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

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

Detailed Description of the Invention

[0001]

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]

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]

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]

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.

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]

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.

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] 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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

(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.

(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.

(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.

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.

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]

[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.

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. .

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]

【The invention's effect】

(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.

(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.

(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.

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.

(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.

(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.

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.

(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.

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.

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.

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.

(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.

(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]

[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.

<< 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).

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%.

<< 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.

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.

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.

<< 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.

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.

<< 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.

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)

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.

<< 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.

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.

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.

<< 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

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.

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.

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.

<< 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.

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.

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.

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.

<< 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).

Waste 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

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.

Incidentally, 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

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.

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.

<< 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.

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.

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.

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.

[Brief description of the drawings]

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.

FIG. 2 is a diagram showing test results of surface hydrophobicity of egg shell membrane fine powder and feather fine powder.

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.

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.

FIG. 5 is a table showing the evaluation of the eggshell membrane fine powder-containing paper and the oil absorption test results.

FIG. 6 is a diagram showing the relationship between the compounding ratio of eggshell membrane fine powder and the oil absorption rate.

FIG. 7 is a table showing the results of palladium adsorption test on paper containing egg shell membrane fine powder.

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.

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)

[Claims] 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. 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. 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. 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. 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.