JPH0755986B2 - Fine animal hair powder and method of making the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fine powder obtained by extremely finely crushing animal hair, particularly a scaly fine powder, and a method for producing the same.

[Conventional technology]

Animal hair, human hair, bird's feathers, feathers, etc. contain a large amount of keratin as a main component. Keratin is naturally insoluble and resistant to enzymatic and chemical modification reactions. However, the content of cystine as a constituent amino acid is high, and since it has a large amount of cystine residues and other functional side chains, it is highly reactive with metals and the like.
Therefore, fine powders of keratin substances include, for example, heavy metal adsorbents, keratographic carriers for heavy metal separation, feeds, medical polymers, carriers for immobilizing enzymes, carriers for affinity chromatography, pharmaceutical bases or cosmetic bases. Is expected to be used.

Conventionally, as a method of powdering keratin substances such as animal hair,
Japanese Patent Application Laid-Open No. 57-163392 discloses a method in which a keratin substance is treated with water or the like to give a water-containing substance, which is then frozen at -80 ° C or lower and then pulverized into a powder. Further, JP-A-57-192309 discloses a method of swelling a keratin substance by treating it with steam at high temperature and high pressure, and suggests a method of pulverizing this.

Furthermore, an attempt to apply wool powder to cosmetics has been made in JP-A-49-13.
No. 2247, JP-A-55-27120, and JP-A-54-70435.

[Problems to be solved by the invention]

However, the above-mentioned freeze-grinding method (JP-A-57-163392)
No. 1) requires the treatment of extremely bulky wool or the like with water and freezing with liquid nitrogen or the like, which necessitates a large-scale facility, the number of steps is large, and the cost is high. Furthermore, the particle size of the obtained product was also large. Further, in the above swelling and pulverizing method (JP-A-57-192309), in addition to the same drawbacks as described above, there is a serious drawback that wool is chemically damaged by heat and enzymes during treatment in a high-pressure kettle. There was also.

Since wool, feathers, and human hair are soft and have a low specific gravity and are extremely bulky, it is extremely difficult to make them into fine powder. The particle size of wool powder etc. obtained by a commonly used impact type fine pulverizer etc. is up to about 100 μm. In addition, since keratin, which is the main component of wool and the like, is a protein, it is vulnerable to heat, and when exposed to temperatures of several tens of degrees Celsius or more, it causes troublesome problems such as odor and coloring. That is, even if the pulverization is repeated to obtain a fine powder having a finer particle size, it cannot withstand the high temperature at the time of repeated contact with the pulverizing blade. Therefore, a method for producing fine powder such as wool having an average major axis of about 30 μm or less has not been known so far, and such fine powder has not been known.

The wool powder described in JP-A-49-132247, which has been applied to cosmetics, is also large, about 0.3 to 30 mm.
Further, the above-mentioned JP-A-55-27120 and JP-A-54-70435.
The respective publications do not disclose a fine wool powder having an average major axis of 30 μm or less and a method for producing the same.

Therefore, the object of the present invention is fine powder of animal hair, human hair, bird's feather or bird's feather, etc. Moreover, it is to provide keratin without denaturing it.

[Means for solving problems]

The present inventor has found that a fine powder of animal hair having an average major axis of 30 μm or less and an aspect ratio of 4 or more can be prepared by utilizing the circulating vacuum grinding technique. Therefore,
The present invention provides a fine powder of animal hair having an average major axis of 30 μm or less and an aspect ratio of 4 or more.

Furthermore, the present invention provides a method for producing a fine powder of animal hair having an average major axis of 30 μm or less and an aspect ratio of 4 or more, which is characterized in that animal hair is circulated and vacuum pulverized.

As used herein, "animal hair" means animal hair, human hair, bird feathers and bird feathers. Examples of animal hair include wool, mink hair, ordinary goat hair, mohair hair, Tibetan hair, camel hair, cashmere hair, llama hair, alpaca hair, guanaco hair, angora rabbit hair, cow hair, ordinary rabbit hair, horse hair, cats. There is hair, pig hair, etc. The feathers and feathers of birds include, for example, feathers and feathers of moths, ducks, other waterfowls, chickens and the like.

The fine powder of the present invention can be prepared, for example, by the method of the present invention by circulating vacuum pulverizing the animal hair. The circulation vacuum pulverization is carried out by using a circulation type vacuum pulverization apparatus which is a further improvement of the known vacuum pulverization apparatus (Japanese Patent Publication No. 52-11787) according to the present invention. The known vacuum crushing device, as described in the above publication,
(A) Container for crushed material loaded with raw material to be treated, (b) crusher equipped with hammer and ridge, (c) container for crushed material for collecting products, and (d) intervening therebetween And (v) a vacuum pump connected to the crushed material container (a) and the crushed material container (c). The present inventor has improved the vacuum crushing device to replace the hammer and the projecting piece in the crusher (b) with a rotary blade and a fixed blade, and to provide the outlet of the crushed material container (c) and the crushed object. The inlet of the material container (a) was connected to enable circulation and pulverization under vacuum. Circulating vacuum crushing of animal hair using this improved device results in much finer crushing of animal hair than conventional ones.

The circulating vacuum grinding of the present invention is 2 to 30 mmHg, preferably 2 to 30 mmHg.
It is carried out under a vacuum of 10 mmHg. The circulation is performed 2 to 10 times, preferably 3 times. Before carrying out the above-mentioned circulating vacuum crushing, the animal hair as a raw material is treated with an organic solvent such as diethyl ether,
It can be degreased with acetone, chloroform, trichloroethane or the like, or degreased and washed with various surfactants.

A commercially available product after degreasing / washing treatment can be used as it is.

The product is classified after the circulating vacuum milling process. As the classification method, a method known per se, for example, screening with a sieve, wet classification or dry classification can be used. Dry classifiers such as weight classifiers, inertial classifiers, especially centrifugal classifiers, are preferably used, and forced vortex centrifugal classifiers are particularly preferred. Fine powder mainly composed of cuticle (hair scalp) forming the outermost layer of animal hair by adopting an appropriate classification means (in this case, for example, forced vortex centrifugal classifier (separation diameter 0.5 to 50 μm) Preferably 0.5 to 30 μm)], or other parts, ie cortex and cortex (medullary pulp)
A fine powder containing a large amount of can be obtained.

The above-mentioned animal hair dyeing, bleaching, UV treatment, electrostatic treatment, water repellent treatment, insect repellent treatment, antiseptic treatment, antifungal treatment, and other surface treatments may be performed before or after the circulating vacuum pulverization treatment or before or after the classification treatment. Although it can be carried out in any case, it is preferably carried out after the classification treatment.

For dyeing, for example, Red No. 3, Red No. 104, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, Blue No. 2, Red
No. 227, Red 230, Orange 206, Orange 207, Yellow 202
Stain according to a conventional method with natural dyes such as No. 1, No. 201, No. 201, No. 204, No. 205, etc., tarmin, carminic acid, laccaic acid, calsamine, bradylin, crocin, annatto, anthocyanin, safrole yellow, red pickle dye, etc. be able to. Regarding the UV treatment, for example, salicylic acid,
An ultraviolet absorber such as para-aminobenzoic acid or urocanic acid can be adsorbed by a conventional method.

By circulating vacuum crushing and classification, the average major axis of 30μ
A fine powder having a particle size of m or less and an aspect ratio of 4 or more is obtained.
The obtained fine powder is mainly composed of scale-like (plate-like) fine powder.

In the present specification, the size of the fine powder is measured as follows. The fine powder obtained was suspended in a dispersion medium such as acetone, placed on a sample table made of aluminum, dried, and then gold-deposited to form a sample. Take a micrograph.

Since the image figure of the fine powder is indefinite, its longest diameter is defined as "major axis", and at least 50, preferably 100 or more fine powders are measured for major axis, and the average value is "average major axis". To do. In addition, the longest diameter in the direction perpendicular to the above "major axis" is defined as "minor axis", and the biaxial average of each fine powder, that is, ("major axis" + "minor axis") x 1/2 The average value calculated and obtained from the individual biaxial averages in the same manner as above is referred to as "average biaxial average". On the other hand, a sample was prepared from the fine powder in the same manner as above, the sample stage was tilted at about 45 °, and an electron micrograph of the flaky fine powder was taken from the side. The “average thickness” is calculated in the same manner as above. Next, "average biaxial average" /
The "average thickness" is calculated, and this is referred to as the "aspect ratio".

The fine powder of the present invention measured by the above method has an average major axis of 30μ.
m or less, preferably 1 to 20 μm, more preferably 2 to 10 μm
m, an average biaxial average of 1 to 20 μm, preferably 2 to 10 μm, an average thickness of 5 μm or less, preferably 0.1 to 2 μm, and an aspect ratio of 4 or more, preferably 7 to 100.

The surface area of the fine powder according to the present invention is 0.1 m ^{2 when} measured by the BET method.
/ g or more, especially 0.5 to ⁵ m ² / g.

When the fine powder of the present invention is observed with an electron microscope, many scaly powders are visible. Further, in the amino acid composition of the fine powder, since the amounts of serine, proline and cystine are large,
It is considered that cuticle is the main component. Therefore, the circulating vacuum crushing process according to the present invention crushes individual cuticle units. As described above, since individual cuticle units are crushed, the same crushing is performed at least partially on the animal hair cortex (cortex) and medula (hair pulp). It is considered to be a thing.

〔The invention's effect〕

The fine powder according to the present invention is extremely finely and relatively uniformly pulverized as compared with the conventional powder, and moreover, since it is scaly (or tabular) as a whole, the surface characteristics of the keratin substance are more effective. Can be used for.

Therefore, adsorbents for heavy metals (mercury, copper, cadmium, chromium, etc.) adsorbents, chromatographic carriers for separating heavy metals, feeds, medical polymers, and enzymes are immobilized as they are or after subjecting the fine powder of the present invention to an appropriate treatment. It can be used as a carrier for pharmaceuticals, a carrier for affinity chromatography, a pharmaceutical base and a cosmetic base. Further, since the fine powder of the present invention exhibits an excellent emulsifying action, it can be used also as an emulsifier. Further, among the fine powders of the present invention, colored fine powders themselves containing a pigment are in the form as they are, or fine powders which themselves do not contain a pigment or do not have a desired color tone are appropriately dyed. Later, those colored or colored fine powders can be used as pigments or dyes.

Since the circulating vacuum pulverization method according to the present invention performs pulverization in the absence of air, the powder keratin substance is not oxidized by oxygen, and the frictional heat of the pulverizer under high-speed rotation is dissipated to the outside. Degeneration of the keratin substance due to heat is also unlikely to occur. Therefore, animal hair is finely pulverized without being chemically altered, and chemical denaturation does not occur in the subsequent classification treatment.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
This does not limit the invention.

Example 1 (a) Preparation of fine powder according to the present invention 50 kg of merino wool that had been degreased / washed by the usual method and chopped in advance was vacuum-milled (Sawawa Kasei: SWM-48).
(Type) circulation-type improving apparatus was loaded into a crushed object container, the inside of the system was evacuated (5 mmHg), and then crushed by operating for 6 hours under the conditions of 5.5 Kwh and 3000 rpm. If the same crushing is performed without circulating this device, the required time is 2
Since it was time, this treatment means that the milling treatment was repeated three times on average.

Next, a forced vortex centrifugal classifier (Nissin Engineering: T
C-15N type (separation diameter 20 μm)]
4.5 kg of fine powder having a size of μm or less was obtained. The results of observing the resulting fine powder with a scanning electron microscope (JEOL: JSM-T100 type) are shown in FIGS. 1 and 2.

It is considered that the fine powder thus obtained substantially contains cuticle as a main component. The reason is as follows.

(1) The amino acid composition of the fine powder is in good agreement with the amino acid composition of the raw wool cuticle [see (c) below].

(2) The shape of the fine powder shown in the electron micrographs (FIGS. 1 and 2) is scale-like, which matches the shape of the cuticle.

(3) The yield of fine powder is almost equal to the weight ratio of cuticle in wool (about 10%).

(B) Preparation of fine powder for control The product obtained by operating the improved apparatus of Example 1 (a) for 6 hours in the same manner without applying a vacuum, and observing the result with a scanning electron microscope in the same manner, It is shown in the photograph of Fig. 3. As is clear from FIG. 3, the cuticle was partially peeled off and the fiber tissue was partially destroyed, but most of the wool remained in a long fibrous state. In addition, coloration was recognized with the naked eye, and there was also a sulfur-like odor.

Table 1 below shows the dimensions of each powder.

(C) Amino acid analysis 10 mg of merino wool as a starting material and 10 mg of fine powder as a product of Example 1 (a) were precisely weighed into a test tube for hydrolysis, 2 ml of 6N hydrochloric acid was added, and the mixture was evacuated. I sealed it. Then, it was completely hydrolyzed at 110 ° C. for 24 hours. The obtained decomposition liquid was concentrated under reduced pressure to remove hydrochloric acid, and then diluted to obtain a sample for amino acid analysis. These samples were analyzed by a fully automatic high speed amino acid analyzer JLC-300 (JEOL). Data processing is performed by the data processing device 7000B (System Instruments)
Done by. The results obtained are shown in Table 2.

As is clear from Table 2, the fine powder of the present invention contains a large amount of serine, cystine and proline, and it is found that the cuticle content is large when compared with literature values.

(D) Measurement of particle size distribution The particle size distribution of the fine wool powder of the present invention of Example 1 (a) was measured. Microtrac particle size distribution meter
Laser analysis was performed using a 7995-30SPA model (Nikkiso). Table 3 below shows the particle size classification, the distribution ratio and the average particle size in each particle size classification.

Table 3 Upper limit of particle size classification (μm) Distribution rate (%) 42.21 0.0 29.85 0.0 21.10 0.0 14.92 2.1 10.55 22.2 7.46 17.3 5.27 11.7 3.73 15.6 2.63 16.3 1.69 9.1 1.01 3.8 0.66 1.6 0.43 0.0 0.34 0.0 0.24 0.0 0.17 0.0 Average Particle size 4.81μ In the above-mentioned measurement method using the Microtrac particle size distribution meter, the sample dispersion liquid is flowed in one direction to uniformly disperse the sample. In the case of the above-mentioned wool fine powder, since the sample is scaly, the major axis of most of the particles is almost parallel to the flow method. Laser irradiation is performed from the direction perpendicular to this flow direction, and the particle size is measured by diffraction of the scattered light. Therefore, the average particle size according to Table 3 is the average of the biaxial averages of all particles, that is, the average biaxial. It is close to the average.

(E) Measurement of water absorption and oil absorption The limit of the amount that the powder can absorb the liquid is usually called the liquid absorption, and the liquid is added little by little to 100 g of the powder, and the condition of the powder is observed while kneading, The point of forming one lump from the dispersed state was found, and the weight (g) of the liquid added up to that point was taken as the liquid absorption amount of the powder. Although the liquid absorption varies greatly depending on the surface properties of the liquid, it is said that the size of the particles has a particularly large effect, and the smaller the particle size, the larger the liquid absorption.

The results of measuring the water absorption using distilled water and the oil absorption using liquid paraffin and isopropyl myristate as oil are shown in Table 4 below.

Example 2 When the feathers of moth birds were treated in the same manner as in Example 1 (a) above, the same fine powder was obtained.

Example 3 When mohair was treated in the same manner as in Example 1 (a) above, the same fine powder was obtained.

Comparative example Merino wool 10 degreased and washed by the usual method
Soak 0g in 1.0kg of water for 3 hours, then spin-dry.
The water content was 80 g. This was frozen in liquid nitrogen (-196 ° C) and pulverizer [Fuji Denki Kogyo: Sample Mill (K II-
1 type)]. The results of observing the thus obtained wool powder with a scanning electron microscope (JEOL: JSM-T100 type) are shown in FIG. As is clear from FIG. 4, it was found that the conventional freeze-grinding method can only cut the wool fiber into slices and cannot substantially destroy the fiber structure.

[Brief description of drawings]

1 and 2 are electron micrographs showing the shape of the fine wool powder of the present invention obtained by utilizing circulating vacuum crushing. FIG. 1 shows a magnification of 1000 times, and FIG. 2 shows a magnification of 5000 times. belongs to. FIG. 3 is an electron micrograph showing the shape of wool powder obtained by circulating pulverization under non-vacuum at a magnification of 100 times. FIG. 4 is an electron micrograph at 100 × magnification showing the shape of wool powder obtained by freeze-grinding.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Nakano 1-2-14, Nunoichi-cho, Higashi-Osaka-shi, Osaka Prefecture Seiwa Kasei Co., Ltd. (72) Inventor Takashi Adachi 1 Nunoichi-cho, Higashi-Osaka, Osaka No. 2-14 Stock Company Seiwa Kasei

Claims (2)

[Claims] 1. An average major axis of 30 μm or less and an aspect ratio of 4.
The above is a fine powder of animal hair. 2. A method for producing a fine powder of animal hair having an average major axis of 30 μm or less and an aspect ratio of 4 or more, characterized by circulating vacuum pulverizing animal hair.