JPH06345976A - Surface modifier consisting mainly of feather meal and urethane-modified feather meal - Google Patents

Abstract

PURPOSE:To effectively utilize feather keratin excellent in oil absorption, antiperspirant effect, etc., as a surface modifier. CONSTITUTION:The surface of a work is modified by containing it with an optionally urethane-modified feather meal as a main active ingredient. For example, due to its high oil absorption, the feather meal can be used for removing oil from the work surface by absorption. Due to its high antiperspirant effect, the feather meal can be used for absorbing sweat components to check perspiration. Molding the feather meal into a sheet heightens the usefulness thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a feather fine powder and a surface modifier containing a urethane modified product as a main component, and effectively utilizes feather keratin which exhibits excellent properties such as oil absorption rate, antiperspirant ability and water retention ability. It was done.

[0002]

BACKGROUND OF THE INVENTION Keratin, which is a kind of hard protein and is also called keratin, is almost insoluble in water, but it is a stable protein and is highly soluble in feathers, animal hair, hair, hoofs, nails, horns, scales, etc. It is contained. 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, but to effectively utilize the above-mentioned keratin which has not received much attention in the past industrially. That is, it is required to meet the demands of the times by substituting raw materials for existing products with keratin, or by increasing the added value of products.

However, whether or not there is a possibility of effectively and practically using the above-mentioned keratin substance depends on how to solve the requirements such as availability of the keratin and securing of abundant supply. However, the fact that a large amount of feathers are discharged from chickens for meat is only used as livestock feed or fertilizer, and most of the rest is discarded. Is in For example, the number of broilers shipped in Japan in 1991 was about 7.
The total number of feathers is 400 million, and the dry weight of the feathers emitted from the feathers is about 350,000 tons. Therefore, when the keratin substance is industrially used, it is realistic to select the feather keratin as an object of use.

[0004]

2. Description of the Related Art The present applicant has previously filed Japanese Patent Application Laid-Open No. 4-31253.
No. 4 discloses a feather fine powder characterized by immersing feathers in an alcoholic solvent, subjecting to stone mill type rotary grinding, and further pulverizing by a ball mill method, and a method for producing the same. The medicines and cosmetics used are also shown.

[0005]

[Prior Art] The applicant of the present invention is the Japanese Patent Application No. 4-1771.
No. 83, colored feather fine powder obtained by dyeing the feather fine powder with a tar dye, an organic pigment using the colored feather fine powder or the undyed feather fine powder, and a cosmetic containing the organic pigment. I first proposed paints and printing inks.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive and continuous studies on feather fine powder even after the application of the above-mentioned prior art and prior art, and as a result, elucidated in more detail the excellent properties of the feather fine powder. I got an opportunity. The main properties among them are as follows.

(1) Absorb oil and retain water. In particular, the oil absorption rate was high, and for example, powder having a particle size of about 50 to 5 μm exhibited a very high oil absorption rate of about 550 to 180%. Also, it has a low water absorption but a high water retention capacity. (2) In relation to (1) above, the extensibility and adhesion to the skin are good, and the effect of preventing sweating on the skin surface is great. The coated surface of the fine feather powder can keep the treated surface smooth. Also,
The effect of removing makeup is also great. (3) It has high dispersibility in water and oil and forms a stable dispersion system. (4) The fine feather powder obtained by the above-mentioned grinding and pulverization has an internal hollow matrix structure and a lining structure as the surrounding environment, and the surface area and bulk specific gravity of the powder are large. (5) It has a UV-blocking function due to the synergistic effect of the protein-derived ultraviolet ray absorbing action and the powder-derived ultraviolet ray shielding action.

Incidentally, the oil absorption rate of (1) and the antiperspirant function of (2) can be estimated to be basically derived from the matrix structure of (4) and the lining structure thereof, but these heights are predicted. It is greatly expected to expand the scope of application development of fine feather powder by using the above properties, or to substitute fine feather powder for raw materials of existing products. . As described above, the present invention makes it an urgent technical task to utilize the above-mentioned research results of feather fine powders more effectively, based on the above-mentioned conventional and prior arts, to further effectively utilize the powders.

[0009]

The present inventor mainly
Focusing on the function of (1) or (2), the fine feather powder is brought into contact with the part to be treated, and the surface is oil-absorbed, antiperspirant, or water-retained, and the surface is widely modified with the fine feather powder. And to improve the effect of the surface modification by modifying the fine feather powder with urethane, and to improve the convenience by processing the fine feather powder into a sheet form like a nonwoven fabric. Therefore, the present invention has been completed.

That is, the present invention 1 is characterized in that the fine feather powder is used as an effective main component, and the fine feather powder is brought into contact with an object to be treated to modify the surface thereof. Is. The present invention 2 is a surface-modifying agent, characterized in that the fine feather powder of the first invention is a urethane modified product of the fine feather powder whose surface is urethane-modified with isocyanates and polyols. The present invention 3 is characterized in that the surface modifier of the above invention 1 or 2 is an oil absorbing agent, and is configured to absorb and remove the oil content of the surface to be treated by the fine powder of feathers and modify the surface. Is an oil-absorbing agent whose main component is fine feather powder. This invention 4 is the above invention 1
Alternatively, the surface modifier of 2 is an antiperspirant, which absorbs sweat components on the skin surface, which is the surface to be treated, by the fine powder of feathers for antiperspirant,
It is an antiperspirant composed mainly of feather fine powder, which is characterized in that its surface is modified.

A fifth aspect of the present invention is the sheet-like surface modifier obtained by molding the fine feather powder into a sheet according to any one of the first to fourth aspects. The present invention 6 is a coating method with a surface modifier, which comprises coating the surface modification agent of the invention 5 onto the surface of another material. Invention 7
Is a surface modifier characterized in that the surface modifier according to any one of the present inventions 1 to 4 is in the form of powder or lumps, and the surface modifier is dispersed and coated on the surface of another material. It is a coating method with an agent.

The above-mentioned fine powder of feathers can be obtained by crushing with various crushers such as crushers and mills or by freeze crushing of feathers, but without heating, for example, as in the above-mentioned prior art or prior art, Is preferably pre-washed, pulverized, and then filtered, washed and dried. In the preliminary washing, washing is performed with water and then with an alcohol solvent to dissolve and remove oil and fat adhering to the feathers, and feathers that are not well compatible with water are made into a dip suitable for wet pulverization in the next step.

The advantage of the above-mentioned alcohol cleaning is that the residual water content after the water cleaning does not pose a problem and the 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 sterilizing and disinfecting effect of the feathers can be simultaneously exerted. ~ 7
It is preferably 0%. The alcohol used is saturated,
A wide variety of unsaturated aliphatic and aromatic mono-, di-, and polyhydric alcohols can be used, but ethanol,
Isopropanol is preferred, and those listed in the Japanese Pharmacopoeia can be used as 70% ethanol, 30% and 50% isopropanol.

In the above fine pulverization, the above-mentioned alcohol-immersed material of feathers is repeatedly subjected to stone mill type rotary grinding and ball mill type pulverization to obtain a pulverized material suspension. The stone mill type grinder consists of two upper and lower special grinders, and the impact generated between the upper grinder on the fixed side and the lower grinder on the rotating side.
The raw material is crushed by a force such as shearing, compression and rolling friction. 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. The alcohol-immersed keratin material to be added has a dipping ratio of 1:
It may be 0.5 (solid: dispersion medium (V / V)) or more, and in practice, it is preferably used in the range of 1: 1 to 1:10. During operation, continuous grinding treatment is also effective, in which what is once ground is repeatedly fed into a grinding machine. Further, if the alcohol dispersion medium is exchanged during the continuous grinding treatment, the cleaning effect can be further promoted.

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 keratin substance which is the object 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 ball is washed and the pulverized product is washed with alcohol or other volatile organic solvent to remove the residual oil and fat derived from the feathers, and then dried to obtain a fine feather powder (with a minimum particle diameter of about several microns). In this final-stage washing, the original feather volume 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 individually or in combination, but it is preferable to use acetone or ether.

Since the above-mentioned fine feather powder retains the original hollow matrix structure of the raw material, which is the raw material, and its lining structure inside, it retains hydrophobicity as an attribute of keratin and also traps oil morphologically. It has a structure that makes it easy to do. However, in the above-mentioned feather miniaturization step, as the miniaturization progresses, the degree of surface hydrophobicity of the feather fine powder decreases,
The hydrophilic part of keratin is easily exposed, and the internal hollow structure derived from the feather fiber tends to be easily subject to mechanical destruction, but on the other hand, the particle diameter of the feather powder becomes smaller, and not only oil but water. Dispersibility into

The above-mentioned fine feather powder is used as a treatment agent for surface-modifying an object to be treated, which includes oil absorption, antiperspirant, water retention, moisture absorption, dew condensation prevention, and light resistance. , Is a superordinate concept including various functions such as UV cut, and the surface to be processed includes a skin surface. Therefore, for example, in the case where the surface modifier is subordinately limited to the antiperspirant, the fine anti-perspirant powder is used as the main active antiperspirant, and the antiperspirant is added with or without the addition of the perfume and the dispersant. This is applied to the surface of the skin to be treated to prevent sweating.

The urethane modified product of the above-mentioned fine powder of feathers includes isocyanates and polyols in toluene, DMSO and D.
Basically, the feather fine powder is allowed to act in one or two steps in the presence of a solvent such as MF. For example, in the case of reacting in two steps, feather fine powder and isocyanates are added to the above solvent, the reaction of the first step is performed by stirring at room temperature for several days, and then polyol is added to the isocyanated feather fine powder. The mixture is added to the above solvent and the mixture is stirred at room temperature for several days to carry out the second stage reaction to obtain a urethane modified product of fine feather powder. However, the solvent used in the first-step reaction and the second-step reaction may be the same or different. The isocyanates refer to a compound having an isocyanate group, which reacts with a polyol to form a urethane layer, and on the other side, the isocyanate group can bond to amino groups, carboxyl groups, hydroxyl groups, etc. of feather proteins. It serves as a crosslinking means between the fine feather powder and the urethane layer coating the surface thereof.

The polyisocyanates are, for example, toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI) and hexamethylene diisocyanate.
(HMDI), isophorone diisocyanate (IPDI) and the like are preferable. The polyol is generally a diol or triol. Examples thereof include neopentyl glycol, glycols such as 1,4-butanediol, nonionic polyether glycols such as polyethylene glycol and polypropylene glycol, and cationic systems such as N-methyldiethanolamine. Anionic diols such as diol and dimethylolpropionic acid are preferable.

The surface modifying agent is a single use of the feather fine powder and the urethane-modified feather fine powder as an effective main component.
Alternatively, they are used in combination. However, the surface modifier refers to the whole of a plurality of components prepared by blending feather fine powder with various additives, dispersants, solvents, etc., and also refers to a single feather fine powder that does not include these additives. Be done. The form of the surface modifier may be sheet, powder, lump, or the like.

The above-mentioned sheet-like surface modifier is basically formed by adding a binder to fine feather powder or a urethane modified product thereof, but it is preferable to form it by combining pretreatment and finishing treatment. The pretreatment is a treatment in which at least one of additives such as lactic acid, urea, and thioglycolic acid is allowed to act on the fine feather powder in water, and appropriate modification such as cleavage of cystine bond or hydrogen bond is performed. Specifically, the additive is added to the fine feather powder in the presence of water and stirred to obtain suspension water of the fine feather powder. The treatment time is arbitrary, and the treatment temperature may be room temperature, but the treatment time can be shortened by heating. When the additive is lactic acid or urea, it is preferable to allow the prepared suspension water to stand as it is overnight for aging.

The above-mentioned binder is polyvinyl alcohol, gum such as gellan gum, phenol resin, silicone,
Preferred are starch, gelatin, casein, latex, sorbitol, pulp, and fibrous materials such as methylcellulose, carboxymethylcellulose, and cellulose. The binder is added as it is to the suspension water of the fine feather powder obtained in the above-mentioned pretreatment, or the suspension water is filtered through a filter to remove the liquid component, and then water is again added to the remaining fine feather powder. A suspension may be obtained and a binder may be added thereto. Once the binder has been added to the suspension water, the whole is stirred, and any paper such as a handmade Washi paper manufacturing method, a mechanical method, or a casting method in which the suspension is thinly applied and dried on a substrate is dried. A sheet material of fine feather powder is obtained based on the manufacturing process. If the pretreatment method is selected, the binder can be omitted.

When the above surface modifier is coated on another material such as a sheet material, a plate material, or a cloth material such as leather, rubber, or plastic, the surface of the other material is oil-absorbing, antiperspirant, moisture-proof, and dew-preventing. , Various properties such as light resistance and light resistance can be easily added, and on the contrary, durability such as strength can be added to the surface modifier.
Its convenience is enhanced. However, as the method for coating the surface modifier, the sheet-like surface modifier may be stuck to another material, or a powdery surface modifier may be dispersed and applied to the surface of the other material, or a lump-like material. The surface modifier may be attached in a dispersed form.

The oil absorbing agent may be in the form of sheet, powder,
It does not matter whether it is lumpy or not. It may be covered with another material or housed in a bag. For example, when the sheet-like surface modifier is used as it is as an oil absorbing agent, it is useful for absorbing and removing floating oil of the sea or river. In addition, when a powdery oil-absorbing agent or its dispersion is applied to oil-stained equipment, household tableware, or a bathtub with scales and polished with a wear tool such as cloth or brush, the oil-absorbing ability and feathers are reduced. The abrasive effect of the particles makes it possible to very effectively clean oil-contaminated surfaces.

However, as described above, as the fineness of the fine feather powder progresses, the internal hollow structure tends to collapse and the oil absorption tends to decrease. However, as will be described later, other materials such as talc and silk powder may be used. Since the feather fine powder by comparison shows a marked oil absorption rate, there is no particular obstacle to practical oil absorption performance, and conversely, by controlling the particle diameter of the feather fine powder, the oil absorbing agent of each form The function used can be adjusted appropriately.

The form of the antiperspirant may be liquid, paste, powder or the like. When the particle diameter of the fine feather powder is set to about a micron unit, dispersibility in the dispersion medium is increased and the risk of clogging of the injection nozzle can be eliminated, which is preferable as an antiperspirant for aerosols. In the antiperspirant for aerosol, fine feather powder may be dispersed in an alcohol-based dispersion medium so that the fine feather powder can be jetted by a propellant composed of compressed gas, or the fine feather powder can be liquefied gas such as LP gas. It is also possible to directly disperse the powder and inject the fine feather powder with this liquefied gas. In addition, fragrances and antioxidants may be added as additives. In particular, since most of the fragrances are lipophilic, they can be easily impregnated into the feather fine powder characterized by a high oil absorption rate (Note that if this oil absorption capacity is used in reverse, the feather fine powder will carry the fragrance. Promising as a base material).

[0027]

[Operation and effect of the invention]

(1) Most of the feathers that have been disposed of are miniaturized and used as a surface modifier, so that effective use of waste materials and labor saving of resources can be achieved at the same time. Further, since it is a surface modifier that takes advantage of the characteristics of natural feather keratin, 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) Since the fine feather powder has excellent properties as described above, various uses are expected as a surface modifier. First, the surface modifier of the present invention is extremely effective as an oil absorbing agent. That is, an oil absorbing agent having an oil absorbing / capturing function is already on the market under the name of oil catcher and the like, but its main uses are as follows. Environmental protection such as factory wastewater, factory waste oil and oil leakage, oil spilled into rivers and oceans, floating oil treatment, floating oil absorption in oil / water separation tanks, waste oil treatment in restaurants, restaurants, etc., oil absorption around machinery, road surface, Absorption of spilled oil into paddy fields.

The above-mentioned commercial products are, for example, those obtained by crushing waste paper and subjecting it to special treatment, imparting oil absorption to ceramics, or those based on highly oil-absorbing resins.
The oil absorbing agent of the present invention 3 has a large oil absorbing efficiency, and is very effective in cleaning equipment such as oil-stained equipment and removing oil pollution of rivers and oceans. Also, if you spray a powdery oil-absorbing agent on oil-dirty dishes or bathtubs with scales and polish it, you can easily remove oil with the oil-absorption capacity and the polishing power of the powder, so use ordinary household detergents. Can be omitted or the amount used can be suppressed, and domestic wastewater can be cleaned. However, when this oil absorbent is used in combination with a detergent, the cleaning effect is further enhanced. On the other hand, since this oil absorbent is composed mainly of feather fine powder, there is no danger of environmental pollution, it can be decomposed naturally by microorganisms and is easily disposed of after use. It is suitable as a product. Further, the oil absorbing agent is promising for removing sebum and removing makeup.

(3) The surface modifier of the present invention is effective as an antiperspirant. That is, as described above, fine feather powder has a large oil absorption rate and water retention capacity, and has high adhesion and spreadability to the skin. When it comes out, the fine particles widely and uniformly adhered to the skin surface efficiently absorb sebum and water and perspire. This antiperspirant can be used as an aerosol type antiperspirant spray or antiperspirant powder, as well as wristbands, hairbands,
It can also be used as a sweat pad for armpits, or as a sweat-absorbing anti-slip tape for tennis racket and bat grips.

Further, as in the case of the present invention 6 or 7, when the surface modifier such as a handrail, a door knob, a surface of office equipment or a desk, etc., which is in direct contact with the skin is coated with sweat,
It can absorb sebum and retain its surface with a smooth feel. Since the fine feather powder has high dispersibility and does not aggregate, a suspension of the antiperspirant can be easily prepared.

(4) As mentioned above, since the fine feather powder has a large water-retaining power, this surface modifier is also effective as a moisture-proofing agent and an anti-condensation agent. In particular, when the surface modifier is compounded in a laminated form on the surface of the wallpaper or floor material as in the case of the sixth or seventh aspect of the present invention, a moisture protection function is added to these indoor materials to enhance the commercial value.

(5) Feather fine powder has oil absorption, antiperspirant, water retention,
Since it has various functions such as moisture absorption and UV protection, this surface modifier can be effectively applied to cosmetics as a cosmetic disintegration preventive.
That is, when the surface modifier of the present invention is added to cosmetics and applied to the skin, it spreads thinly and evenly on the skin surface and adheres well, and it spreads well with sebum and does not leave a white residue, thus preventing makeup loss. Can be exhibited satisfactorily. In this case, due to the amphoteric electrolyte on the surface of the fine feather powder, the coating surface of the lower layer serves as a binder to bond the upper layer, so that smooth overcoating can be performed.

Further, the fine feather powder has an ultraviolet absorbing effect due to the property of the protein, which is its attribute, and since it scatters ultraviolet rays due to the shielding effect of the fine particles covering the adhering surface of the skin, it is effective for UV protection. The cosmetics to be applied include basic cosmetics such as cream and lotion, and finish cosmetics such as foundation and white powder. The cosmetics may be in the form of liquid, paste, powder or the like.

(6) Usually, the paint is a mixture of a color-developing agent consisting of a film-forming component, an additive and a solvent, and an organic pigment, but the fine powder of feathers has an ultraviolet absorption ability, dispersion stability and moisture resistance. Or, since it has various functions such as glossiness and colorability, the present surface modifier can be effectively applied as a film modifier also to paints. In this case, the present surface modifier is blended in the paint as an additive for coating film modification that imparts ultraviolet absorption, moisture resistance, etc., but as in the prior art mentioned above or the prior art, It does not prevent blending as a system organic pigment.

By the way, the fine feather powder dyed / impregnated with a tar dye or a colored fat-soluble vitamin or the fine feather powder undyed is easy to mix the colors and gives a delicate shade. When a surface modifier is added to a paint as a natural organic pigment, it has excellent gloss and a rich color tone.

(7) When the feather fine powder is modified with urethane as in the case of the present invention 2, the interaction with other materials is changed to adapt to various surface environments such as plastic materials, rubber materials, glass materials and metal materials. To have. For this reason, when the urethane-modified feather fine powder is coated on another material, the adhesion is improved, and the coating treatment is practical when the surface modification effect described in (1) to (6) above is applied to another material. It ’s even easier,
Various functionalities such as touch, gloss and smoothness can be added to other materials. Further, when the present surface modifier is coated on another material such as a rubber material or a plastic material as in the case of the present invention 6 or 7, the urethane-modified surface modifier is used so that it is well compatible with other materials. The coating adhesion strength can be improved. Furthermore, when a polyol such as the nonionic type is selected during the urethane modification, the hydrophilicity of the urethane layer formed can be sufficiently retained, so that the oil-absorbing property and the water retention capacity of the surface modifier after the urethane modification can be relatively easily performed. Can be compatible.

[0038]

[Examples] In the following, preparation examples of fine powder of feathers, urethane modification examples of the fine powder of feathers, examples of sheeting, and comparative examples of oil absorption ratio between fine powder of feathers and other commercial products, particle size A test example of the oil absorption rate variation due to the difference is shown, and in addition, a cleaning test example and an antiperspirant test example of oil of fine powder of feathers will be sequentially described. However, the present invention is not limited to the following examples.

<< Preparation Example of Feather Fine Powder >> Feathers of chickens were washed with water to remove blood and meat pieces, air-dried, degreased with ether, and immersed in 70% ethanol. The ethanol-soaked material of defatted feathers was circulated three times by a stone mill type grinder (mass colloider MKZA6-5; manufactured by Masuyuki Sangyo), and then ground, then filtered, washed with water and filtered again to obtain the first-stage ground product. Obtained. Then, the first-stage ground product was prepared so as to be a slurry having a solid concentration of about 7% with respect to water, and a vibrating ball mill grinding machine (SWECO vibration mill M-18L; manufactured by Shinko Pantech Co., Ltd.) was used. It is ground for 20 hours with 1/2 inch alumina media, washed with water, washed with ethanol and acetone, and then the second-stage ground product (F
P-20H) was recovered. However, in the second step, an appropriate amount of the milled product for the first 5 hours is taken out every hour, washed under the same conditions as the milled product for 20 hours, and then collected as a dry powder, respectively, and these Mechanically ground material FP-1
H, FP-2H, FP-3H, FP-4H, FP-5H
As individualized.

As a third stage grinding treatment, a planetary ball mill grinder (Hisie BX254; manufactured by Kurimoto Iron Works Co., Ltd.) was used, and FP-5H, which was the ground product for 5 hours, was made to have a slurry concentration of 20% in ethanol. The product was ground with a zirconia ball having a diameter of 3 mm for 12 minutes, and the ground product was washed with water, washed with ethanol and acetone, and then collected as a dry powder.
At the same time, the particle size of each of the above-mentioned various ground materials was measured by a laser diffraction type particle size distribution measuring device (LA-500; manufactured by Horiba Ltd.).

FIG. 1 shows the relationship between the particle size and the grinding time of fine feather powder. According to FIG. 1, it is observed that in the grinding process of the second step, the particle size of the fine feather powder decreases and becomes finer as the processing time becomes longer. When the particles are ground for 5 hours (FP-5H) or more, the particle diameter reaches 10 μm, and when the particles are ground for 20 hours (FP-20H), the particle size is reduced to 10 μm or less. In addition, in the grinding process of the third step, a fine powder having a minimum particle diameter of 4.08 μm was obtained.

FIG. 2 shows the composition analysis results of the fine feather powder (FP-5H) obtained in the second step. According to the same results, protein accounted for approximately 70% (by Kjeldahl method), followed by ash content of approximately 20%, and the fine feather powder was a proteinaceous organic powder containing a high proportion of water-insoluble protein. I understand.

<< Urethane Modification Example 1 of Feather Fine Powder >> Feather fine powder (FP-5H) and 2,4-T obtained by the above grinding treatment.
DI was added to a solvent of toluene in the following ratio and stirred at room temperature for several days to perform a first-step reaction for isocyanate conversion of fine feather powder to obtain 416.4 mg of a product. As a result of IR analysis of the product, a wave number of 228
An absorption peak due to N = C = O could be confirmed at ⁰ to 2290 cm ^-1 . FP-5H 500mg 2,4-TDI 1.4g Toluene 50ml

Next, the above-mentioned finely powdered feathers (hereinafter, referred to as isocyanate FP) and neopentyl glycol were added in a solvent of DMSO at the following ratios and stirred at room temperature for several days to modify the fine feathers with urethane. The second step reaction was carried out. Isocyanate FP 200 mg Neopentyl glycol 52 mg DMSO 30 ml The reaction product of the second step was collected by filtration, washed with DMSO and dichloromethane in this order, and then dried to 161.2 m.
g product was obtained. As a result of IR analysis of the product, the absorption peak due to N = C = O at a wave number of 2270 cm ^-1 disappeared, conversely, at a wave number of 2950 cm ^-1 , the aliphatic hydrocarbon C-
Since an absorption peak derived from methyl was observed, it was confirmed that a urethane-modified product of fine feather powder was produced. In this example, the solvent used in the first step reaction may be replaced with toluene by DMSO. In addition, regardless of the reaction in the first step and the second step, an appropriate period of 1 to 7 days could be selected as each reaction time.

<< Urethane Modification Example 2 of Fine Feather Powder >> Under the same conditions as in Modification Example 1 above, the fine feather powder (FP-5H) was subjected to the first step reaction to obtain isocyanate FP. Next, the isocyanate FP and 1,4-butanediol were added to the solvent of DMSO at the following ratio, and the mixture was stirred at room temperature for several days to carry out the second reaction. Isocyanate FP 200 mg 1,4-butanediol 46 mg DMSO 30 ml

The reaction product of the second step is recovered by filtration,
It was washed with DMSO, dichloromethane, water, methanol, water, and dichloromethane in this order, and then dried to obtain 162.8 mg of a finely powdered urethane modified product. However, the following conditions and the following conditions in Modification Example 2 are the same as Modification Example 1 described above.
Is the same as. Replace the first step reaction solvent from toluene with DMSO. The reaction time in the 1st and 2nd steps should be an appropriate period of 1 to 7 days.

On the other hand, as another example of the present urethane modification, feather fine powder (FP-5H) and XDI were added to a solvent of toluene at the following ratios to carry out the first step reaction, and then D
The second stage reaction may be carried out with 1,4-butanediol using MSO as a solvent. FP-5H 500 mg XDI 1.5 g Toluene 50 ml In this case, other conditions in the reactions of the first and second steps may be the same as those in Modification Example 1. Further, the above XDI may be replaced with 1.35 g of HMDI. In that case, the mixing ratio and the conditions of the selective solvent are the same as in the usage example of XDI.

<< Example 1 of Feather Fine Powder Sheeting >> The feather fine powder obtained by the above grinding treatment was first pretreated. That is,
The above-mentioned FP-5H and lactic acid were added to water at the following ratio, and the mixture was stirred at room temperature for 1 to 3 minutes and then left standing overnight for aging to denature the fine feather powder. Lactic acid 7.5g FP-5H 10g Water 1l

PVA as a binder was added to the suspension water of the above pretreatment.
(Fibribond; manufactured by Kuraray Co., Ltd.) (10 g) was added, and the mixture was stirred and then subjected to a finishing treatment using a commercially available handmade Japanese paper manufacturing tool to obtain a sheet material of fine feather powder. That is, the above-mentioned Japanese paper manufacturing tool is composed of a rectangular receiving box with a fine mesh wire mesh and a rectangular holding frame fitted into the receiving box from above. While pouring the suspension of the fine powder and holding the receiving box with the holding frame, when the solid substance spreads thinly on the wire net, the receiving container is turned over and the solid substance is transferred onto a cloth or filter paper. Take a cloth or filter paper in the same manner from above, absorb water on the front and back of the solid matter, press it with a roll or the like, dry it, and iron it as necessary to produce a sheet of fine feather powder. did.

In the present sheet forming example, the above PVA can be replaced with 1 to 2 g of gellan gum (manufactured by Sanei Chemical Co., Ltd.) previously dissolved in hot water as the binder.
It is also possible to omit the aging and immediately add the binder to the pretreatment suspension. Further, the pretreated suspension may be filtered to remove the drug solution, and then the binder may be added to the suspension prepared by adding water again to the fine feather powder.

On the other hand, the method of forming the suspension of the fine feather powder into a sheet is not limited to the above-described Japanese paper manufacturing method, and, for example, as described above, on a plastic or metal tray or a glass flat plate. There is no problem even if it is manufactured by a casting method in which the suspension is applied thinly, dried and then peeled off. In this case, if a metal tray or glass flat plate is selected as the base material because of the relationship with the hydrophobic function of the surface of the fine feather powder, peeling from the base material is relatively easy. If the material is selected, the sheet can be easily manufactured. On the other hand, feather fine powder (particularly the urethane modified product) has high adhesion strength to the rubber plate and is difficult to peel, so by using this sheeting method, the suspension of feather fine powder is used as a paint. it can. That is, by selecting a rubber material or the like having high adhesion strength as a coating target material, a thin film of feather fine powder can be applied as a coating for surface modification on the surface of the target material, and various materials can be coated on the surface of other materials. Functionality can be added.

<< Example 2 of Feather Fine Powder Sheeting >> FP
Pretreatment was carried out by adding -5H and urea in water at the following ratios to obtain a sheet of fine feather powder using PVA as a binder. Urea 20g FP-5H 10g Water 1l In this sheeting example 2, the reaction conditions of pretreatment, the amount of PVA added, the sheeting method by Japanese paper production, or the possibility of replacing PVA with gellan gum, etc. are the above sheeting examples. It was similar to 1.

<< Example 3 of Sheeting Feather Fine Powder >> FP
-5H and thioglycolic acid were added to water in the following ratios, pH was adjusted to 10 or less with sodium hydroxide, and pretreatment was performed to obtain a sheet of fine feather powder with PVA as a binder. Thioglycolic acid 0.9g FP-5H 10g Sodium hydroxide 0.26g Water 1l

In the present sheet example 3, after adding thioglycolic acid and stirring for 2 to 3 minutes, it is necessary to immediately shift to the finishing step of adding the binder. Therefore, the aging as in the sheet forming examples 1 and 2 is omitted. However, the other amount of PVA added, the sheeting method by the production of Japanese paper, the possibility of substituting PVA for gellan gum, etc. are the same as those in the sheeting examples 1 and 2.

<< Comparative Test Example of Oil Absorption Rate >> Various finely ground materials of fine feather powder prepared by the above grinding treatment (FP-1 to FP-2)
0H) having an arbitrary particle size is selected, and the oil absorption of linseed oil is determined by the following method based on a general pigment test method.
Commercially available talc (manufactured by Kanto Kagaku), silk powder (manufactured by Sumitomo Seika), and defatted wheat flour (commercially available defatted hexane) were measured as comparative examples. In this measurement method, a certain amount of feather fine powder is weighed in a tray, and linseed oil collected in a buret is dropped on the tray powder one by one, and the feather fine powder is kneaded with a spatula at each dropping. Repeatedly, the time when the fine feather powder became a paste and the spatula tailed (that is, the time when the fine feather powder reached a saturated oil absorption state) was taken as the end point, and the total consumption of linseed oil at that time was calculated as The oil absorption rate was obtained by dividing by the amount of powder weighed and converted to%.

FIG. 3 shows the comparison result. For example, the feather fine powder B having a particle diameter of 33.5 μm has an oil absorption rate of 467% (that is, it absorbs an oil content of about 4.7 times its own weight). hand,
Silk powder with a particle size of 32.1 μm (feather and silk composed of fibroin are common in that they are animal hard protein fibers) shows only 70% oil absorption, and other materials of similar particle size. The oil absorption of the fine powder of feathers was much higher than that of. Further, it has been found that the oil absorption rate is far higher than that of wheat flour, which has heretofore been known as having a high oil absorption ability. In addition, ND in the column of wheat flour in FIG. 3 indicates that when the wheat flour was treated with hexane, it became almost pasty and the particle diameter could not be measured.

<< Example of Oil Absorption Rate Test with Variation in Particle Size >> With respect to the various finely ground materials (FP-1 to 20H) of the above-mentioned fine feather powder, the change in oil absorption rate was measured when the fine particle diameter of the fine feather powder was different. Then, the relationship between the particle size and the oil absorption rate was investigated. However, the oil absorption rate was measured by the method of the oil absorption rate comparison test example.
FIG. 4 shows the results, and it is clearly recognized that the oil absorption rate of the fine feather powder decreases as the particle diameter becomes smaller, and the particle diameter is larger than the inflection point of about 20 μm. The decrease in oil absorption rate with the decrease in diameter was relatively gradual, but the decrease in oil absorption rate was large in the lower range.

From the above, the high oil absorption rate of the fine feather powder originates from the internal hollow structure of the feather fiber, and the hollow structure is mechanically destroyed as the particle size is further refined. It can be estimated that the oil absorption rate decreases. However, FIG.
As shown in Fig. 3, the oil absorption rate of 180% was maintained even with the fine feather powder having a minimum particle size of 6.7 µm, while the oil absorption rate of talc of 8.7 µm was as shown in the comparative test example (see Fig. 3). Oil absorption of 90%, 32.1μm silk powder is 7
Since it shows only 0%, the high oil absorption rate of the fine feather powder is still significant as compared with other materials even when the refinement progresses.

<< Cleaning Test Example of Oil of Fine Powder of Feather >> A pottery dish having a predetermined shape used for ordinary household tableware is selected, 1 ml of salad oil is dripped on the surface of the dish to spread evenly, and the dish is washed once with water. After that, 1 g of feather fine powder (FP-2H) was sprayed on the dish, and the remaining adherent salad oil was polished with a sponge for about 1 minute, washed again with water, and then dried, without using the fine feather powder. The cleanliness of the dish was visually inspected by using the case of polishing with a sponge as a comparative example.

As a result, when polishing was performed without using the feather fine powder, the residual adhesion of the salad oil was clearly observed almost uniformly over the entire surface of the dish, but when the feather fine powder was used, No trace of the sticking of salad oil was observed, and the visual inspection showed that the cleanliness of the dish surface was sufficiently achieved by removing the oil. In addition, in the test, in addition to the high oil absorption of FP-2H selected as the feather fine powder, the particle diameter was about 35.
It can be estimated that the polishing effect of the powder having a particle size of μm contributed to the cleaning.

On the other hand, paying attention to the oil removing function of the fine feather powder, when cleaning an oily body, by using the fine feather powder before washing with a detergent such as soap, the cleaning effect can be improved. It can be further increased. Also,
In the case of washing dishes in the kitchen, the use of the fine powder of feathers can eliminate or suppress the use of detergent.

<Example of antiperspirant test using fine powder of feathers> A panelist was prepared by arbitrarily selecting 10 people with hyperhidrosis or those with a strong tendency, and 100 mg of fine powder of feathers on the palm of each panelist.
(FP-5H) was attached and imprinted, and the sticky feeling of palm (that is, antiperspirant ability) after about 5 minutes was compared with that before use, and a sensory test was conducted. Figure 5 shows the result, and "no stickiness" is 3
There were 3 people who were "smooth" and 2 who were "smooth"
A person, "Kasatsuki," got a feeling of use of two people. Therefore, the evaluations of ◯ and ◎ reached 80%, and there was no unacceptable evaluation. Also, the evaluation was "△" for the "bulky" feeling of use, which indicates the above-mentioned high oil absorption rate of the fine powder of feathers. It seems that the feeling of use is improved by diluting it with other antiperspirant such as talc.

On the other hand, paying attention to the antiperspirant function of the fine feather powder, the sheet material of the fine feather powder is used as a door knob,
When it is attached to handrails, other indoor building materials, office equipment, etc., and covered, it gives a soft, dry, non-greasy feel to the surface.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the grinding time and the particle size of fine feather powder.

FIG. 2 is a chart showing the results of composition analysis of feather fine powder.

FIG. 3 is a table showing the results of a comparative test of oil absorption between fine feather powder and other materials.

FIG. 4 is a graph showing the relationship between the particle diameter of fine feather powder and the oil absorption rate.

FIG. 5 is a table showing the results of an antiperspirant test of fine feather powder.

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[Procedure amendment]

[Submission date] November 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

The surface modifying agent is a single use of the feather fine powder and the urethane-modified feather fine powder as an effective main component.
Alternatively, they are used in combination. However, the surface modifier refers to the whole of a plurality of components prepared by mixing feather fine powder with various additives, dispersants, materials, etc., and also refers to a single feather fine powder that does not include these additives. Be done. The form of the surface modifier may be sheet, powder, lump, or the like. The above-mentioned sheet body has already been described at the beginning of this item.
As described above, it means a sheet form similar to non-woven fabric, and paper
Starting with shaped workpieces, non-woven fabrics, or other planar processing
Including things.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

When the above surface modifier is coated on another material such as a sheet material, a plate material, or a cloth material such as leather, rubber, or plastic, the surface of the other material is oil-absorbing, antiperspirant, moisture-proof, and dew-preventing. , Various features such as light resistance and light resistance can be easily added.
Its convenience is enhanced. However, as the method for coating the surface modifier, the sheet-like surface modifier may be stuck to another material, or a powdery surface modifier may be dispersed and applied to the surface of the other material, or a lump-like material. The surface modifier may be attached in a dispersed form. For example, if you use a sheet-like surface modifier as artificial leather or
Laminated on the surface of leather such as natural leather,
When fine powder is kneaded into rubber or plastic materials, various
It is possible to widely improve the tactile sensation of contact points of goods or facilities. Well
The fine feather powder is used as a vehicle by utilizing its good dispersibility.
For example, it is mixed with the ink composition to form paper (for example, PPC
When applied to the back side of (paper) etc., pressure sensitive such as carbon paper
It is effective for paper manufacturing. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 28, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

The surface modifying agent is a single use of the feather fine powder and the urethane-modified feather fine powder as an effective main component.
Alternatively, they are used in combination. However, the surface modifier refers to the whole of a plurality of components prepared by blending feather fine powder with various additives, dispersants, solvents and the like, and also refers to a single feather fine powder that does not include these additives. Be done. The form of the surface modifier may be sheet, powder, lump, or the like. As described above in the beginning of this item, the sheet body means a sheet form similar to a non-woven fabric, and includes paper-like processed products, non-woven fabric-shaped products, and other planar processed products. However, in this sheet-shaped processed product,
It is also conceivable to replace part of the fine powder with pulp.
As mentioned above, the fine powdered feathers have a hollow matrix inside.
Since it retains a casks structure,
When the total ratio is 50% and the rest is pulp, the whole amount is pulp.
Compared to the normal paper produced, under the same thickness condition,
The weight per unit area can be reduced by about 25%. this child
And, conversely, replace part of the pulp with fine feather powder
And means that you can increase the area of paper per unit weight
Reduce the consumption of pulp,
Effective utilization and labor saving of pulp resources can be achieved at the same time.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C09D 175/04 PHM

Claims (7)

[Claims] 1. A surface modifier comprising a fine feather powder as an effective main component, which is configured to bring the fine feather powder into contact with an object to be treated to modify the surface thereof. 2. A surface modifier, wherein the fine feather powder according to claim 1 is a urethane-modified product of the fine feather powder, the surface of which has been urethanized with isocyanates and polyols. 3. The surface modifying agent according to claim 1 or 2 is an oil absorbing agent, which is configured to absorb and remove oil components on the surface to be treated by fine feather powder and modify the surface. An oil-absorbing agent whose main component is fine feather powder. 4. The surface modifying agent according to claim 1 or 2 is an antiperspirant, which absorbs perspiration components of the skin surface, which is the surface to be treated, by the fine powder of feathers for antiperspiring to modify the surface. An antiperspirant containing feather fine powder as a main component. 5. The sheet-like surface modifier according to any one of claims 1 to 4, wherein the fine feather powder is formed into a sheet. 6. A coating method with a surface modifier, which comprises coating the surface modification agent of claim 5 on the surface of another material. 7. The surface modifier according to any one of claims 1 to 4 which is in the form of powder or lumps, and the surface modifier is dispersed and coated on the surface of another material. A method for coating with a surface modifier.