JP3261593B2 - Powdered animal protein foaming agent, method for producing the same and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foaming agent made from keratin protein, which is made from feathers of birds such as chickens, which are of little use value as raw materials and may cause disposal pollution. Foaming agent having superior foaming properties, stability, odorlessness and workability, a method of producing the same, and various excellent concretes produced using the powdered foaming agent, which are superior to collagen protein foaming agents About the product.

[0002]

The use of hydrolyzed proteins as foaming agents is already known. Conventionally, collagen proteins such as animal skins, tendons, and bones were used as raw materials and hydrolyzed with alkali to produce peptide-like foaming agents, but these raw materials are useful as edible proteins. Therefore, the raw materials are not inexpensive and there are many raw materials that are so impure that the raw materials have to be purified. Therefore, problems such as washing and drainage have arisen, and living environment, location, and economy have been greatly restricted. In addition, these proteins are relatively expensive as a raw material, and have a peculiar odor when the product decomposes collagen protein, there is a sense of resistance during use, and the odor of concrete products produced using this protein is bad. There were remaining disadvantages. In addition, keratin protein foaming agents made from hooves and horns of cows and horses are also used, but because they are not easily degraded, it is difficult to obtain peptides with a narrow molecular weight distribution, and the growth and history of animals are constant. Therefore, it is difficult to obtain a certain quality with varying degrees of decomposition of the raw materials,
In particular, keratin protein belongs to hard protein and is not easily degraded, so this tendency is remarkable.

[0003] Further, conventional foaming agents comprising collagen protein and keratin protein are required to be 40% in view of their production.
% To 50% strength aqueous solution. As a result, the degradation of the product over time due to the progress of time-dependent hydrolysis of the protein, decay and the like, and a decrease in the foaming power have occurred.
Furthermore, since a stabilizer for obtaining the stability of the bubbles is dissolved, this causes a chemical reaction with the protein to form an insoluble precipitate, which significantly destabilizes the quality. Furthermore, after producing the product, there is generation of offensive odor due to the hydrolysis and the like, and it was difficult to obtain an odorless foam.

[0004]

DISCLOSURE OF THE INVENTION The present invention is useful as a raw material from feathers, which are to be produced in large quantities in bird processing plants such as edible chicken processing plants and the like, and are of little utility value. Moreover, the present invention provides a powdery protein foaming agent having a foaming power superior to that of a conventional foaming agent, and comprises an odorless, closed cell having a fine and uniform foam diameter using the foaming agent. The purpose is to provide concrete products and the like.

[0005] The conventional protein foaming agent is an aqueous solution having a concentration of 40% to 50% and has many problems in storage due to aging, and also has problems in transportation. These problems can be solved by drying and pulverizing the powder, or directly pulverizing the powder in a spray dryer. Particularly, a powder product spray-dried is a porous material, and is excellent in solubility and foaming property and gives the most preferable result.

In addition, since conventional protein foaming agents require raw materials for animals such as cattle and horses, they lack long-term supply stability, and vary in the components of raw materials and the degree of cross-linking depending on the history of animal growth. The different degrees of decomposition and the odor limit the application. In addition, foamed concrete products manufactured using these conventional foaming agents are unstable in quality, making it difficult to obtain a constant product, resulting in irregular air bubbles and an unpleasant odor in the finished product. There were drawbacks. The powdered protein foaming agent according to the present invention is made into an aqueous solution immediately before use, and since a mixture of the aqueous solution of the foaming agent and the aqueous solution of the stabilizer is used, constant air bubbles are always obtained, and the mixing ratio with concrete is also high. It becomes constant and a stable foam concrete product can be obtained. Furthermore, since the foaming agent is almost odorless, the finished concrete product can be almost odorless.

[0007]

The protein foaming agent of the present invention is obtained by decomposing a keratin protein into a polypeptide having a molecular weight of 1,000 to 2,000.
It is composed of a protein hydrolyzate hydrolyzed to 00 to 2000 polypeptides.

The keratin protein has a disulfide bond (-S
-S-), it is difficult to decompose because of the net-like bond, and it is difficult to obtain a product of a constant quality in terms of raw materials. The present invention has been completed by focusing on the fact that the composition is substantially constant, and therefore, the feather composition quality is constant and the growth period is young, so that decomposition is easy.

In the present invention, as a keratin protein raw material, feather meal processed for feed can be used as a raw material, but it is advantageous to use bird feather directly as a raw material in terms of cost. The feathers coming out of the chicken processing plant are clean enough to be used as they are, and can be used as they are.
With a water content of 70% to 70%, it produces over 1,000 tons per month, and can be used as a raw material. In particular, feathers coming from the chicken processing plant must be of the same breed to raise chickens of a certain quality in order to keep chickens of a certain quality, and it is uneconomical for meat production to breed unnecessarily for a long time. Therefore, after breeding for a certain period of time, the meat is processed at once, so the growth rate is the same. Therefore, the content of the starting protein, the constituent amino acids of the protein, and the degree of cross-linking are the same, and the decomposition can be easily performed to the same molecular weight.

As a result of further research, the present inventor has found that the use of keratin protein as a foaming agent requires a molecular weight of 1000-20.
It has been found that a good foaming effect can be obtained with the polypeptide of 00. Here, the molecular weight means the average molecular weight. The measurement of the molecular weight may be performed by a usual method, for example, by a sedimentation equilibrium method by ultracentrifugation, or simply by a viscosity measurement method. In the present invention, those having a molecular weight of 1,000 or less are not preferable in terms of foam strength and foam stability because the film strength and film forming ability are low, and those having a molecular weight of 2,000 or more have poor foaming properties. Was empirically recognized.

As described above, in the case of the conventional protein raw material of the foaming agent, for example, when animal skin is used, most of the skin has hair on the surface of the animal skin. The molecular weight and protein constituent molecules of the obtained polypeptides were different, and the foaming power was uneven. In addition, when the growth period is prolonged, the degree of the network structure due to cystine bonds and disulfide bonds (-SS-) in the keratin protein becomes large, so that the degree of degradation tends to be uneven, and it is difficult to obtain a certain polypeptide.

Since the present invention uses feathers of a constant growth rate from a chicken processing plant, it can be easily hydrolyzed and a good foaming agent having the above-mentioned molecular weight distribution can be obtained. The feather contains some other proteins in addition to the keratin protein. In the present invention, these proteins are considered to contribute to the foaming power in some form. Various feathers such as chickens and ducks are considered as the raw material,
From the viewpoint of the availability of raw materials and the uniformity of quality, it is preferable to use chickens from egg production plants or edible chicken factories, and feathers of chickens bred within one year, such as broilers, are preferable.

The method for producing the protein foaming agent of the present invention will be specifically described with reference to FIG. In the present invention, in order to decompose the raw material feathers, well-washed feathers continuously coming out of a chicken processing plant are put into a decomposition pot. In the raw material feather treatment step of FIG. 1, a surfactant such as sodium dodecylbenzenesulfonate (for example, sodium dodecylbenzenesulfonate ( DBS). The amount of the surfactant is slightly different depending on the kind, but in the case of DBS, about 1% is added in powder form to the feather. Then, add an appropriate amount of water. The amount of water is about 5 times the weight of the dried feathers.

Next, the feathers placed in the reactor are hydrolyzed. The hydrolysis is performed by adding an alkaline decomposition solution. Specifically, an appropriate amount of alkaline agent such as caustic soda and slaked lime is used for the raw material feathers, and mercaptoethanol and thioglycolic acid for cutting cystine bonds are added, and further, sodium bisulfite, sodium sulfide, etc. It is preferable to add a reducing agent and a side reaction inhibitor. These chemicals are dissolved in water and added as an aqueous solution.

In the case of keratin protein degradation, extremely stable lanthionine produced by secondary reaction of thiol group, vinyl group, aldehyde group and the like by-produced when the cystine bond is cleaved significantly inhibits alkali decomposition. There is a theory. As a result of the research, the inventor found that hydrazine,
It has been found that when hydroxylamine, piperazine, and methylamines are added as a complex reaction inhibitor (side reaction inhibitor) to inactivate the aldehyde group and the thiol group, alkali decomposition is rapidly performed. A constant amount is determined empirically as the amount of chemical used. The decomposition conditions are preferably performed in a pressure cooker at 100 ° C. to 120 ° C. for about 1 hour from the viewpoints of workability, economy and quality stability. After completion of the decomposition, the liquid hydrolyzed in the filtration step is filtered to separate into a decomposed liquid and a residue. Since the residue contains a large amount of organic substances, it can be used, for example, as a fertilizer. Next, the decomposition solution is neutralized with phosphoric acid or the like.
Stop the decomposition reaction at pH 7.0.

[0016] The proteolytic solution used as a foaming agent is
It is desirable that the protein be decomposed into a polypeptide having a molecular weight of about 1,000 to 2,000. Therefore, it was found that a good result can be obtained by using lime having a slower action than caustic soda as the alkali used for the hydrolysis. Also,
When the solution is neutralized at the end of decomposition, caustic soda increases the amount of salt remaining in the foaming agent as salt, but when using lime, most of the insoluble salts are neutralized with phosphoric acid or oxalic acid. And settles down, so that it is easily removed in the filtration step after neutralization. Further, the insoluble salt generated at this time is coprecipitated with impurities in the decomposition solution, and thus has an advantage of clarifying the filtrate. Filtration residue in the process when phosphoric acid is used as a neutralizing agent, since calcium phosphate is obtained,
Can be used as fertilizer.

The filtrate obtained in the above filtration step is 40 to 50%
Since it is obtained at the following concentration, it is concentrated to a concentrated liquid of 50% or more by adding a foam stabilizer as necessary. Concentration may be by a method of evaporating water by heating or a vacuum concentration method,
If desired, a freeze-drying method or the like can also be used. Conventionally known foam stabilizers can be used. When the surfactant is used as the foam stabilizer, an anionic surfactant such as DBS is used. The amount used is 2-3% based on 50% decomposed concentrate
Add some.

A conventional foaming agent is prepared by adding an aluminum salt, a chromium salt, an iron salt, an aldehyde or the like as a foam film stabilizer to the protein decomposition solution obtained in the above-described steps. Although commercially available, according to the study of the present inventors, since these stabilizers have strong reactivity with proteins, when they are contained in a foaming agent solution, they cause various insolubilization reactions during storage and cause insolubility. It was found that there was a defect that coagulated matter was precipitated and the quality was unstable. Therefore, in the present invention, the decomposed concentrate obtained above is used as it is, or the decomposed concentrate containing an anionic surfactant is dried and powdered. Since the product of the present invention uses an aqueous solution of a powdered foaming agent and an aqueous solution of a stabilizer immediately before use, the above-mentioned drawbacks of the conventional foaming agent can be completely overcome. It was also found that a surfactant could be used as a foam enhancer and stabilizer. As described above, anionic surfactants can be used as the surfactant, and cationic and nonionic surfactants are not preferred.

The obtained concentrated concentrate is filtered, if necessary, and then dried. Drying is preferably carried out directly with a spray drier to obtain a dry powder. In addition, a concentrated solution is passed through a disk or a drying drum and dried to obtain flakes, which are pulverized as required to obtain a powder. The particle size of the obtained dry powder varies depending on the concentration of the hydrolyzed solution and the size of the water droplet at the time of spraying, but it is preferable that the size of the obtained powder falls within a particle size distribution of 40 to 50 microns. When the spray method is used, the obtained powder is a porous body, so that the solubility is good and the workability is improved.
When it is in the form of flakes, the volume is about three times that of the powder obtained by the spray method, but the solubility is also good.

Spray drying of the hydrolyzate is usually performed by spraying the hydrolyzate in a hot air stream that does not oxidize the protein in the air, but when the protein has a large molecular weight, it is oxidatively decomposed during this drying. The molecular weight may be adjusted. Spray drying may be performed in a non-oxidizing gas such as nitrogen gas or carbon dioxide gas if necessary. Since the conventional foaming agent contains a stabilizer, when the powder is finished into a powder, a chemical reaction proceeds during heating and drying, and the foaming agent becomes completely insoluble and cannot be used. In the case of the present invention, such a phenomenon does not occur at all because the foaming agent main body and the conventional stabilizer are separate and used at the time of use. When the surfactant is used as a stabilizer, the above reaction does not occur during drying by heating.

According to the present invention, ammonia, hydrogen sulfide, and the like which are generated during the protein decomposition step and dissolved in the decomposition solution,
Since malodorous gas components such as mercaptan are scattered and removed by a drying / pulverizing process of a decomposition solution by a spray drier or the like, the obtained product is almost odorless and can be developed for various uses. For example, conventional keratin protein-based foaming agents have been used for foam concrete or foam fire extinguishers used in parts where odor is not a problem because the above-mentioned odor remains in the product. Since it does not emit an odor, it can be used to produce artificial wood with cellular concrete by adding fragrances and fragrances in addition to conventional uses. The bubbles obtained by the aqueous solution of the foaming agent of the present invention are stronger than conventional ones and exhibit a long-time bubble state. For reference, Fig. 2 shows the strength of the bubble coating of various protein foaming agents and surfactants.
Shown in As can be seen from the figure, the keratin protein shows a strong foam film strength at a low concentration.

[0022]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 1 kg of chicken wings from a chicken factory was collected in a pressure cooker, 10 L (liter) of water was added, and a surfactant (DBS) was added to emulsify the oils and fats in the wings and improve the penetration of chemicals. Add 1% to feathers and mix well. Then slaked lime
100 g, sodium bisulfite 10 g and hydrazine 10
Add 100 g and decompose at 100 ° C to 120 ° C for 1 hour. After the decomposition is completed, the decomposition residue and the supernatant are separated, and then pH 7.0 ~ with phosphoric acid.
Neutralize to 7.5. The neutralized solution is filtered to remove generated calcium phosphate, and the filtrate is spray-dried to finish into a powder. A powdered foaming agent is obtained in an amount of about 40% by weight, based on the weight of the dry bird wings.

Example 2 400 g of dry feathers and 2000 cc of water were charged into a pressure cooker, and 20 g of a surfactant was added and stirred well. Next, 100 g of slaked lime, 5 g of sodium sulfide and 10 g of methylamine are added, and the mixture is heated to 100 ° C.
Decomposes at ~ 120 ° C for 1 hour. After completion of the decomposition, the decomposition residue and the supernatant are separated, and then neutralized to pH 7.0 to 7.5 with phosphoric acid.
The neutralized solution is filtered to remove calcium phosphate, and the filtrate is spray dried to finish into a powder. Obtain 150 g of a dry powder product.

Example 3 Portland cement 5000 g Sand 5000 g Water 2000 cc The above mixture was put into a kneading mixer and kneaded well for 2-3 minutes. A foam liquid obtained by foaming a foaming agent liquid is mixed with the cement mixture as described above. Powder foaming agent 40 g Water 1000 cc Foaming stabilizer 2 g The above foaming agent mixture is stirred and dissolved, and put into a foaming machine to foam well for 1-2 minutes. The complete foaming liquid, which is an aggregate of foams having a size of 20 to 30 μm (microns), is mixed with the above mixture of cement and sand, kneaded well for 2 to 3 minutes, and when completely mixed, forms a mold. Set to pour. The thus set cement hardened material was covered with a foamed polyurethane sheet containing water and cured for about one week according to a conventional method to obtain a completely hardened product. The obtained cured cement was lightweight concrete in which fine bubbles were uniformly dispersed and contained. After that, this cement hardened material was left in a well-ventilated shade and dried, as described later,
It was not damaged even when heated to the extent that it glowed red with a gas burner flame. On the other hand, a cement hardened material similarly hardened using a conventional commercially available liquid keratin protein foaming agent was easily broken by heating the burner. In addition, a lightweight concrete plate having a thickness of 30 mm was prepared from the above composition, and a glass tube was set up on the plate surface and water was added to the plate.
As a result of a test of (permeability test of asbestos slate), it was confirmed that the water permeability was 3 mm or less, that the water was completely waterproof, and that the bubbles were closed cells. In the above, the powder foaming agent used in Example 1 was used.

Example 4 Portland cement 5000 g Sand 5000 g Water 2500 cc The above mixture was put into a kneading mixer and kneaded well for 2 to 3 minutes to obtain a mixture having a volume of about 6000 cc and a specific gravity of 2.1. The cellulosic liquid obtained by the method of Example 3 was blended in the amount described below with the cement mixture thus obtained, and the mixture was cured to obtain a lightweight concrete with cells, and its specific gravity was measured.

[Table 1] The specific gravity of the concrete shown in the above Table 1 almost coincides with the calculated value, and it is recognized that the obtained lightweight concrete does not have a volume reduction during hardening, which is generally called “thinning”.

Example 4 A mixture obtained by adding 2000 cc of the foam liquid to the cement mixture of Example 3 was placed in a plastic bat having a capacity of 1000 cc, set with a trowel, set well, and allowed to stand for 24 hours. A gap at the boundary surface was observed, and it was confirmed that there was no gap and the volume did not decrease.

Example 5 Portland cement 2500 g Sand 2500 g Gravel 2500 g Water 1500 cc A foam mixture of 4000 cc was mixed with the above cement mixture to prepare a concrete plate having a thickness of 10 cm and a specific gravity of 1.4 in the same manner as in Example 3. This is cut after solidification. Examination of the cross section revealed that sand and gravel were uniformly dispersed.

Example 6 When the foam liquid was mixed with the cement mixture of Example 3, a fragrance of a cypress scent was mixed into the foam liquid to form a cement-bubble mixture, which was hardened into a wood-like form to produce a pseudo-wood. As a result, a conventional wood-like concrete material having no bad smell was obtained.

[0029]

Compared with the conventional foaming agent based on animal protein and the foaming agent based on bird feather keratin protein of the present invention, the keratin protein degradation of the present invention is as follows. It can be seen that the foaming agent is superior. 1. The conventional keratin proteolytic foaming agent has a peculiar odor, such as mercaptan, hydrogen sulfide, and ammonia, derived from cystine, and has a resistance to work, and the odor remains in the foamed concrete. The keratin proteolytic foaming agent from bird feathers of the present invention has a low growth rate of feathers as a raw material and is easy to decompose. Since it dries, the odorous gas is scattered, and a product with almost no odor is obtained.

2. Conventionally, hooves and horns of cattle and horses, which are used as raw materials for keratin protein foaming agents, require 5 to 6 hours to decompose, but bird feather keratin protein is easily decomposed and made into a solution, and one hour is sufficient. Therefore, it is very advantageous in terms of workability and fuel cost. In the case of hoofs and horses, they cannot be used as raw materials as they are and must be crushed in advance, which requires cost and labor. However, in the case of feathers, there is no such problem at all.

3. When making aerated concrete products using keratin protein foaming agents, the conventional foaming agents leave a bad smell on the concrete products and the quality of the foaming agents is not stable, so it is possible to obtain a uniform and uniform product. Can not. When the foaming agent of the present invention is used, the resulting concrete product is almost odorless, the foaming agent is used separately from the foaming stabilizer in the form of a powder, and is blended immediately before use, so that the quality is always constant. A foam is obtained. Accordingly, a constant aerated concrete can be always obtained. Since fine bubbles having stable and uniform size are uniformly distributed in the concrete product, it is possible to produce cellular concrete excellent in soundproofing, moistureproofing and heat resistance.

4. A simple test method was used to compare the conventional keratin protein-decomposing foaming agent made from hoof of horses and horses with the foaming agent according to the present invention with respect to the foaming properties and foam stability. The results are shown below.

Test method 0.6 cc of the foaming agent stock solution was diluted to 20 cc with water, placed in a 200 cc graduated cylinder, covered, shaked vigorously up and down several times to foam, and the height of the generated bubbles was measured on the graduated cylinder. (Cm ³ ) The measurement was performed immediately after lathering,
10 hours later. As the stock solution, the stock solution of the present invention uses a 40% aqueous solution of the powdered foaming agent obtained in Example 1 above, and a solution obtained by adding 10 g of aluminum sulfate to the stock solution. A mixture prepared in the same manner as in Example 1 except that the mixture was hydrolyzed with caustic soda for 5 hours and blended with aluminum sulfate was used.

[0034]

[Table 2]

As can be seen from the results in Table 1, the foaming agent of the present invention maintains the foaming state for a long time. Further, since the foaming property is good, a foaming state can be obtained by simple stirring. Therefore, it can be used for conventional foam concrete production, foam fire extinguisher, and the like, and can be used for various foaming applications. Since the foaming agent of the present invention may be stored and supplied in powder form and liquefied at the time of use, storage costs and transportation costs are not required, and unlike conventional water-soluble agents, a stabilizer such as a preservative is added. Since there is no need, there are many excellent advantages such as use without impairing the original foaming power of the foaming agent. The powdered foaming agent of the present invention was used as an aqueous solution even if it was stored for one year or longer because a desiccant or an oxygen absorbent was put in a plastic container, a metal can, or the like and sealed, and stored for one year or more. Occasionally, the foaming power was not different from that at the time of production.

In the independent foamed concrete body manufactured according to Example 3, the distribution of foaming was uniform at each portion, and the aggregate sand was evenly dispersed without separation. In the foamed concrete body using the conventional foaming agent, the sand of the aggregate tends to separate because the film strength of the foam is weak, the distribution of foaming is uneven, the foam size is also uneven, and the quality is constant. Did not.
Therefore, since the cellular concrete body produced in Example 3 has a constant quality, it exhibits particularly excellent effects on heat resistance, moisture resistance and soundproofing. As an example, take the foamed concrete body with a thickness of about 5 cm, put a matchstick shaft on it, heat it with a direct flame of gas from the bottom, and glow red until the heated surface reaches 800-1000 ° C and elapse for more than 1 hour Nevertheless, the axis of the matchstick maintained its shape. Also, the red-heated foamed concrete body kept its original shape in a ceramic form without being collapsed or deformed even after cooling. 500 to 6 for conventional cellular concrete
It is common that cracks occur at about 00 ° C. to cause breakage. Therefore, using the powdered protein foaming agent of the present invention in the production of a cellular concrete body using a conventional foaming agent or in the cellular concrete method, immediately before use, a foaming agent and a stabilizer are mixed as an aqueous solution and foamed. It is considered that a large improvement can be obtained in various aspects which have been carried out so far by performing a method of forming a cellular concrete body. The various uses and application aspects are listed below.

(1) Injection into the back of a tunnel (2) Injection during shield construction (3) Filling of cavities created by dropping or subsidence of land (4) Injection of backing to reinforce slope walls and masonry (5) Embankment Filling the back of concrete with voids (6) Various injection work (7) Insulation and injection into backside of insulation (8) Lightweight panels for houses (9) Simulated wood and other artificial products (10) Other lightweight concrete products, ( 11) Panels for fire-resistant structures and fire-resistant structures for on-site casting, ceilings, roofs, floors, etc. (12) Manufacture of foamed mortar moldings and foamed gypsum products

[Detailed description of drawings]

FIG. 1 is a flow sheet showing a method for producing the foaming agent of the present invention.

FIG. 2 is a graph showing the foam film strength of various foaming agents.

Claims (2)

(57) [Claims] Claims: 1. Feathers such as caustic soda, slaked lime, etc.
Potassium agent, sodium bisulfite as reducing agent or
Sodium sulfide and hydrazi as a side reaction inhibitor
Obtained by alkaline hydrolysis with methylamine or methylamine.
Dried 1000 to 2000 molecular weight polypeptide
Foamed concrete comprising dried animal protein
Foaming agent for cleats . 2. An aqueous solution of caustic soda, slaked lime, etc.
Potassium agent, sodium bisulfite as reducing agent or
Sodium sulfide and hydrazi as a side reaction inhibitor
Addition of polyamine or methylamine
The polypeptide obtained by alkaline hydrolysis to a peptide
Neutralize the aqueous tide solution with phosphoric acid and remove the resulting calcium phosphate
After filtration, the filtrate is dried to a powder with a spray dryer or the like.
Manufacture of foaming agent for foamed concrete characterized by drying
Construction method .