JP2011236131A - Insoluble collagen-containing powder originated from fish scale - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new water-insoluble collagen-containing fine powder containing insoluble collagen obtained from fish scales, to provide a new production method therefor, and to provide a new utilization thereof.SOLUTION: The water-insoluble collagen-containing fine powder is produced by the following two treatments: (1) thermally treating fish scales in heated water of 90 to 95°C, separating the thermally treated product as a composition containing water-insoluble collagen, and then drying the product; or (2) thermally treating fish scales in heated water of 100 to 140°C under pressurization, decoloring the obtained colored thermal treatment product, separating the decolored product as a composition containing the water-insoluble collagen, and then drying the product, and subsequently subjecting each dried product to a roughly crushing treatment (particle diameters of about 1 to 2 mm) and then to a fine crushing treatment (particle diameters of about 0.4 to 200 μm). The obtained water-insoluble collagen-containing fine powder is used as a new scrubbing agent, keratin-removing agent, or moisturizing agent to be added to cosmetics.

Description

  The present invention relates to a fish scale-derived insoluble collagen-containing powder, a production method, and a method for using the same.

Collagen is a major component other than the connective tissue between skin and cells, bone and tooth minerals, and is known as a collagen containing about 18 kinds of amino acids such as glycine, proline and lysine. Such collagen is considered to be a substance having an action of enhancing the ability to retain moisture, which is important for maintaining skin tension and elasticity. In addition to being blended into cosmetics and dietary supplements, it is used as a medical material for immobilizing substances using collagen as a carrier. These are used in the state of solubilized collagen by degrading collagen under enzyme or alkaline conditions. On the other hand, insolubilized collagen is actively used as a medical material as fibrous insolubilized collagen without being decomposed.
In any case, since collagen is widely present in many animals including humans, it has a wide range of uses because it acts safely and effectively on humans. The company of the present inventors succeeded in using solubilized collagen to form fibrous solubilized collagen (Patent Document 1 JP 2006-342472 A).

  Conventionally, cattle and pigs have been used as raw materials for producing solubilized collagen. Faced with mad cow disease, it is necessary to switch raw materials from cattle to other animals as a countermeasure, and the use of fish scales has been studied as part of this. The use of fish scales is being promoted as a result of diversification of raw materials as part of measures against mad cow disease.

Fish scales, which are raw materials, have a calcium-containing substance that is hydroxyapatite on the outside. Its properties are hard to protect internal materials. In order to extract collagen from fish scales, it is necessary to remove the calcium-containing substance that forms the outside of the fish scales. This is called decalcification. Although the size and composition differ somewhat depending on the fish species, the calcium content is generally about 30%. The collagen extraction rate by boiling from demineralized scale is about 30%, and at most less than 40%, and it is pointed out that the yield from fish scale is poor and expensive (Patent Document 4). Further, it usually contains about 50% ash and about 40% protein. It is known that most of the ash is calcium phosphate (hydroxyapatite), and about 80% of the protein is collagen.
As a method for extracting solubilized collagen from fish scales, a method for extracting directly from fish scales with hot water and a method for extracting directly with acetic acid are known (Non-patent Document 1 Journal of Japanese Society of Fisheries Science 54 (11), 1987-1992). (1988)). The hot water treatment is to extract decalcified and solubilized collagen.
For fish-derived collagen, atelocollagen is soluble in water by washing, degreasing, acid treatment or enzyme treatment, salting-out, dialysis, or other separation means such as fish skin and bone, or by treating with enzyme protease instead of acid treatment Examples of collagen derivatives include acylated and esterified collagen derivatives such as succinylated collagen obtained by treating atelocollagen with succinic anhydride, myristylated atelocollagen treated with myristic anhydride (Patent Document 2) 2003-183219).
Gelatin is produced from fish scales and enzymatically decomposed to obtain low molecular weight collagen (Patent Document 3 Japanese Patent Application Laid-Open No. 2008-86219). Collagen molecules contained in many raw materials are insoluble with three peptide chains forming a helical structure, having a molecular weight of about 300,000. Since this large molecular weight collagen is difficult to be digested and absorbed even when ingested, it is reduced in molecular weight and used as a solubilized collagen in beverage products. Collagen is decomposed considering that it is difficult to be digested and absorbed.
Similarly, after decalcification of scales, by using an extraction residue obtained by boiling and extracting collagen in hot water at 90 to 100 ° C. as a raw material, after acting an acidic protease that is a proteolytic enzyme, decolorization with activated carbon A method for producing low molecular collagen (Patent Document 4, Japanese Patent Application Laid-Open No. 2008-220208) is known.

When using fish scales, it is an important issue to solve the problem to effectively perform the decalcification operation of the fish scales and the subsequent operation of decomposing it into collagen. As described above, deashing is complicated, and from the point of view of use, if it can be done without deashing, it will not be over. Specifically, the following methods are known.
In the method of directly crushing fish scales without causing decalcification and allowing the protease to act (Patent Document 5), the fish scale raw material is washed as necessary, dried, and mechanically dry-type or wet-ground. After making into a cotton or powder form, a collagen peptide is produced by allowing a proteolytic enzyme to act on this fish scale without decalcification treatment. In order to obtain mechanically dry or wet-pulverized cotton-like or powder-like scales, specifically, an impact with a medium-speed rotational motion mechanism, a type to be ground by shearing, or an impact with a high-speed rotational motion mechanism The type that is pulverized in the above is preferable. Therefore, the operation of directly pulverizing is difficult and is not preferred.
In Patent Document 7, when collagen is extracted from fish scales, a method of extracting decalcified scales by high pressure treatment without pulverizing treatment or a method by hydrolysis with an enzyme is employed. This is considered problematic in terms of preprocessing.
In addition to the enzyme, the fish scale is enzymatically decomposed with a proteolytic enzyme and an enzyme that destroys the structure of the fish scale, based on a method of allowing an enzyme such as chitinase to act so that the fish scale is easily decomposed (Patent Document 6). It is a feature to obtain.
Conventionally, the essential desalting treatment and mechanical destruction of the fiber structure of collagen are unnecessary, so that the manufacturing process can be shortened and the manufacturing cost can be reduced. In addition, since the amount of water used for the decomposition is small compared with the conventional method of decomposing without mechanical destruction, the advantage that collagen peptides can be extracted at a high concentration is emphasized.
In addition, the method in which various proteases are allowed to act in the basic region (Patent Document 8) is characterized in that an oligopeptide having an extremely small molecular weight can be obtained by the action of alkali. The method of directly crushing fish scales to allow proteolytic enzymes to act is very difficult to crush fish scales due to the strong triple helix structure unique to collagen and decalcification is not performed. Subsequent separation and removal of calcium is required. There were problems such as the purchase of expensive crushers and separation devices. In addition, a method in which a proteolytic enzyme is allowed to act after an enzyme such as chitinase is acted so that fish scales are easily decomposed increases the yield to some extent, but a considerable residue remains. In addition, since various enzymes having different molecular weights are used in combination, it is difficult to remove the enzyme protein from the degradation product. In addition, it has been pointed out that the method in which an alkaline protease is allowed to act in the basic region is mainly decomposed by alkali, and only oligopeptides (amino acids having a trimer or less and a molecular weight of about 200 or less) can be obtained.

Conventionally, it has been usual to use soluble collagen as a cosmetic. A cosmetic (Patent Document 9 Japanese Patent Application Laid-Open No. 2004-250421) containing a water-insoluble collagen as an essential component is known. It is a cosmetic containing, as an essential component, a water-insoluble collagen that is a residue after being decalcified and then decomposed by acid or enzyme to elute water-soluble collagen. Unfortunately, the specification of this invention does not reveal specific processing means and water insoluble collagen. Thus, the decalcification process is performed and the complicated process is inevitably performed. In addition, although the water-insoluble collagenous substance, which is a residue, is an essential component, the water-soluble collagenous substance must be taken out as a by-product, and the method is not good. Even the cosmetics containing water-insoluble collagen as an essential component are not disclosed in the present invention.
In addition, as a method for producing a water-soluble low-molecular and insoluble high-molecular-weight collagen and chitin complex obtained by decalcifying a relatively hard fish scale, after using a relatively hard scale as a raw material, An invention for producing a transparent, thin-film crude raw material composite is known (Patent Document 10 Japanese Patent Application Laid-Open No. 2003-23970). About 6 times the amount of purified water is added to the obtained crude raw material composite and put into a high-pressure reaction tank, and the treatment is performed for about 1 to 5 hours in the range of 0.1 to 0.2 megapascal. Then, it is fractionated into an insoluble polymer and a water-soluble low-molecular complex. The insoluble polymer composite remaining by this treatment is filtered with a cotton cloth, washed with water, dried and pulverized to obtain a raw material such as a tablet. On the other hand, the water-soluble low-molecular complex contained in the filtrate is concentrated to an appropriate concentration, usually 10%, and then used as an aqueous solution or as a water-soluble powder in a spray-drying device or the like as a product. . Although depending on the high-pressure treatment conditions, the insoluble polymer composite yields 10-15% of the original crude raw material composite. It has been confirmed that the insoluble polymer complex contains approximately 1 to 9% of chitin and the remainder is collagen having an average molecular weight of 100,000 to 200,000. Use is for food additives.
A collagen peptide-containing solution (Patent Document 11 Japanese Patent Application Laid-Open No. 2004-91418) is known in which crude collagen from which fish scales have been decalcified is appropriately hydrolyzed in an alkaline aqueous solution in which an alkali salt is dissolved in a pressurized atmosphere. It has been. A method for producing a collagen peptide-containing powder includes a step of decalcifying fish scales to obtain crude collagen, and a step of appropriately hydrolyzing the crude collagen in an aqueous alkaline solution in which an alkali salt is dissolved in a pressurized atmosphere. . It will be described that the yield of collagen peptide can be increased by gelatinizing crude collagen. Since such a collagen peptide-containing powder is a powder in the final form, it has an advantage that it can be easily added when manufacturing cosmetics and functional foods.
In the conventional example, although insoluble collagen is the target substance, it is not sufficient in that water-soluble collagen is contained.
The present inventors have been forced to develop a substance containing insoluble collagen using fish scales as a raw material, and have been required to develop a rational manufacturing process therefor.

Cosmetic additives include the water-insoluble collagenous material of Patent Document 9 whose meaning is unknown. By the way, the scrub agent used as a cosmetic is as follows.
It is well known that the physical detergency effectively removes wastes, sebum, keratin, dust adhering to the skin surface, and the like, and a massage effect on the skin by stimulation. Further, although not a scrub, as a tool for removing keratin, as disclosed in Japanese Patent Application Laid-Open No. 2001-105331, skin abrasion is achieved by adding vegetable abrasive particles as a core and a silk component thereto. Skin scrubbing tools that add a skin beautifying effect to the function are also known. The vegetable abrasive particle layer is composed of plant abrasive particles obtained by drying and crushing a plant material having an appropriate hardness. Examples of the plant material include fruit cores such as peach seeds, apricot seeds, and walnut shells, and corn cobs.
Originally, a scrubbing agent that has a good feel and that is coated with a powder with an amino acid or a polypeptide to enhance familiarity with the skin is known (for example, Japanese Patent Publication No. 1-50202 and Japanese Patent Application Laid-Open No. 5186706, Patent Document 15 Japanese Patent Laid-Open No. 3-200909, Patent Document 16 Japanese Patent Laid-Open No. 9-328413, Japanese Patent Laid-Open No. 10-226626, and the like.
Although these prior documents describe that the coated powder has a smooth feel and high affinity with the skin, the conventional scrubbing agent is hard, and the physical irritation is highly satisfactory. There was no state.

JP 2006-342472 A JP 2003-183129 A JP 2008-86219 A JP 2008-220208 A JP 2004-057196 A JP 2006-000089 A JP 2003-327599 A JP 2001-2111895 A JP 2004-250421 A JP 2003-23970 A JP 2004-91418 A JP-A-2001-105331 Japanese Patent Publication No. 1-50202 JP-A-5-186706 JP-A-3-200909 JP 9-328413 A Japanese Patent Laid-Open No. 10-226626

Japanese Journal of Fisheries Science 54 (11), 1987-1992 (1988)

An object of the present invention is to provide a novel substance containing insoluble collagen using fish scales as a raw material, and to provide a novel scrubbing agent or exfoliating agent and moisturizing agent to be added to cosmetics.

The present inventors diligently studied the above problems, and found the following to complete the present invention.
(1) Conventionally, after demineralizing fish scales, the product is decomposed with acid or enzyme, and water-soluble collagenous substance, which is a residue after elution of water-soluble collagenous substance, is obtained as an essential component. The cosmetic used is used.
(2) The present inventors considered that the production of water-soluble collagenous material is not a target substance in the above-described method, and thus is not a preferable method in this respect.
However, fish scales are difficult to be finely pulverized only by decalcification, and this is a problem.
(3) Therefore, it will be examined how to create a situation that facilitates crushing. That is, it is important to denature fish scales so that they can be easily crushed.
At that time, since the water-insoluble collagen is taken out from the final product, it is necessary to avoid the production of water-soluble collagen as much as possible, and it is necessary to create a situation in which it is difficult to produce water-soluble collagen. In this way, a water-insoluble collagen substance can be obtained. This can be obtained as a new scrubbing agent, exfoliating agent, or foundation moisturizing agent because it has been obtained in the past in terms of hardness and touch. Whether or not a process like the above inference can be developed is an important key.
(4) The present inventors examined a specific processing method for making the fish scales easy to be crushed. Conventionally, when fish scales are treated with hot water, it has been carried out for the purpose of obtaining water-soluble collagen. Therefore, demineralized fish scales are not used in conventional hot water treatment, but are treated in hot water such as immersing in hot water for a short time so as not to decompose, or heat treatment in heated water under pressure, in autoclaves When the pulverization treatment is performed after the treatment with the above, finely pulverized water-insoluble collagen-containing fine powder can be obtained, and further classification can obtain finely pulverized water-insoluble collagen-containing fine powder in a narrow particle size range. I found out that I can do it. This insoluble collagen-containing fine powder is different from the conventional insoluble collagen-containing fine powder and has water retention, flexibility and fine powder shape retention, and cosmetics contained in the insoluble collagen-containing fine powder as a component are physically With its cleansing power, it can efficiently remove wastes, sebum, keratin, dust adhering to the skin surface, and effectively stimulates the skin when applied to the skin surface. Massage the body together to promote blood flow and activate skin cells. Including water does not scratch the skin surface. Although it is softer than conventionally used scrubbing agents, it has a scrubbing effect.
(5) In the present invention, a novel water-insoluble collagen-containing fine powder can be obtained by the following production method.
(6) The fish scales are obtained by heat-treating the fish scales in heated water at 90 to 95 ° C., separating the heat-treated product as a composition containing water-insoluble collagen, drying it, and then crushing it. Water-insoluble collagen-containing fine powder.
(7) The fish scales are heat-treated in heated water at 100 to 140 ° C. under pressure, and the resulting colored heat-treated product is decolorized and separated as a composition containing water-insoluble collagen. A fine powder containing water-insoluble collagen, which is obtained by pulverizing into water.

According to the present invention, insoluble collagen-containing fine powder can be obtained without producing soluble collagen using fish scales as a raw material. Cosmetics containing fine powders containing insoluble collagen as raw materials or ingredients can efficiently remove wastes, sebum, keratin, dust attached to the skin surface, etc. generated by the physical detergency. When applied to the surface of the skin, it provides effective stimulation to the skin, massages the skin, and promotes blood flow and activates skin cells. Including water does not scratch the skin surface. Although it is softer than a conventionally used scrub agent, it has a scrub effect.
Moreover, since the insoluble collagen-containing fine powder obtained by the present invention has high hygroscopicity, a foundation with high moisture retention can be obtained by containing it in the foundation.

Results of DSC analysis after washing and decalcifying tilapia fish scales, results of DSC analysis after washing and decalcifying tilapia fish scales and heat treatment, and washing and decalcification of tilapia fish scales It is a figure which shows the result of having performed DSC analysis after carrying out drying processing after heat processing, and then grind | pulverizing. It is a figure which shows the particle size distribution of the obtained water-insoluble collagen containing fine powder.

The water-insoluble collagen-containing fine powder of the present invention is a novel water-insoluble collagen-containing fine powder produced by the following two production methods.
(1) Fish scales are heat-treated in heated water at 90 to 95 ° C., and the heat-treated product is separated as a composition containing water-insoluble collagen, then dried and then pulverized for production.
(2) Fish scales are heat-treated in heated water at 100 to 140 ° C. under pressure, and the resulting colored heat-treated product is decolorized and separated as a composition containing water-insoluble collagen. It is crushed and manufactured.

The fish scales used as the raw material for the above production method are as follows.
Collagen is a major component of biological proteins and is contained in almost all animals, so it can be extracted from mammals, birds, fish and the like. Generally, collagen is boiled and extracted from sites with high collagen content such as cow skin, pig skin, chicken skin, fish skin, fish scales, etc., and collected (see Non-Patent Document 1).
The fish scales used in the present invention may be any scale of fish such as freshwater fish and saltwater fish. Generally, fish scales such as tilapia (Izumidai), oysterfish, nauru pouch (Chikadai), red snapper, sardine, etc. are mentioned.
Fish scales have a triple helix structure peculiar to collagen, and this state can be confirmed by DSC analysis (FIG. 1). As a result of DSC analysis after washing and decalcifying tilapia fish scales, the peak top can be observed at 113.4 ° C., which is within the range of 107.6-115.8 ° C. (by dry measurement).

  Fish scales have a calcium content of about 30% as hydroxyapatite, although the size and composition differ slightly depending on the fish species. In order to wash the fish scales, degrease, and decalcify the fish scales (calcium removal), for example, after immersing the fish scales in about 20 to 30 times the amount of water, 1.2 to 1. Add 5 times the amount of hydrochloric acid and stir for 10-30 minutes to remove as aqueous calcium chloride solution. Thereafter, washing with water is repeated to wash away the acid content to obtain decalcified scale.

The 1st manufacturing method of the water-insoluble collagen containing fine powder is as follows.
Fish scales are heat-treated in heated water at 90 to 95 ° C., and the heat-treated product is separated as a composition containing water-insoluble collagen, and then dried and then pulverized for production.
This heat treatment is an operation for facilitating the subsequent grinding process. It gives brittleness to fish scales. Here, it should be avoided to adopt an alkaline state or an acidic state so that unnecessary decomposition or the like does not occur.
In the method, after the fish scales are washed and degreased, the fish scales are fed into hot water heated to 90 to 95 ° C. The hot water may be a flow system or in a container.
When feeding fish scales, the ratio is 0.5 to 5.0 (liters) of hot water to 100 g of fish scales (solid content 80.5 g).
Even if it is a flow system, the same processing may be performed. The reason for heating to 90 to 95 ° C. is to make the fish scales easily pulverized without promoting the decomposition reaction. By this temperature treatment, the fish scales show a decrease in weight before and after that, so that some insoluble collagen components are decomposed to become water-soluble substances and are considered to have dissolved in hot water. Moreover, it is limited to this range from the viewpoint of largely preventing denaturation. The processing time may be about 10 to 60 minutes.
The remaining fish scales are given brittleness to the hydrothermal treatment product. The fish scale hydrothermal treatment product is obtained in an uncolored state. Good results are also obtained in the subsequent pulverization process. Before this treatment, there is a triple helix structure peculiar to collagen. There is no collagen specific triple helix structure at a later stage of this treatment. It is judged that the triple helix structure is unwound by heat and degeneration occurs.
In addition, a longer treatment time is not preferable because it leads to a result of decalcification of fish scales and degradation of collagen. This result is shown in Table 1, which was over 15 minutes.

After the heat treatment operation, the fish scales in the hot water are separated. A heat treatment product is taken out by, for example, injecting hot water and a heat treatment product after the heat treatment operation into a means for separating solid substances in the liquid, for example, on the surface of a plate having holes. Inject cold water without impurities to remove impurities sufficiently. The heat treatment product taken out is dried by an operation such as blowing air having a temperature higher than room temperature (from room temperature to 70 ° C.). In order to make it easy to grind fish scales, it is necessary to dry until the moisture of the whole fish scales is 5% or less.
In this operation, since coloring is not remarkable, it is not necessary to decolorize. In addition, when it is determined that it is necessary, a decoloring step can be appropriately employed. The decoloring step is a necessary operation in the second manufacturing method, and will be described in detail in the second manufacturing method.

The grinding process is performed in two stages. For example, as the first pulverization treatment, coarse pulverization (particle size of about 1 to 2 mm) is performed using a general-purpose mixer, and subsequently, as the second pulverization treatment, a dedicated pulverizer (for example, “ULTRA CENTREFUGAL MILL” manufactured by RETSCH) ) Is further finely pulverized (particle diameter of 200 μm or less). In addition, what is used for a 1st grinding | pulverization process is not restricted to a mixer, What is necessary is just what can grind | pulverize a grinding | pulverization target object to a particle size of 200 micrometers.
The dedicated pulverizer used for the second pulverization process is a fine pulverizer that continuously performs shear pulverization with a sharp rotating blade and a fixed blade. Suitable for fibrous materials and ductile materials, which is impossible with impact pulverization. The pulverized raw material is collected into the lower tank through a mesh screen. Slow rotation and shear pulverization minimize the generation of fine powder. It has a structure that does not generate frictional heat and is suitable for pulverizing materials to be processed that are sensitive to heat.

The results of the particle size distribution and further classified particle size distribution of the pulverized water-insoluble collagen-containing fine powder are shown in FIG.
What is obtained by the pulverization is that coarse pulverization (particle size of about 1 to 2 mm) is performed using a cutter mill in a pulverizer, and fine pulverization is subsequently performed using an ultra centrifugal mill so that the grain size is 0.4 μm to 200 μm. A water-insoluble collagen-containing fine powder can be obtained. A fine powder having an average particle size of about 45 μm is obtained. Among these, a component suitable for a scrubbing agent in a fine powder containing water-insoluble collagen having a particle size of 0.4 μm to 200 μm (a component having a particle size of 30 to 100 μm), and water having a particle size of 0.4 μm to 200 μm. Component suitable for exfoliating agent in fine powder containing insoluble collagen (component with particle size of 30-100 μm), component suitable for foundation moisturizer in fine powder containing water-insoluble collagen with particle size of 0.4 μm-200 μm (65 μm to 30 μm particle size component) is contained in 65% by volume of the whole, so that a water-insoluble collagen-containing fine powder having a particle size in this range (0.4 μm to 200 μm) is scrubbed or exfoliated, Furthermore, it can be used as a moisturizing agent for foundations.

The water-insoluble collagen-containing fine powder having a particle size of 0.4 μm to 200 μm has an appropriate action depending on the particle size. If it says that it uses only within this range, it can be used as an appropriate range by performing classification operation.
Specifically, classification into the following three ranges is performed.
The water-insoluble collagen-containing fine powder is classified to obtain a water-insoluble collagen-containing fine powder having a particle size of 0.4 to 30 μm (29% by volume) and a water-insoluble collagen-containing fine powder having a particle size of 30 to 100 μm (65% by volume). And classifying into a fine powder (6% by volume) containing water-insoluble collagen having a particle size exceeding 100 μm and 200 μm.
Water-insoluble collagen-containing fine powder having a particle size of 0.4 μm to less than 30 μm is suitable for use as a water-absorbing and moisturizing agent for foundations.
The water-insoluble collagen-containing fine powder having a grain size of 30 μm to 200 μm is suitable for use as a scrubbing agent or exfoliating agent.
Water-insoluble collagen-containing fine powder having a particle size exceeding 100 μm and 200 μm is suitable for use as a face pack moisturizer.

The above is summarized as follows.
(A) Gomage (showing adhesiveness) which has a peak at the central part and becomes a keratin care of 30 to 100 μm and a component which can be used by adding to cosmetics as a scrub cleanser (occupies 65% of the total).
(B) Components that can be used for foundations (barrier function, moisturizing function) of less than 30 μ (occupy 29% of the total).
(C) A component (occupies 6% of the total) that can be used in a face pack (moisturizing property) of 200 μm exceeding 100.
These can be separated and used for each application.

The second method is as follows.
Fish scales are heat-treated in heated water at 100 to 140 ° C. under pressure, and the resulting colored heat-treated product is decolorized, separated as a composition containing water-insoluble collagen, dried, and then pulverized. A water-insoluble collagen-containing fine powder obtained by
Compared to the first method, it is different in that it is heat-treated in heated water at 100 to 140 ° C. under pressure, and the resulting colored heat-treated product is decolorized and separated as a composition containing water-insoluble collagen. . It is the same as the manufacturing method 1 that is obtained by subjecting fish scales to be a raw material and drying treatment followed by pulverization.

This degree of heat treatment can be appropriately performed in an autoclave.
The operation of the autoclave is 100 to 140 ° C for 3 to 10 minutes.
The bath ratio requires 6 to 8 times the amount of water added to the fish scale weight of the raw material.
As a result of the DSC analysis after the heat treatment (FIG. 1), it can be seen that the collagen-specific triple helix structure does not exist and the collagen is changed.
The product is taken out from the heated water and dried by an air stream at about 70 ° C. above room temperature.

Table 3 shows the results of examining the influence on the pulverization when the moisture in the autoclave is changed.

  From the results in Table 3, it is shown that the treatment in the autoclave without water is insufficient. Even when the water is 100% hydrated with respect to the scale weight, a slight burning odor and coloring tend to occur during pulverization. It can be seen that a bath ratio with scales of at least 50% is necessary.

Changes in bath ratio in the autoclave on yield are shown in Table 4.

From the results in Table 4, there was no problem at all levels until coarse pulverization. For the fine pulverization, a bath ratio of 1: 1 was insufficient. If the amount of water is 5 to 10 times the scale, it can be seen that sufficient crushing has been performed.
The yield in the autoclave treatment was found to converge to about 55%.

The molecular weight of the product obtained by the heat treatment obtained in the production of the present invention is obtained in a polymer state that does not dissolve in hot water, and is estimated to be 100,000 or more water-insoluble gelatin.
The extraction residue after boiling and extracting the collagen used in the production of the present invention has a composition of high molecular collagen from a composition containing amino acids such as hydroxyproline, glycine, and proline.
Further, the dried residue is weak in the triple helix structure peculiar to collagen and is easily pulverized.
Table 5 shows the results of DSC depending on the treatment time. In addition, FIG. 1 shows the DSC measurement results during each treatment. The presence and disappearance of the triple helix structure peculiar to collagen can be seen, and it can be seen that collagen has changed.

  In addition, the appearance of the product after the heat treatment exhibits a cream color to a yellow color, and when dried, it changes from a tan color to a brown color.

The use of sodium percarbonate for the decolorization method is not appropriate because the decomposition of fish scales is accelerated and no residue remains. The results are shown in Table 6. It was also confirmed that decolorization could not be performed together during the heat treatment.

When a small amount of sodium percarbonate was used, the effect of decolorizing fish scales could not be obtained.
The results are shown in Table 7. At all levels, bubbles were generated in the aqueous solution of sodium percarbonate, and the fish scales floated even when left standing.

It was possible to decolorize by using hydrogen peroxide as the decolorizing agent.
It was impossible to add hydrogen peroxide in the heat treatment step. The contents are shown in Table 8.

The decoloring effect was good when the hydrogen peroxide concentration was 2% compared to 1%.
The bath ratio is fish scale swollen by heat treatment: 2% hydrogen peroxide, and is 1: 4.
The results are shown in Table 9.

表中、×は不十分、△は効果があるが、不十分、〇は同等の結果を示す。 The treatment time with hydrogen peroxide was examined.
Table 10 shows a comparison with the case of performing a decolorization treatment of 2.0% hydrogen peroxide / 50 ° C./18 hours. From this result, it can be seen that decolorization with 2.0% aqueous hydrogen peroxide requires treatment at 50 ° C. for 5 to 7 hours.

In the table, × is insufficient, Δ is effective, but insufficient, ○ indicates an equivalent result.

表中、×は不十分、△は効果があるが、不十分、〇は同等の結果を示す。 Table 11 shows a comparison between the case where the decolorization treatment is performed at 2.0% hydrogen peroxide / 50 ° C./18 hours and the case where the treatment is performed at 0.3 to 0.5% hydrogen peroxide. It can be seen that the treatment with 0.3 to 0.5% hydrogen peroxide requires treatment at 50 ° C. for 15 hours.

In the table, × is insufficient, Δ is effective, but insufficient, ○ indicates an equivalent result.

The neutralization after the treatment with hydrogen peroxide was carried out by a method of treating with rinse water and a treatment with dilute alkaline water. The results are shown in Table 12 and Table 13, respectively.

  After completion of the neutralization treatment, the product was dried in the same manner as in Production Method 1, and then pulverized to obtain the desired product.

  The treatment of fish scales is an important means for waste treatment, and it is an important technique for effective use of unused resources.

Claims (6)

  Water that is obtained by heat treating fish scales in heated water at 90 to 95 ° C., separating the heat treated product as a composition containing water-insoluble collagen, drying it, and then crushing it. Fine powder containing insoluble collagen.   Fish scales are heat-treated in heated water at 100 to 140 ° C. under pressure, and the resulting colored heat-treated product is decolorized, separated as a composition containing water-insoluble collagen, dried, and then pulverized. A water-insoluble collagen-containing fine powder obtained by   The water-insoluble collagen-containing fine powder according to claim 2, wherein the heat treatment in heated water at 100 to 140 ° C under pressure is a heat treatment in an autoclave.   The water-insoluble collagen-containing fine powder according to claim 2, wherein the decolorization treatment is performed with a hydrogen peroxide solution and then neutralized.   2. The pulverization includes two processes of a coarse pulverization process (particle diameter of about 1 to 2 mm) and a fine pulverization process (grain defect 0.4 μm to 200 μm) performed after the coarse pulverization process. Or the water-insoluble collagen containing fine powder of 2.   6. The water-insoluble collagen-containing fine powder according to claim 5 is classified to obtain a water-insoluble collagen-containing fine powder having a particle size of 0.4 μm to less than 30 μm, a water-insoluble collagen-containing fine powder having a particle size of 30 μm to 100 μm, a particle size exceeding 100 μm. A water-insoluble collagen-containing fine powder classified according to particle size, characterized in that it is a fine powder containing water-insoluble collagen of 200 μm.

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