned production example
Regarding -A, the moisture absorption time curve when the relative humidity was changed and the moisture release time curve after moisture absorption were examined. That is, the eggshell membrane fine powder ESMP-A was housed in a desiccator and allowed to stand in different humidity environments of relative humidity of 79.3%, 52% and 20%, respectively, and the time-dependent change in moisture absorption of the eggshell membrane fine powder was measured. . In addition, water was stored in the bottom of the desiccator, and the measurement conditions were 100% relative humidity. Then, after the adsorption test was completed, each sample having a different humidity environment was transferred into a dry desiccator that had been dehumidified with calcium chloride, and the change with time of moisture release was measured.

【００５０】一方、本出願人は、先に、特開平７−２０
９１６５号公報で、羽毛微細粉末が水分に対して高い吸
着及び放出能力を有することを開示したが、この羽毛微
細粉末を卵殻膜微細粉末に替えて配合した紙を本吸湿・
放湿試験の参照例とした。上記羽毛微細粉末は、卵殻膜
微細粉末と同様の湿式粉砕処理により製造したものであ
り、粒子径を３９.９３μｍ程度に整えた粉末を参照例
１とし、粒子径５.３６μｍ程度の粉末を参照例２とし
た。但し、当該羽毛微細粉末では、相対湿度７９.３％
の環境での吸湿と、その後の放湿の挙動のみを測定し
た。On the other hand, the applicant of the present invention has previously described the Japanese Patent Application Laid-Open No. 7-20.
In 9165 gazette, it was disclosed that fine feather powder has a high ability to adsorb and release moisture. However, paper prepared by substituting this fine feather powder for eggshell membrane fine powder is used for moisture absorption.
It was used as a reference example for the moisture release test. The above-mentioned fine feather powder is produced by the same wet pulverization process as the eggshell membrane fine powder, and the powder whose particle diameter is adjusted to about 39.93 μm is used as Reference Example 1, and the powder having a particle diameter of about 5.36 μm is referred to. Example 2 is given. However, with the fine feather powder, relative humidity is 79.3%.
Only the behavior of moisture absorption in the environment and the subsequent moisture release was measured.

【００５１】図１Ａは卵殻膜微細粉末ＥＳＭＰ−Ａ並び
に参照例の吸湿経時曲線、図１Ｂはこれらの放湿経時曲
線を夫々示す。２０％の低湿度環境を含めた全ての湿気
環境で、卵殻膜微細粉末ＥＳＭＰ−Ａは最初の略５〜１
０時間の範囲で高い吸湿速度及び放湿速度を示した。従
って、卵殻膜微細粉末は、低湿度から高湿度(20〜100
％)までの種々の湿度環境で高い吸湿及び放湿の応答速
度を示し、調湿効果が高いことが判った。しかも、湿気
の吸着と放出の平衡に達するまでの時間が短いので、速
やかに調湿効果を発揮できる。一方、羽毛微細粉末(参
照例１及び２)は、卵殻膜微細粉末ＥＳＭＰ−Ａと同様
に、吸湿開始後の最初の略５〜１０時間の範囲で高い吸
湿及び放湿速度を示したが、図１Ａに示すように、平衡
状態の吸湿量は卵殻膜微細粉末ＥＳＭＰ−Ａの方が羽毛
微細粉末より３０％程度大きかった。FIG. 1A shows the moisture absorption time curves of the eggshell membrane fine powder ESMP-A and the reference example, and FIG. 1B shows the moisture release time curves thereof. Eggshell membrane fine powder ESMP-A is the first approximately 5-1 in all humidity environments including low humidity environment of 20%.
It showed a high moisture absorption rate and high moisture desorption rate in the range of 0 hours. Therefore, the eggshell membrane fine powder should have low to high humidity (20-100
%), It showed a high response rate of moisture absorption and moisture release in various humidity environments, and it was found that the humidity control effect was high. In addition, since it takes a short time to reach the equilibrium of adsorption and release of moisture, the humidity control effect can be promptly exhibited. On the other hand, the feather fine powder (Reference Examples 1 and 2), like the eggshell membrane fine powder ESMP-A, showed a high moisture absorption and desorption rate in the first approximately 5 to 10 hours after the initiation of moisture absorption, As shown in FIG. 1A, the moisture absorption amount in the equilibrium state was about 30% larger in the eggshell membrane fine powder ESMP-A than in the feather fine powder.

【００５２】《卵殻膜微細粉末の表面疎水性試験例》卵
殻膜微細粉末の表面疎水性環境の程度(表面の疎水基の
量)を８−アニリノナフタレンスルホン酸(ＡＮＳ)を蛍
光プローブとして用いて測定した。即ち、卵殻膜微細粉
末の１ｍｇ／ｍｌ水懸濁液中に、ＡＮＳ−Ｎａ塩を終濃
度１０-5Ｍになるように調整し、励起波長３７７ｎｍ、
蛍光波長４６３ｎｍにおける相対蛍光強度を測定した。
一方、比較例として、卵殻膜と同様の天然タンパク質で
ある羽毛の微細粉末の表面疎水性を測定した。尚、上記
卵殻膜微細粉末は粒子径２７μｍ程度のものを用いた。
また、羽毛微細粉末は羽毛を卵殻膜微細粉末と同様の湿
式粉砕処理方式で製造したもので、粒子径を変化させた
各種粉末について表面疎水性を測定した。<< Example of Surface Hydrophobicity Test of Eggshell Membrane Fine Powder >> The degree of the surface hydrophobic environment of the eggshell membrane fine powder (the amount of hydrophobic group on the surface) was determined by using 8-anilinonaphthalenesulfonic acid (ANS) as a fluorescent probe. Measured. That is, ANS-Na salt was adjusted to a final concentration of 10 -5 M in a 1 mg / ml aqueous suspension of egg shell membrane fine powder, and the excitation wavelength was 377 nm.
The relative fluorescence intensity at a fluorescence wavelength of 463 nm was measured.
On the other hand, as a comparative example, the surface hydrophobicity of fine powder of feathers, which is a natural protein similar to eggshell membranes, was measured. The eggshell membrane fine powder used had a particle diameter of about 27 μm.
In addition, the feather fine powder was produced by a wet pulverization treatment method similar to that of the eggshell membrane fine powder, and the surface hydrophobicity of various powders having different particle diameters was measured.

【００５３】図２はその結果であり、同図では相対蛍光
強度が高いほど表面疎水性が高いことを示す。この測定
結果によると、卵殻膜微細粉末は羽毛微細粉末に比べて
表面疎水性の程度はあまり高くなく、比較的親水性であ
り、水に分散し易いことが認められた。そこで、界面活
性剤の存在下に、卵殻膜微細粉末の懸濁水がどのような
分散性を示すかを試験した。The results are shown in FIG. 2, which shows that the higher the relative fluorescence intensity, the higher the surface hydrophobicity. According to this measurement result, it was confirmed that the eggshell membrane fine powder had a surface hydrophobicity not so high as compared with the feather fine powder, was relatively hydrophilic, and was easily dispersed in water. Therefore, the dispersibility of the water suspension of the eggshell membrane fine powder in the presence of a surfactant was tested.

【００５４】《卵殻膜微細粉末の分散性試験例》水の中
に前記卵殻膜微細粉末ＥＳＭＰ−Ａを入れ、種々の界面
活性剤により懸濁水を調製し、当該懸濁水における卵殻
膜微細粉末の分散、或は膨潤の度合を試験した。分散条
件は、卵殻膜微細粉末を２重量％、界面活性剤を０.０
０２〜０.６重量％の所定割合で加え、残りを精製水で
調整して１００重量％とし、ホモミキサーで６０００ｒ
ｐｍ、３分間撹拌した。<< Dispersion Test Example of Eggshell Membrane Fine Powder >> The eggshell membrane fine powder ESMP-A is put in water to prepare suspension water with various surfactants, and the egg shell membrane fine powder in the suspension water is prepared. The degree of dispersion or swelling was tested. Dispersion conditions are 2% by weight of eggshell membrane fine powder and 0.0% of surfactant.
It is added at a predetermined ratio of 02 to 0.6% by weight, and the rest is adjusted to 100% by weight with purified water, and 6000 r with a homomixer.
pm, stirred for 3 minutes.

【００５５】使用した界面活性剤は、下記の通り、(1)
〜(6)のカチオン系界面活性剤(具体的には、４級アンモ
ニウム塩類)と(7)〜(12)のノニオン系界面活性剤であ
る。 (1)塩化ベンザルコニウム(関東化学製) (2)塩化ベンゼトニウム(関東化学製) (3)ジアルキルジメチルアンモニウムクロライド(アーカ
ード2HT-75;ライオン製) (4)塩化ラウリルトリメチルアンモニウム(カチオーゲン
TML;第一工業薬品製) (5)塩化セチルトリメチルアンモニウム(カチオーゲンTM
P;第一工業薬品製) (6)塩化ステアリルトリメチルアンモニウム(カチオーゲ
ンTMS;第一工業薬品製) (7)ポリオキシエチレンノニルフェニルエーテル(ノイゲ
ンEA-170;第一工業薬品製) (8)ポリオキシエチレンドデシルフェニルエーテル(ノイ
ゲンEA-73;第一工業薬品製) (9)ポリオキシエチレンラウリルエーテル(ノイゲンET-1
70;第一工業薬品製) (10)ポリオキシエチレンオレイルエーテル(ノイゲンET-
80;第一工業薬品製) (11)ポリオキシエチレン(EO6)ソルビタンモノオレエー
ト(ニッコーTS-106;日光ケミカルズ社製) (12)ポリオキシエチレン(EO20)ソルビタンモノオレエー
ト(ニッコーTS-10;日光ケミカルズ社製)The surfactant used is as follows (1)
To (6) cationic surfactants (specifically, quaternary ammonium salts) and (7) to (12) nonionic surfactants. (1) Benzalkonium chloride (manufactured by Kanto Chemical) (2) Benzethonium chloride (manufactured by Kanto Chemical) (3) Dialkyldimethylammonium chloride (ARCARD 2HT-75; manufactured by Lion) (4) Lauryltrimethylammonium chloride (catiogen)
(TML; manufactured by Dai-ichi Kogyo Yakuhin) (5) Cetyltrimethylammonium chloride (CationogenTM)
P; manufactured by Dai-ichi Kogyo) (6) Stearyl trimethyl ammonium chloride (Cathogen TMS; manufactured by Dai-ichi Kogyo) (7) Polyoxyethylene nonylphenyl ether (Neugen EA-170; manufactured by Dai-ichi Kogyo) (8) Poly Oxyethylene dodecyl phenyl ether (Neugen EA-73; manufactured by Daiichi Pure Chemicals) (9) Polyoxyethylene lauryl ether (Neugen ET-1
70; manufactured by Daiichi Kogyo Yakuhin) (10) Polyoxyethylene oleyl ether (Neugen ET-
80; Dai-ichi Kogyo KK) (11) Polyoxyethylene (EO6) sorbitan monooleate (Nikko TS-106; Nikko Chemicals) (12) Polyoxyethylene (EO20) sorbitan monooleate (Nikko TS-10) (Manufactured by Nikko Chemicals)

【００５６】その結果、上記４級アンモニウム塩類(1)
〜(6)では、配合率０.２％以上でほとんどが上層にケー
ク層を形成したが、０.１％以下ではノニオン系(7)〜(1
2)との比較で、いずれも沈殿物の形成界面が明瞭でな
く、上部からわずかづつ水層が見られる程度であった。
即ち、４級アンモニウム塩類の配合により、卵殻膜微細
粉末はきわめて高い膨潤状態を示し、良好な分散性が観
察された。尚、上記４級アンモニウム塩類(1)〜(6)の適
正濃度は次の通りであった。 (1)〜(2)＝０.０１％ (3) ＝０.０５％ (4)〜(6)＝０.０２％ そこで、上記４級アンモニウム塩類の存在下で、卵殻膜
微細粉末と繊維組成物を水に分散して紙料を調製し、こ
れを湿式抄紙する卵殻膜微細粉末配合紙の製造例を述べ
る。As a result, the quaternary ammonium salt (1)
In the case of (6)-(6), the cake layer was formed on the uppermost layer at the compounding rate of 0.2% or more, but in the case of 0.1% or less, the nonionic type (7)-(1
In comparison with 2), the formation interface of precipitates was not clear in all cases, and only a small water layer was seen from the top.
That is, the egg shell membrane fine powder showed an extremely high swelling state due to the incorporation of the quaternary ammonium salt, and good dispersibility was observed. The appropriate concentrations of the above quaternary ammonium salts (1) to (6) were as follows. (1) to (2) = 0.01% (3) = 0.05% (4) to (6) = 0.02% Then, in the presence of the above quaternary ammonium salt, eggshell membrane fine powder and fiber A production example of a paper containing eggshell membrane fine powder in which the composition is dispersed in water to prepare a paper stock, and the paper stock is wet-made will be described.

【００５７】《卵殻膜微細粉末配合紙の製造実施例》一
方のタンクに水と前記卵殻膜微細粉末ＥＳＭＰ−Ａを加
え、４級アンモニウム塩類(具体的には、前記カチオーゲ
ンＴＭＰ使用)を繊維総重量に対して０.０２重量％の条
件下で配合して、ＥＳＭＰ−Ａの分散液を製造した。ま
た、他方のタンクにカナディアン標準濾水度(ＣＳＦ;JI
S-P-8121に準拠するパルプの濾水度試験方法)６５０ｍ
ｌに叩解されたＮＢＫＰの分散液を収容し、卵殻膜微細
粉末と木材パルプの二つの分散液をビーターにて下記の
組成で混合するとともに、同一粒子表面に４級アルキル
アミン基とカルボキシル基を併せ持つ両性イオンラテッ
クス系紙力増強剤(アコスターＣ−１２２;三井サイテッ
ク社製)を添加し、解離機で充分に撹拌・解離して、均一
な紙料を調製した。但し、当該紙力増強剤は、繊維総重
量に対して３.０重量％の条件で添加した。上記紙料を
ＪＩＳ−Ｐ−８２０９に従って湿式抄紙し、約１１０℃
で乾燥し、卵殻膜微細粉末配合紙を夫々得て、これらを
試料１〜３とした。<< Production Example of Eggshell Membrane Fine Powder Blended Paper >> Water and the eggshell membrane fine powder ESMP-A were added to one tank, and quaternary ammonium salts (specifically, the Cthiogen TMP was used) were added to the whole fiber. A dispersion of ESMP-A was prepared by blending it under the condition of 0.02% by weight based on the weight. In addition, the Canadian standard freeness (CSF; JI
Pulp freeness test method based on SP-8121) 650 m
A dispersion of NBKP beaten in 1 was stored, and two dispersions of eggshell membrane fine powder and wood pulp were mixed in a beater with the following composition, and a quaternary alkylamine group and a carboxyl group were formed on the same particle surface. A zwitterionic latex-based paper strength enhancer (Acostar C-122; manufactured by Mitsui Cytec Co., Ltd.) was also added and sufficiently stirred and dissociated by a dissociator to prepare a uniform paper stock. However, the paper strengthening agent was added under the condition of 3.0% by weight based on the total weight of the fibers. Wet papermaking of the above-mentioned stock according to JIS-P-8209, at about 110 ° C.
And dried to obtain eggshell membrane fine powder-containing papers, which were used as Samples 1 to 3.

【００５８】上記試料１〜３における卵殻膜微細粉末Ｅ
ＳＭＰ−ＡとＮＢＫＰの配合率は次の通りである。 (1)試料１ 卵殻膜微細粉末：ＮＢＫＰ＝６０重量％：４０重量％ (2)試料２ 卵殻膜微細粉末：ＮＢＫＰ＝４０重量％：６０重量％ (3)試料３ 卵殻膜微細粉末：ＮＢＫＰ＝２０重量％：８０重量％ 一方、湿式抄紙の条件を上記製造実施例と同様に設定し
て、ＮＢＫＰの配合率を１００重量％にし、卵殻膜微細
粉末を省略したものを比較例とした。Eggshell membrane fine powder E in Samples 1 to 3
The compounding ratio of SMP-A and NBKP is as follows. (1) Sample 1 Eggshell membrane fine powder: NBKP = 60% by weight: 40% by weight (2) Sample 2 Eggshell membrane fine powder: NBKP = 40% by weight: 60% by weight (3) Sample 3 Eggshell membrane fine powder: NBKP = 20% by weight: 80% by weight On the other hand, a wet papermaking condition was set in the same manner as in the above-mentioned Production Examples, the NBKP content was set to 100% by weight, and the eggshell membrane fine powder was omitted as a comparative example.

【００５９】尚、上記４級アンモニウム塩類は、前述し
たように、０.０１〜０.０５重量％程度の幅で配合可能
である。また、パルプ(ＮＢＫＰ)の標準濾水度は用途に
よって異なり、ビーターによって適正に濾水度を下げて
も良い。さらには、卵殻膜微細粉末ＥＳＭＰ−Ａとパル
プは１液方式により、ビーターに同時に混合しても差し
支えない。そこで、この卵殻膜微細粉末配合紙により、
吸湿並びに放湿試験を行った。The quaternary ammonium salt can be compounded in a range of about 0.01 to 0.05% by weight, as described above. Further, the standard freeness of pulp (NBKP) varies depending on the application, and the freeness may be appropriately lowered by a beater. Furthermore, the eggshell membrane fine powder ESMP-A and the pulp may be mixed in the beater at the same time by the one-liquid system. So, with this egg shell membrane fine powder blended paper,
A moisture absorption and moisture release test was conducted.

【００６０】《卵殻膜微細粉末配合紙による吸湿・放湿
試験例》前記試料１〜３の卵殻膜微細粉末配合紙につい
て、比較例と対比しながら、吸湿及び放湿試験を行っ
た。即ち、５０mm×５０mmの矩形に整えた試料１〜試料
３並びに比較例を、JIS-P-8127(紙及び板紙の水分試験
方法)に準拠して、充分に乾燥して前処理を行った後、
温度２０℃、相対湿度９３％に保持したデシケータ内に
静置して、９６時間経過するまでの間、各試験片の吸湿
量の経時変化を測定した。但し、上記吸湿量は、下式の
ように、乾燥処理前・後の重量差に基づいて、測定試験
片の含水率として表した。 〔(試験片の乾燥前の測定重量)−(絶乾重量)／(測定重
量)〕×１００<< Moisture Absorption / Desorption Test Example Using Eggshell Membrane Fine Powder Blended Paper >> The moisture absorption and moisture release tests were performed on the eggshell membrane fine powder blended papers of Samples 1 to 3 in comparison with Comparative Examples. That is, after the samples 1 to 3 arranged in a rectangle of 50 mm × 50 mm and the comparative example are sufficiently dried and subjected to a pretreatment in accordance with JIS-P-8127 (a moisture test method for paper and paperboard). ,
The test piece was allowed to stand in a desiccator maintained at a temperature of 20 ° C. and a relative humidity of 93%, and the change in moisture absorption of each test piece with time was measured until 96 hours had elapsed. However, the moisture absorption amount was expressed as the water content of the measurement test piece based on the weight difference before and after the drying treatment, as in the following formula. [(Measured weight of test piece before drying)-(Measured weight) / (Measured weight)] x 100

【００６１】また、上記９６時間経過後、直ちに、温度
２０℃、塩化カルシウムで脱湿したデシケータ内に移し
て静置し、１０時間経過するまでの間、各試験片の放湿
量の経時変化を測定した。但し、当該放湿量も、前記吸
湿量と同様に、試験片の含水率として表した。Immediately after the lapse of 96 hours, the sample was transferred to a desiccator dehumidified with calcium chloride at a temperature of 20 ° C. and left standing for 10 hours, and the moisture release amount of each test piece changed with time. Was measured. However, the moisture release amount was also expressed as the water content of the test piece, like the moisture absorption amount.

【００６２】図３Ａは卵殻膜微細粉末配合紙の吸湿試験
結果、図３Ｂはその放湿試験結果、図４Ａは吸湿経時曲
線、図４Ｂは放湿経時曲線(但し、図４では試料２を省
略)を各々示す。図３〜図４によると、試料１〜３の吸
湿及び放湿量は比較例に比べて大きく、特に、吸湿開始
から１０時間以内の範囲で吸湿量が大幅に増え、大きな
吸湿応答速度を示した。その一方、湿気の吸着後、直ち
にその放出が行われ、特に、吸湿終了後の初期段階での
放湿速度(放湿開始後２〜４時間以内の応答速度)がきわ
めて大きかった。即ち、卵殻膜微細粉末配合紙は吸湿と
放湿が可逆的で(高い復元力を示して)、湿度環境の調節
機能を有効に果すことが判る。FIG. 3A is a moisture absorption test result of eggshell membrane fine powder blended paper, FIG. 3B is a moisture release test result thereof, FIG. 4A is a moisture absorption time curve, and FIG. 4B is a moisture release time curve (however, sample 2 is omitted in FIG. 4). ) Are shown respectively. According to FIGS. 3 to 4, the moisture absorption and desorption amounts of Samples 1 to 3 are larger than that of the comparative example, and in particular, the moisture absorption amount significantly increases within a range of 10 hours from the start of the moisture absorption, and shows a large moisture absorption response speed. It was On the other hand, the moisture was released immediately after it was adsorbed, and in particular, the moisture release rate (the response rate within 2 to 4 hours after the start of moisture release) in the initial stage after the end of moisture absorption was extremely high. That is, it is understood that the paper containing the eggshell membrane fine powder has reversible moisture absorption and moisture release (showing a high restoring force) and effectively fulfills the function of controlling the humidity environment.

【００６３】また、図３〜図４に示すように、当該配合
紙の吸湿量及び放湿量に関して、卵殻膜微細粉末を６０
重量％配合した試料１の方が、２０重量％配合した試料
２より多く、卵殻膜微細粉末の配合率の増加に伴って吸
・放湿の度合は増大した。但し、卵殻膜微細粉末の配合
率が２０重量％程度の場合でも、比較例との差異は明白
であり、充分に実用性のある調湿結果を示した。そこ
で、この卵殻膜微細粉末配合紙の各種項目別の評価試験
を行うとともに、吸油並びに金属吸着の試験例を述べ
る。Further, as shown in FIGS. 3 to 4, regarding the amount of moisture absorption and the amount of moisture release of the compounded paper, the eggshell membrane fine powder was adjusted to 60%.
Sample 1 containing 20% by weight was more than Sample 2 containing 20% by weight, and the degree of absorption and desorption increased as the mixing ratio of the eggshell membrane fine powder increased. However, even when the mixing ratio of the eggshell membrane fine powder was about 20% by weight, the difference from the comparative example was clear, and the humidity control result was sufficiently practical. Therefore, an evaluation test for each item of this egg shell membrane fine powder blended paper is performed, and test examples of oil absorption and metal adsorption are described.

【００６４】《卵殻膜微細粉末配合紙の評価並びに吸油
の試験例》先ず、卵殻膜微細粉末の配合率を１０〜７０
重量％の範囲で１０重量％ごとに変化させた７種類の配
合紙(パルプにはＮＢＫＰを使用)を用意し、各試料１〜
７とした。各試料と配合率の関係は次の通りである。 試料ｎ：卵殻膜微細粉末の配合率ｎ×１０重量％(ｎ＝
１、２…７) そして、当該試料１〜７に関し、秤量、紙厚、密度、引
張り強度(伸び)、裂断長、引裂の各項目の評価試験を、
温度２０℃、相対湿度６５％の条件下で、比較例と対比
しながら行った。但し、秤量はJIS-P-8124に、紙厚・密
度の評価方式はJIS-P-8118に、裂断長はJIS-P-8113に、
比引裂度はJIS-P-8116に各々準拠した。また、引張り強
度の項目の伸びは、引張った紙が裂けた時点での伸び率
を示す。<< Evaluation Example of Eggshell Membrane Fine Powder Blended Paper and Test Example of Oil Absorption >> First, the blending ratio of the eggshell membrane fine powder was 10 to 70.
Prepare 7 kinds of blended papers (NBKP is used for pulp) that are changed in 10% by weight range in the range of 1% by weight for each sample 1
7 was set. The relationship between each sample and the compounding ratio is as follows. Sample n: Mixing ratio of fine eggshell membrane powder n × 10 wt% (n =
1, 2, ... 7) Then, with respect to the samples 1 to 7, an evaluation test of each item of weighing, paper thickness, density, tensile strength (elongation), breaking length, tearing,
The comparison was performed under the conditions of a temperature of 20 ° C. and a relative humidity of 65% while comparing with the comparative example. However, the weighing is JIS-P-8124, the paper thickness and density evaluation method is JIS-P-8118, the breaking length is JIS-P-8113,
The specific tear degree was in accordance with JIS-P-8116. In addition, the elongation in the item of tensile strength indicates the elongation rate at the time when the pulled paper is torn.

【００６５】図５はその結果を示し、各試料は、比較例
に比べて、７割弱〜５割弱の密度であり、軽量で、使い
勝手が良いうえ、卵殻膜特有の暖かみのある風合が備わ
っていた。また、各試料の裂断長は、配合率が最大の試
料７で１.５４を示したが、これは、例えば、ティッシ
ュペーパーの示す数値(１.０程度)より大きいことなど
から、実用性に全く問題はない。引張り強度や引裂に関
しては、(例えば、ティッシュペーパーの引張り強度は
２５mm幅で４００ｇｆ程度であることから)試料におけ
る卵殻膜微細粉末の配合率が高い場合でも、紙として充
分に実用に足る数値を示した。尚、当該裂断長、引裂な
どの紙の強度は、抄造時に混入した両性イオンラテック
スバインダーが相乗的に寄与しているものと推定でき
る。FIG. 5 shows the results. Each sample has a density of slightly less than 70% to less than 50% as compared with the comparative example, is lightweight, is easy to use, and has a warm feeling peculiar to the eggshell membrane. Was equipped with. Further, the breaking length of each sample was 1.54 in Sample 7 having the highest compounding ratio, which is, for example, larger than the numerical value (about 1.0) indicated by the tissue paper, and therefore practical. There is no problem at all. Regarding the tensile strength and tearing (for example, the tensile strength of tissue paper is about 400 gf in the width of 25 mm), even if the mixing ratio of the eggshell membrane fine powder in the sample is high, it shows a value sufficient for practical use as paper. It was Incidentally, it can be estimated that the paper length such as the breaking length and tearing is synergistically contributed by the zwitterionic latex binder mixed during the papermaking.

【００６６】一方、上記各試料の吸油速度、並びに吸油
倍率を下記(1)〜(2)の手法で、比較例と対比しながら試
験した。 (1)吸油速度 各試料に軽油(１号軽油)を注射針(Ｈ５号)を通して１滴
(約４ｍｇ)滴下し、各試料が軽油の吸収を完了して、反
射による光沢がなくなるまでの時間(秒数)を測定した。 (2)吸油倍率 各試料を大豆油に１５秒間浸漬したのち、油中から取り
出し、手で１０秒間保持した時点での各試料の重量増加
率を測定した。On the other hand, the oil absorption rate and the oil absorption ratio of each of the above samples were tested by the methods (1) and (2) below in comparison with the comparative example. (1) Oil absorption rate One drop of light oil (No. 1 light oil) through each needle through each sample.
(About 4 mg) was dropped, and the time (seconds) until each sample completed absorption of light oil and lost gloss due to reflection was measured. (2) Oil Absorption Ratio Each sample was immersed in soybean oil for 15 seconds, taken out from the oil, and held for 10 seconds by hand, and the weight increase rate of each sample was measured.

【００６７】図５はその結果を示し、図６は吸油速度の
結果をグラフ化したものである。図５及び図６による
と、卵殻膜微細粉末の配合率が増すのに伴い吸油速度は
増大し、例えば、試料７は比較例より表・裏ともに略６
倍速かった。また、図５によると、吸油倍率でも、各試
料１〜７は比較例より略１.２５〜１.６５倍大きかっ
た。FIG. 5 shows the results, and FIG. 6 is a graph showing the results of the oil absorption rate. According to FIG. 5 and FIG. 6, the oil absorption rate increases as the blending ratio of the eggshell membrane fine powder increases.
It was twice as fast. Further, according to FIG. 5, the oil absorption ratios of the samples 1 to 7 were about 1.25 to 1.65 times larger than that of the comparative example.

【００６８】《卵殻膜微細粉末による金属吸着試験例》
各種の重金属塩を混合した疑似廃液を調製し、前記製造
実施例で得られた卵殻膜微細粉末ＥＳＭＰ−Ａを試料と
して、当該試料を１０ｇ／ｌの割合で疑似廃液中に加
え、ｐＨ２、室温の条件下で１７時間撹拌を続けて濾過
した後、疑似廃液中の重金属の各濃度を測定した。下記
に示す表は、疑似廃液に含まれる各種重金属の初期濃度
と、卵殻膜微細粉末を接触させた後の残液の各濃度であ
る(尚、濃度は、ｐｐｍで示す)。<< Example of Metal Adsorption Test with Eggshell Membrane Fine Powder >>
A pseudo-waste liquid mixed with various heavy metal salts was prepared, and the eggshell membrane fine powder ESMP-A obtained in the above-mentioned Production Example was used as a sample, and the sample was added to the pseudo-waste liquid at a rate of 10 g / l, pH 2, room temperature. After continuously stirring for 17 hours under the conditions described in 1. above, each concentration of heavy metals in the simulated waste liquid was measured. The table below shows the initial concentrations of various heavy metals contained in the simulated waste liquid and the respective concentrations of the residual liquid after contact with the eggshell membrane fine powder (the concentration is indicated in ppm).

【００６９】 廃液含有重金属 Ｐｂ2+ Ｓｎ4+ Ｆｅ2+ Ｎｉ2+ Ｃｕ2+ Ｚｎ2+ 初期濃度 １ − ５０ ５６ ５０ ４１ ＥＳＭＰ−Ａ ０ − ０ ５０ ０ １８Waste liquid-containing heavy metal Pb 2+ Sn 4+ Fe 2+ Ni 2+ Cu 2+ Zn 2+ Initial concentration 1−50 56 50 50 41 ESMP-A 0−0 50 0 18

【００７０】上表によると、疑似廃液に卵殻膜微細粉末
を接触させると、Ｆｅ2+やＣｕ2+を円滑に除去できるう
え、特に、各種の重金属が競合する中で、微量含有され
ているＰｂ2+を完全に除去することができた。According to the above table, when the eggshell membrane fine powder is brought into contact with the pseudo waste liquid, Fe 2+ and Cu 2+ can be smoothly removed, and in particular, in the presence of competition among various heavy metals, a small amount is contained. Pb 2+ could be completely removed.

【００７１】因みに、前記特開昭５８−１５０４３３号
公報では、卵殻膜を凍結乾燥後、ハンマーミルで粉砕し
て４０メッシュの篩通しをした乾式粉砕の卵殻膜粉末を
用いて、当該粉末０.５ｇを硝酸鉛溶液(Ｐｂとして１
０、５０及び１００ｐｐｍ)５０ｍｌに加えて撹拌し、
４、８及び２４時間後に各５ｍｌづつをサンプリング
し、これらを濾紙で濾過したのち、濾液の鉛濃度(ｐｐ
ｍ)を測定した試験結果を次のように記載している(同公
報の試験方法、試験結果及び第１表参照)。 ４時間 ８時間 ２４時間 １０ｐｐｍ ０.２ ０.２ ０.１ ５０ｐｐｍ ０.２ ０.１ ０.２ １００ｐｐｍ ０.４ ０.４ ０.４Incidentally, in the above-mentioned Japanese Patent Laid-Open No. 58-150433, the egg shell membrane powder is freeze-dried, then pulverized with a hammer mill and sieved through 40 mesh to obtain a dry pulverized egg shell membrane powder. 5g of lead nitrate solution (1 as Pb
0, 50 and 100 ppm) 50 ml and stirred,
After 4, 8 and 24 hours, 5 ml of each sample was sampled and filtered with a filter paper, and then the lead concentration (pp
The test results obtained by measuring m) are described as follows (see the test method, test results and Table 1 in the same publication). 4 hours 8 hours 24 hours 10 ppm 0.2 0.2 0.1 50 ppm 0.2 0.1 0.2 100 ppm 0.4 0.4 0.4

【００７２】また、卵殻膜を各種条件で恒温器或はマッ
フル炉で加熱乾燥、又は凍結乾燥したのち、各乾燥品を
スパイラルミルで粉砕して篩通しをした乾式粉砕の卵殻
膜粉末を用いて、当該９種類の粉末を硝酸鉛溶液(Ｐｂ
として１００ｐｐｍ)に加えて撹拌し、１、２、３、４
時間後に夫々サンプリングして、上記試験方法に従って
液の鉛濃度(ｐｐｍ)を測定した試験結果(比較例は除く)
を次のように記載している(同公報の実施例及び第２表
参照)。 １時間後：３５.６〜０.４ｐｐｍ ２時間後：２４.８〜０.６ｐｐｍ ３時間後：１２.３〜０.５ｐｐｍ ４時間後： ５.８〜０.４ｐｐｍ 即ち、同公報の技術では、鉛１種類の含有溶液に乾式粉
砕処理の卵殻膜を接触させて、その除去効率を調べたこ
とが記載されているだけで、本試験例のように、他の重
金属が競合する溶液での鉛の除去試験は全く行われてい
ない。また、本試験例の試料溶液の鉛濃度が１ｐｐｍと
微量であるのに対して、同公報の鉛の含有濃度は１０ｐ
ｐｍ〜１００ｐｐｍとオーダーが大きい。しかも、本試
験例では競合重金属の存在下で、１７時間後の鉛の濃度
が０ｐｐｍであったのに対して、同公報(例えば、前記第
１表)では、１０ｐｐｍの鉛溶液の濃度は２４時間後で
も０.１ｐｐｍに止まった。The eggshell membranes were heat-dried under various conditions in a thermostat or a muffle furnace or freeze-dried, and then each dried product was pulverized with a spiral mill and sieved to obtain dry-pulverized eggshell membrane powders. , Nine kinds of powders are mixed with lead nitrate solution (Pb
As 100 ppm) and stirred, 1, 2, 3, 4
Test results obtained by measuring the lead concentration (ppm) of the liquid according to the above test method by sampling after each time (excluding comparative examples)
Is described as follows (see Examples of the publication and Table 2). 1 hour later: 35.6 to 0.4 ppm 2 hours later: 24.8 to 0.6 ppm 3 hours later: 12.3 to 0.5 ppm 4 hours later: 5.8 to 0.4 ppm That is, the technique of the publication. Then, it is described that the removal efficiency was investigated by contacting the solution containing one kind of lead with the eggshell membrane subjected to the dry pulverization treatment, and as in this test example, in a solution in which other heavy metals compete with each other. No lead removal test has been conducted. Further, while the lead concentration of the sample solution of this test example is as small as 1 ppm, the lead content concentration of the publication is 10 p.
The order is large at pm to 100 ppm. Moreover, in this test example, the lead concentration after 17 hours was 0 ppm in the presence of competing heavy metals, whereas in the same publication (for example, Table 1 above), the lead solution concentration of 10 ppm was 24 ppm. Even after an hour, it remained at 0.1 ppm.

【００７３】従って、本発明の卵殻膜微細粉末を重金属
の捕集剤として使用すると、多くの重金属が競合する廃
液でも、水質汚濁防止の見地から特に規制の厳しい鉛を
有効に吸着して捕集できる。このため、当該卵殻膜微細
粉末を主成分とする金属捕集剤は、例えば、ハンダメッ
キ液を始め、その他の金属メッキ液や種々の重金属を含
む廃液の除害処理に好適である。そこで、前記製造実施
例で示した卵殻膜微細粉末の配合紙に関し、パラジウム
を代表とする貴金属に対する捕集作用を試験した。Therefore, when the eggshell membrane fine powder of the present invention is used as a heavy metal scavenger, even a waste liquid in which many heavy metals compete with each other is effectively adsorbed and collected as lead, which is particularly regulated from the viewpoint of preventing water pollution. it can. Therefore, the metal scavenger containing the eggshell membrane fine powder as a main component is suitable, for example, for removing harmful substances such as a solder plating liquid, other metal plating liquids, and waste liquids containing various heavy metals. Therefore, the egg-shell membrane fine powder compounded paper shown in the above Production Examples was tested for its ability to collect precious metals represented by palladium.

【００７４】《卵殻膜微細粉末配合紙の貴金属吸着試験
例》先ず、卵殻膜微細粉末の配合率(パルプにはＮＢＫ
Ｐを使用)を下記のように変化させた３種類の卵殻膜微
細粉末配合紙を用意し、各試料１〜３とした。当該配合
紙の製法は前記製造実施例の手法を基本とした。 (1)試料１：卵殻膜微細粉末の配合率は２０重量％ (2)試料２：同４０重量％ (3)試料３：同７０重量％ 次いで、濃度１０００ｐｐｍに調整したパラジウム標準
液１０ｍｌをシャーレーに入れ、上記試料１〜３をこの
標準液に所定時間だけ夫々浸漬して、その残液のパラジ
ウム濃度を原子吸光分析又はプラズマ発光分光分析(Ｉ
ＣＰ)法で測定して、標準液の初期濃度との差異によ
り、各試料１〜３のパラジウム吸着量を算出した。但
し、試料１と２に関しては、パラジウム標準液への浸漬
時間を３時間と８時間の２通りに設定して、浸漬時間と
吸着量との関係を調べた。<< Example of Noble Metal Adsorption Test of Eggshell Membrane Fine Powder Blended Paper >> First, the blending ratio of eggshell membrane fine powder (NBK for pulp is
Three types of eggshell membrane fine powder blended papers in which P was used) were changed as described below were prepared as Samples 1 to 3. The manufacturing method of the compound paper is based on the method of the manufacturing example. (1) Sample 1: 20% by weight of fine powder of eggshell membrane (2) Sample 2: 40% by weight (3) Sample 3: 70% by weight Next, 10 ml of palladium standard solution adjusted to a concentration of 1000 ppm was petri dish. The samples 1 to 3 are immersed in this standard solution for a predetermined time, and the palladium concentration in the residual solution is analyzed by atomic absorption spectrometry or plasma emission spectroscopy (I
CP) method, and the palladium adsorption amount of each sample 1 to 3 was calculated from the difference from the initial concentration of the standard solution. However, with respect to Samples 1 and 2, the immersion time in the palladium standard solution was set to two ways of 3 hours and 8 hours, and the relationship between the immersion time and the adsorption amount was investigated.

【００７５】図７はその結果であり、例えば、試料３を
１時間に亘り浸漬した場合、パラジウム標準液の濃度は
７２５ｐｐｍ(=ｍｇ/ｌ)を示したので、当該標準液の初
期濃度が１０００ｐｐｍであることから、試料３のパラ
ジウム吸着量は、次の通りであった。 (１−０.７２５)ｍｇ／ｍｌ×１０ｍｌ＝２.７５ｍｇ 従って、試料３の重量は０.１２６ｇなので、試料３の
単位重量当たりのパラジウム吸着量(以下、単に吸着量と
いう)は、２.７５ｍｇ／０.１２６ｇ＝２１.８ｍｇ／ｇ
となった。FIG. 7 shows the result. For example, when the sample 3 was immersed for 1 hour, the concentration of the palladium standard solution showed 725 ppm (= mg / l), so the initial concentration of the standard solution was 1000 ppm. Therefore, the palladium adsorption amount of Sample 3 was as follows. (1-0.725) mg / ml × 10 ml = 2.75 mg Therefore, since the weight of the sample 3 is 0.126 g, the palladium adsorption amount per unit weight of the sample 3 (hereinafter, simply referred to as the adsorption amount) is 2. 75 mg / 0.126 g = 21.8 mg / g
It became.

【００７６】この１時間浸漬での試料３の吸着量２１.
８ｍｇ／ｇは、８時間浸漬での試料１の吸着量１７.２
ｍｇ／ｇや試料２の同吸着量１７.６ｍｇ／ｇより多い
ことから、卵殻膜微細粉末の配合率が増すのに比例し
て、パラジウムの吸着量も増し、吸着時間も短縮できる
ことが判る。また、試料の種類を固定して浸漬時間と吸
着量の関係を調べると、試料１では、浸漬時間が３時間
から８時間に長くなっても吸着量に差異がほとんどな
く、試料２でも、３時間から８時間に増すと、吸着量が
若干増えている程度である。このため、２０〜４０重量
％の範囲の卵殻膜微細粉末配合紙では、パラジウム吸着
の応答速度が速く、浸漬時間を長くしなくてもパラジウ
ムを有効に吸着できることが判る。Adsorption amount of sample 3 in this 1 hour immersion 21.
8 mg / g is the adsorption amount of Sample 1 of 17.2 after immersion for 8 hours.
Since it is more than mg / g or the same adsorption amount of Sample 2 as 17.6 mg / g, it is understood that the adsorption amount of palladium increases and the adsorption time can be shortened in proportion to the increase of the blending ratio of the eggshell membrane fine powder. Moreover, when the relationship between the immersion time and the adsorption amount was examined while fixing the type of sample, there is almost no difference in the adsorption amount with the sample 1 even when the immersion time is increased from 3 hours to 8 hours, and with the sample 2 as well, 3 When the time is increased from 8 hours to 8 hours, the adsorption amount is slightly increased. Therefore, it can be seen that in the egg shell membrane fine powder blended paper in the range of 20 to 40% by weight, the response speed of palladium adsorption is fast, and palladium can be effectively adsorbed without prolonging the immersion time.

【００７７】即ち、本実施例の卵殻膜微細粉末配合紙
は、例えば、前記特開昭５８−１５０４３３号公報には
全く記載、或は示唆のないパラジウムを代表とする貴金
属を吸着できる点で、新規の用途を期待できる。That is, the egg shell membrane fine powder blended paper of this example is capable of adsorbing noble metal typified by palladium, which is not described or suggested in JP-A-58-150433. Expect new uses.

【図面の簡単な説明】[Brief description of the drawings]

【図１】卵殻膜微細粉末の吸湿並びに放湿挙動を示し、
図１Ａは同粉末の吸湿経時曲線図、図１Ｂは同粉末の放
湿経時曲線図である。FIG. 1 shows moisture absorption and desorption behavior of eggshell membrane fine powder,
FIG. 1A is a moisture absorption time-lapse curve diagram of the powder, and FIG. 1B is a moisture release time-lapse curve diagram of the powder.

【図２】卵殻膜微細粉末と羽毛微細粉末の表面疎水性の
試験結果を示す図である。FIG. 2 is a diagram showing test results of surface hydrophobicity of egg shell membrane fine powder and feather fine powder.

【図３】卵殻膜微細粉末配合紙の吸湿並びに放湿挙動を
示し、図３Ａは配合紙の吸湿試験結果、図３Ｂは配合紙
の放湿試験結果を各々示す図表である。FIG. 3 shows the moisture absorption and desorption behavior of eggshell membrane fine powder blended paper, FIG. 3A is a chart showing the moisture absorption test result of the blended paper, and FIG. 3B is a table showing the moisture release test result of the blended paper.

【図４】図４Ａは上記卵殻膜微細粉末配合紙の吸湿経時
曲線図、図４Ｂは同配合紙の放湿経時曲線図である。FIG. 4A is a moisture absorption time-dependent curve diagram of the eggshell membrane fine powder-containing paper, and FIG. 4B is a moisture release time-dependent curve diagram of the same paper.

【図５】上記卵殻膜微細粉末配合紙の評価、並びに吸油
試験結果を示す図表である。FIG. 5 is a table showing the evaluation of the eggshell membrane fine powder-containing paper and the oil absorption test results.

【図６】卵殻膜微細粉末の配合率と吸油速度の関係図で
ある。FIG. 6 is a diagram showing the relationship between the compounding ratio of eggshell membrane fine powder and the oil absorption rate.

【図７】卵殻膜微細粉末配合紙のパラジウム吸着試験結
果を示す図表である。FIG. 7 is a table showing the results of palladium adsorption test on paper containing egg shell membrane fine powder.

【図８】図８Ａは卵殻膜微細粉末配合紙の倍率３００倍
での顕微鏡写真、図８Ｂは同１０００倍の顕微鏡写真で
ある。FIG. 8A is a micrograph of a paper containing egg shell membrane fine powder at a magnification of 300 times, and FIG. 8B is a micrograph at a magnification of 1000 times.

フロントページの続き (72)発明者 横田 博志 香川県仲多度郡多度津町山階1316番地 (72)発明者 国武 哲則 愛媛県川之江市川之江町2451―１番地 井 川ビル405号 (72)発明者 村山 明徳 東京都渋谷区渋谷１丁目４番13号 キュー ピー株式会社内Front page continuation (72) Inventor Hiroshi Yokota 1316 Yamashina, Tadotsu-cho, Nakatado-gun, Kagawa (72) Inventor Tetsunori Kunitake 2451-1, Kawanoe-cho, Kawanoe-shi, Ehime Igawa Building 405 (72) Inventor Akinori Murayama 4-1-4 Shibuya, Shibuya-ku, Tokyo QP Corporation

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 卵殻膜を水及びアルコール系溶媒の少な
くともいずれかに浸漬し、石臼式回転磨砕及びボールミ
ル式粉砕の少なくともいずれかを施して卵殻膜の湿式粉
砕粉末を製造し、この卵殻膜微細粉末の繊維構造を絡み
合わせてシート形態に加工することを特徴とする卵殻膜
微細粉末配合紙。1. An egg shell membrane is dipped in at least one of water and an alcoholic solvent and subjected to at least one of stone mill type rotary grinding and ball mill type grinding to produce a wet pulverized powder of the egg shell membrane. An egg shell membrane fine powder compounding paper, characterized in that the fiber structure of fine powder is entangled and processed into a sheet form. 【請求項２】 ４級アンモニウム塩類などのカチオン系
界面活性剤により卵殻膜微細粉末と繊維組成物を水に分
散させて紙料を調製し、湿式抄紙することを特徴とする
請求項１に記載の卵殻膜微細粉末配合紙。2. The wet papermaking process according to claim 1, wherein the eggshell membrane fine powder and the fiber composition are dispersed in water with a cationic surfactant such as a quaternary ammonium salt to prepare a paper stock, and wet papermaking is performed. Eggshell membrane fine powder compound paper. 【請求項３】 請求項１又は２に記載の卵殻膜微細粉末
配合紙を湿度環境に接触させて、環境中の湿気の吸収と
放出により湿度調節可能にすることを特徴とする卵殻膜
微細粉末を利用した調湿紙。3. An egg shell membrane fine powder, characterized in that the paper containing the egg shell membrane fine powder according to claim 1 or 2 is brought into contact with a humidity environment to allow humidity control by absorbing and releasing moisture in the environment. Humidity control paper. 【請求項４】 請求項１又は２に記載の卵殻膜微細粉末
配合紙を被処理物に接触させて、有効主成分である卵殻
膜により被処理物の油分を吸収除去可能にすることを特
徴とする卵殻膜微細粉末を利用した吸油紙。4. The eggshell membrane fine powder-containing paper according to claim 1 or 2 is brought into contact with an object to be treated, and the eggshell membrane as an effective main component makes it possible to absorb and remove the oil content of the object to be treated. Oil-absorbent paper using eggshell membrane fine powder. 【請求項５】 請求項１又は２に記載の卵殻膜微細粉末
配合紙を被処理物に接触させて、被処理物中の貴金属、
重金属などの金属を吸着可能にすることを特徴とする卵
殻膜微細粉末を利用した金属捕集紙。5. The eggshell membrane fine powder-containing paper according to claim 1 or 2 is brought into contact with an object to be treated, and a noble metal in the object to be treated,
Metal collecting paper using eggshell membrane fine powder, which is capable of adsorbing metals such as heavy metals.
JP35012095A 1995-12-22 1995-12-22 Eggshell membrane fine powder blended paper, and various functional papers using eggshell membrane fine powder Expired - Fee Related JP3567308B2 (en)

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WO2004005607A1 (en) * 2002-07-05 2004-01-15 Idemitsu Technofine Co., Ltd. Fiber processing agent and fiber processed with the fiber processing agent
JP2008127604A (en) * 2006-11-17 2008-06-05 Kyushu Univ Method of recovering noble metal element
JP2010270972A (en) * 2009-05-21 2010-12-02 Daikin Ind Ltd Heat exchanger and method of manufacturing the same
US9297587B2 (en) 2009-05-21 2016-03-29 Daikin Industries, Ltd. Method for manufacturing a heat exchanger
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