CN112143243A - Scale-derived articles of daily use and method for making same - Google Patents

Abstract

The embodiment of the application provides a manufacturing method of scale-derived articles for daily use, which comprises the steps of obtaining a plurality of scales, treating the scales with alkali liquor to obtain a plurality of purified scale materials, washing the purified scale materials, drying the washed purified scale materials, crushing the dried purified scale materials into a plurality of particles to be molded, wherein the particles to be molded comprise a plurality of first particles, mixing the first particles with liquid to form a mixture, and granulating the mixture to obtain a plurality of scale soft beads. The purified flake material described above contains 50 to 90% collagen. A ratio of a weight of the plurality of first particles to a volume of the liquid is 1:1 to 1: 12, and the weight of the first particles in grams (grams) and the volume of the liquid in milliliters (ml).

Description

Scale-derived articles of daily use and method for making same

Technical Field

The invention relates to a scale-derived daily necessity, in particular to a scale-derived daily necessity which can be degraded in natural environment.

Background

In recent years, the concept of green color has led consumers to prefer environmentally friendly articles for daily use, and common articles for daily use, such as detergent, cosmetics, disposable tableware, straw, and drinking cup, are mostly made of plastics, and particularly in cleaning products or cosmetics, Plastic beads (Plastic beads) are commonly added to increase friction or cleaning power.

The plastic particles in these cleaning products or cosmetics are small in size, so they cannot be intercepted by drainage systems and sewage treatment plants, and are prone to adsorb various toxic organic compounds, algae, microorganisms, environmental hormones, and the like. When the plastic particles absorb the harmful substances and flow into the ocean through a sewage discharge system, the plastic particles cannot be decomposed by the environment and are ingested by organisms to enter an ecological food chain. Finally enters the human body through the food chains buckled with the rings. At present, the research finds that plastic particles may cause the problems of carcinogenesis, interference with the endocrine system of the human body and the like.

In addition, although plastic straws made of plastic have been used for many years in modern society and consumers, the plastic straws are not biodegradable in natural environment, and are often accumulated in large quantities to become environmental burden after use, and if the plastic straws flow into the ocean, the plastic straws may cause ocean pollution, and even if the marine organisms accidentally eat the plastic straws, the plastic straws may cause damage to the organisms.

As can be seen from the above, neither plastic particles nor plastic straws can be decomposed by organisms in the natural environment, so that a large amount of plastic garbage is accumulated, and the ecological environment is affected. Therefore, despite the inconvenience of consumers in life, the current society is still extremely free from or even prohibited to use plastic straws and plastic particles.

Disclosure of Invention

In view of the above, the present invention provides a method for manufacturing a degradable scale-derived living article and a degradable scale-derived living article as a substitute for plastic products. The processed purified fish scales or the Scale materials of the terrestrial animals are used for manufacturing Scale-derived daily necessities mainly composed of collagen, such as Scale soft beads (scales) or Scale straws, wherein the Scale soft beads can be added into daily cleaning articles or cosmetics, and the Scale straws can be used for replacing plastic straws. The degradable scale is used for deriving daily necessities so as to reduce the damage and pollution of the products to the natural environment.

In one embodiment, a method for manufacturing scale-derived articles of daily use includes obtaining a plurality of scales, treating the scales with alkali solution to obtain a plurality of purified scale materials, washing the purified scale materials, drying the washed purified scale materials, crushing the dried purified scale materials into a plurality of particles to be molded, wherein the particles to be molded comprise a plurality of first particles, mixing the plurality of first particles with liquid to form a mixture, and granulating the mixture to obtain a plurality of scale soft beads. The purified flake material described above contains 50 to 90% collagen. A ratio of a weight of the plurality of first particles to a volume of the liquid is 1:1 to 1: 12, and the weight of the first particles in grams and the volume of the liquid in milliliters.

In one embodiment, a method for manufacturing scale-derived articles of daily use includes obtaining a plurality of scales, treating the scales with alkali solution to obtain a plurality of first scale materials, washing the first scale materials, treating the washed first scale materials with a first acid solution to obtain a plurality of purified scale materials, washing the purified scale materials, treating the washed purified scale materials with an edible bleaching agent to obtain a plurality of scale materials, and manufacturing the scale materials to obtain a scale suction pipe. Wherein, the flake materials after being washed again comprise 50 to 90 percent of collagen.

In one embodiment, a scale-derived household item includes a plurality of degradable scale beads. The plurality of degradable scale beads comprises a plurality of first particles and a plurality of second particles. The plurality of first particles is made of at least one scale, and the plurality of first particles includes 50 to 90% of collagen. The plurality of second particles are combined with the plurality of first particles, and each second particle is smaller than each first particle.

In one embodiment, a flake-derived commodity includes a degradable flake straw. The degradable scale straw is made of a plurality of scales and contains 50 to 90 percent of collagen.

In summary, the scale-derived articles of daily use and the manufacturing method thereof according to the embodiment of the invention are suitable for providing an environmentally friendly article of daily use, and the scale-derived articles of daily use have biodegradable properties and can also be used as a substitute for the same type of plastic products. The scale-derived daily necessities which are low in pollution, environment-friendly and low in harm to marine organisms are provided for consumers, so that the green and continuous purpose can be achieved, and the convenience in use for the consumers is provided.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without any creative effort.

FIG. 1 is a flow chart of a method of making a scale-derived household item according to one embodiment of the present invention;

fig. 2 is a flow chart of a method of manufacturing a scale-derived household item according to an embodiment of the present invention:

FIG. 3 is a flowchart of a first embodiment of step S110;

FIG. 4 is a flowchart of a second embodiment of step S110;

FIG. 5 is a flowchart of a third embodiment of step S140;

FIG. 6 is a flowchart of one embodiment of step S170;

FIG. 7 is a flowchart of one embodiment of step S170;

FIG. 8 is a flowchart of one embodiment of step S170;

FIG. 9 is a flow chart of a method of making a scale-derived consumer product according to another embodiment of the present invention;

FIG. 10 is a flowchart of one embodiment of step S230;

FIG. 11 is a flowchart of another embodiment of step S230;

FIG. 12 is a flowchart of one embodiment of step S260;

FIG. 13 is a flowchart of another embodiment of step S260;

FIG. 14 is a flowchart of yet another embodiment of step S260;

FIG. 15 is a photograph of a scale-derived item of everyday life in accordance with an embodiment of the present invention;

fig. 16 is a photograph of a scale-derived item of everyday use in accordance with another embodiment of the present invention;

FIG. 17 is a top left view of a scale suction tube for scale-derived household items according to another embodiment of the present invention;

FIG. 18 is a bottom right view of a scale suction tube for scale-derived household items according to another embodiment of the present invention;

FIG. 19 is a perspective view of a scale suction tube for a scale-derived household item according to another embodiment of the present invention;

FIG. 20 is an enlarged view of the dashed box of FIG. 18;

FIG. 21 is an air-drying drawing of a scale straw for a scale-derived household item according to another embodiment of the present invention;

FIG. 22 is a heat and pressure diagram of a scale suction tube for a scale-derived household item according to another embodiment of the present invention; and

fig. 23 is an acid and alkali resistance experiment chart of the scale soft beads of the scale-derived daily necessities according to the embodiment of the invention.

Description of the reference numerals

S100-S178 steps

S200-S269 Steps

10 region of enlargement

Detailed Description

The terms first, second, third, etc. … are used herein to distinguish one element from another, are not used to distinguish one element from another, and are not used to distinguish one element from another.

In some embodiments, degradable scale beads can be made with scales. Referring to fig. 1 and 2, a plurality of scales are first obtained (step S100). In one embodiment, the scale is scraped from the organism and washed with clean water to remove impurities from the scale, such as: fish meat, fish skin, tissue fluid, blood, etc. In some embodiments, the source of the plurality of scales includes fish scales and scales from terrestrial animals. In one example, after the scales are scraped from the fish, the scales are washed with tap water three times, and the scales having a wet weight of 1000 g or 200 g are taken for use.

After step S100, the scale obtained is treated with a chemical solution to obtain a plurality of purified scale materials (step S110) to remove cells and/or inorganic substances on the scale. Here, the scales after removing the cells are purified scale materials, which mainly consist of collagen. In other words, the purified flake material comprises 50% to 90% collagen. In some embodiments, the lye is a strong alkaline solution, such as sodium hydroxide (NaOH). For example, but not limited to, the lye may be 0.1 to 2 normal (N) sodium hydroxide. By way of example, but not limitation, the steps of the process may be performed at room temperature or at low temperatures (e.g., in a refrigerated cabinet at about 4 degrees celsius).

In a first embodiment of step S110, referring to fig. 3, a plurality of scales are alkali-treated with alkali solution to form a plurality of purified scale materials (step S111). In some embodiments, the lye is a strong alkaline solution, e.g., sodium hydroxide or the like. In some embodiments, the scraped and washed scales are subjected to an alkali treatment with 0.1 to 2N sodium hydroxide (e.g., step S111) to remove cells, e.g., tissues, membranes, etc., on the scales. In some embodiments, the alkali treatment may be performed by a blender at 250 ± 25rpm to assist in the chemical reaction. In other words, the plurality of scales are soaked in the alkali solution under stirring for a predetermined time to form the purified scale material. For example, 1000 g of wet fish scales are taken, 7.5L of 1N sodium hydroxide is added, and the fish scales and the 1N sodium hydroxide are chemically treated with 750 ml of each 100 g of wet fish scales, and simultaneously stirred by a high torque stirrer (16 cm stirring blade) at room temperature at a set rotation speed of 250 + -25 rpm for 2-4 hours.

In a second embodiment of step S110, please refer to fig. 4, the scales obtained by alkali treatment with alkali solution are a plurality of first scale materials (step S115) to remove cells, such as tissues, membranes, etc., on the scales. Next, the first scale materials are washed (step S116), and the washed first scale materials are acid-treated with an acid solution to form a plurality of purified scale materials (step S117), so as to remove most of the inorganic substances, such as hydroxyapatite, on the first scale materials. In some embodiments, the lye is a strong alkaline solution, e.g., sodium hydroxide or the like. In some embodiments, the acid solution is a strong acid solution, e.g., a hydrochloric acid solution, and the like. In some embodiments, the washing solution may be pure water, deionized water, secondary deionized water (DDW), Phosphate Buffered Saline (PBS), or phosphate buffered saline (PB, ph 6.8-7.0). In one embodiment, the first scale material after the strong acid treatment contains less than 1% (by weight) of HA. In one embodiment, the inorganic content of the acid-treated first flake material is reduced and the bonding strength between the collagen proteins is weakened by the acid treatment, thereby softening the first flake material. In some embodiments, the number of times of cleaning in step S116 may not be limited to one time, and may be two times or more. In some embodiments, whether the cleaning step of step S116 is completed can be determined by whether the ph is adjusted to neutral. In one example, the first flake material can be adjusted to ph7.0 to ph7.5 by washing. For example, in one example, the scraped and washed flakes are treated with 0.1 to 1N NaOH to remove cells from the flakes (e.g., step S115). And first scale materials are obtained after removing the cells, and the acid-base value of the first scale materials is adjusted back to neutral with pure water or Phosphate Buffered Saline (PBS) (i.e., step S116). Then, the solution is treated with 0.1 to 1N hydrochloric acid (HCl) (e.g., step S117). In another example, 200 grams of washed fish scales are removed and reacted with 2 liters of 0.3N NaOH to remove cells from the fish scales to obtain a first scale material, wherein the reaction can be performed in a freezer and stirred using a digital electric stirrer at 250 + -25 rpm for 18 to 24 hours (+ -30 minutes). Then, after removing the reacted solution, the first scale material was washed twice with 2 liters of 0.01M (Mohr concentration) phosphate buffer solution (i.e., 1XPBS) in a freezer and stirred using a digital electric stirrer at 250 + -25 rpm for 0.5 to 2 hours. Adjusting the pH value of the first scale material to be neutral. Then, 2L of 0.3N hydrochloric acid solution is used to perform a reaction to remove hydroxyl apatite from the fish scales, wherein the reaction can be performed in a refrigerator, and a digital electric stirrer is used to stir at a rotation speed of 250 + -25 rpm for 0.5-2 hours, and the reaction is repeated once and twice.

After step S110, the plurality of purified scale materials are washed (step S120). A washing process is used to wash away residual pure chemical solution (e.g., alkaline or acid) on the purified scale material and to neutralize the material and to bring the plurality of purified scale materials back to neutral. In some embodiments, the washing solution may be pure water, deionized water, secondary deionized water (DDW), Phosphate Buffered Saline (PBS), or phosphate buffered saline (PB, ph 6.8-7.0). In some embodiments, the cleaning process may be assisted by a blender at 250 ± 25 rpm. In some embodiments, the number of washes may not be limited to one, and may be two or more. In some embodiments, the completion of the cleaning process can be determined by adjusting the pH back to neutral. In one example, the purified flake material can be adjusted to ph7.0 to ph7.5 by washing. In the first embodiment of step S120, the purified flake material after the alkali treatment can be washed with 0.02M phosphoric acid buffer solution (pH6.8-7.0) and pure water. For example, after 1000 g of wet fish scales are treated with 7.5L of 1N NaOH to obtain purified scale material, the purified scale material is washed with 7.5L of 0.02M phosphoric acid buffer solution until its pH value is from pH7.0 to pH 7.5. Wherein the number of washing is about three times, each time for 10 minutes and the washing is assisted by the set rotating speed of the stirrer being 250 +/-25 rpm. Next, the plate was washed with 7.5L of pure water 3 times for 10 minutes each, and assisted with 250. + -. 25rpm, which was the set rotation speed of the mixer.

In a second example of step S120, the acid-treated purified flake material can be washed with 0.01M phosphate buffered saline (i.e., 1X PBS). For example, 200 g of wet-weight fish scales are treated with alkali and acid solution, and the acid-treated purified scale material is washed five times with 2L of 0.01M phosphate buffer solution (i.e., 1 XPBS). In this regard, each wash may be performed at a low temperature (e.g., in a refrigerated cabinet at about 4 degrees Celsius) and stirred using an electric stirrer at 250 + -25 rpm for 0.5 to 2 hours.

After step S120, the plurality of cleaned purified scale materials are dried (step S130). The purified scale material is dried to remove moisture to facilitate comminution. In some embodiments, the drying may be drying on an iron plate, drying in an oven, air drying, or the like. In some embodiments, the drying temperature may be 30 ℃ to 60 ℃. In some embodiments, the drying time may be 12 to 48 hours. For example, in one example, the flakes are dried at 30 ℃ or 37 ℃ for more than 15 hours to remove moisture from the flake material. In another example, the cleaned purified scale material is spread on an iron pan and dried at 30 ℃ for more than 15 hours.

After step S130, the dried plurality of purified flake materials are pulverized into a plurality of particles to be molded (step S140). Wherein the particles to be molded comprise a plurality of first particles. In this way, the purified scale material is crushed into particles to be molded so as to facilitate the subsequent granulation and molding. In some embodiments, the pulverization can be, but is not limited to, crushing, grinding, milling, and the like. Also, the time for pulverization may depend on the state of the purified scale material. In some embodiments, the particles to be molded are differentiated by particle size. By way of example, but not limitation, particles to be molded having an average particle diameter (hereinafter referred to as particle diameter) of less than 500 μm are selected as first particles from the particles to be molded. In one embodiment, the purified flake material is ground into pieces or powder and then screened through screens of different pore sizes. By way of example, but not limitation, the mesh may have an aperture of 1 mm, 0.5 mm, 0.25 mm, 0.1 mm, 0.025 mm, any combination thereof, or the like. In fact, the screen with suitable aperture can be selected according to the use requirement. In one embodiment, the pulverized purified flake material can be screened sequentially by screens with a pore size of 1 mm, 0.5 mm, 0.25 mm, 0.1 mm and 0.025 mm to obtain particles to be molded with different particle size ranges of more than 1 mm, 0.5 mm to 1 mm, 250 microns to 500 microns, 100 microns to 250 microns, 25 microns to 100 microns and less than 25 microns.

In one embodiment of step S140, the purified flake material is pulverized into particles to be molded (step S143), and the particles to be molded having the first particles are further screened out with a screen having a different pore size (step S145). For example, the first particles are selected from the ground purified flake material as particles to be molded having a particle size of less than 500 microns. For example, 500 + -50 g of the dried purified flake material is taken in a roller mill tank and uniformly dispersed, followed by grinding for 5 minutes with a set current of 11 + -1 ampere (A) to obtain a plurality of particles to be molded. Then, the plurality of the to-be-molded particles are sequentially screened by a screen, wherein the to-be-molded particles with the particle size of 100 to 500 micrometers are taken as first particles.

In another embodiment of step S140, referring to fig. 5, the purified flake material is pulverized into particles to be molded (step S143), and the particles to be molded, including the first particles, are further screened by screens with different apertures (step S145). In some embodiments, the particles to be molded may further have second particles, and each first particle is larger than each second particle. For example, particles to be molded having a particle size of 100 to 500 μm screened from the pulverized purified flake material may be used as the first particles, and particles to be molded having a particle size of less than 100 μm but greater than 0 μm screened from the pulverized purified flake material may be used as the second particles. For example, 500. + -.50 g of the dried purified flake material is uniformly dispersed into a roller mill tank and ground for 5 minutes with a current set at 11. + -.1A to obtain a plurality of particles to be molded. Then, the plurality of the to-be-molded particles are sequentially screened by a screen, wherein the to-be-molded particles with the particle size of 100 to 500 micrometers are regarded as first particles, and the to-be-molded particles with the particle size smaller than 100 micrometers are regarded as second particles.

In one embodiment, after step S130, the plurality of first particles and the liquid are mixed (step S150). In another embodiment, after step S130, the plurality of first particles, the plurality of second particles and the liquid are mixed (step S160). In some embodiments, the liquid may be, but is not limited to, pure water, or pure water containing a binder. In some embodiments, the type of adhesive is any one of Cyclodextrin (Cyclodextrin), glycerol, starch pasting fluid, sodium alginate (alginate), gelatin (Gelatine), polylactic acid (PLA), carboxymethyl cellulose, chitosan, or a combination thereof. In one embodiment, 0.5% to 2.5% of the adhesive is added to the pure water to facilitate the adhesion between the first particles.

In one embodiment of step S150, a plurality of first particles is mixed with the liquid to obtain a mixture. Wherein the ratio of the weight of the first particles (grams) to the volume of liquid (milliliters) may be 1:1 to 1: 12. in some embodiments, the liquid is pure water, and a mixing ratio of a volume (ml) of the pure water to a weight (g) of the first particles may be 10: 1 to 1: 1. in other embodiments, the liquid is an aqueous solution of pure water to which a binder is added (hereinafter, referred to as a binder solution), and the mixing ratio of the volume (ml) of the binder solution to the weight (g) of the first particles may be 10: 1 to 1: 1. in this case, the binder may be dissolved in water and then mixed with the first particles in a ratio. In one example, first particles having a particle size of 100 to 500 μm are mixed with pure water, and the ratio of the weight (in grams) of the first particles to the volume (ml) of the pure water is 1: 4. in another example, first particles having a particle size of 100 to 500 microns are mixed with the binder solution, and the ratio of the weight (in grams) of the first particles to the volume (in milliliters) of the binder solution is 1: 4.

in one embodiment of step S160, the first plurality of particles, the second plurality of particles and the liquid are mixed to obtain a mixture (step S160). Wherein each of the second particles is smaller than each of the first particles, and a plurality of the second particles are biological substances, in an embodiment, the plurality of the second particles can be particles to be molded formed by crushing purified flake materials. In other words, a plurality of first particles and a plurality of second particles smaller than the first particles are screened from the pulverized purified scale material in step S140. In another embodiment, the second particles may also be shrimp shell powder, crab shell powder or chitin powder extracted from shrimp and crab shell powder. In some embodiments, the liquid may be an adhesive solution (i.e., pure water containing an adhesive), and the adhesive may be any one of cyclodextrin, glycerol, starch pasting solution, sodium alginate, gelatin, polylactic acid, carboxymethyl cellulose, chitosan, or a combination thereof. In an embodiment, the weight ratio of the first plurality of particles to the second plurality of particles may be 1: 2. in one embodiment, the first particles and the second particles may be mixed randomly when the first particles and the second particles are to-be-molded particles. In some embodiments, the mixing ratio of the weight of the first plurality of particles (in grams), the weight of the second plurality of particles (in grams), and the volume of liquid (in milliliters) may be 1: 2:1 to l: 2: 10. in other embodiments, the mixing ratio of the combined weight (in grams) of the first particles and the second particles to the volume of liquid (in milliliters) may be 1:1 to 1: 10. in some embodiments, the liquid is an adhesive solution, and the amount of adhesive added to the adhesive solution may be in a ratio of 0.02 (grams) by weight of adhesive to the combined weight of the first and second particles (grams): 1 to 0.1: 1 in pure water, or in a ratio of the weight of the binder (grams) to the weight of the first particles (grams) of 0.06: 1 to 0.3: 1 adding into pure water. In an exemplary embodiment, when the second particles are to-be-molded particles obtained by pulverizing a purified flake material, the first particles are mixed with the second particles, and the mixed weight (grams) of the first particles and the second particles and the volume (ml) of the liquid are mixed in a ratio of 1:4 to obtain a mixture. In another example, when the second particles are shrimp shell powder, crab shell powder, or chitin powder extracted from shrimp and crab shell powder, the weight (grams) of the plurality of first particles, the weight (grams) of the plurality of second particles, and the volume (ml) of the liquid are calculated in a ratio of 1: 2: 4 to obtain a mixture.

For example, the shrimp or crab shell powder may be prepared by a mechanical processing method, drying shrimp or crab shells overnight at a high temperature of 100 ℃, pulverizing the dried shrimp or crab shells, and sieving to obtain powder particles having a particle size of 100 to 300 μm.

For example, chitin powder is a powdery particle extracted from shrimp and crab shells through physical and chemical treatment. Firstly, making shrimp and crab shells into shrimp or crab shell powder by a mechanical processing method, drying overnight at a high temperature of 100 ℃, crushing the dried shrimp and crab shells, and sieving to obtain the shrimp and crab shell powder with the particle size of 100-300 microns. And then, soaking the shrimp and crab shell powder by using a 2N hydrochloric acid solution to remove calcium carbonate, and then soaking the shrimp and crab shell powder for 1 hour at 80 ℃ by using a 2N sodium hydroxide solution to remove protein in the shrimp and crab shell powder. Then, soaking the powder for 1 hour in 1% potassium permanganate solution to reduce astaxanthin, soaking the powder in 1% oxalic acid at 600 ℃ for 1 hour to remove the previously used potassium permanganate, and finally, washing the treated shrimp and crab shell powder with distilled water and drying to obtain chitin powder of the shrimp and crab shell powder, wherein the particle size of the chitin powder is between 1 and 100 microns.

After step S150, the mixture is granulated to obtain a plurality of scale beads (step S170). In some embodiments, the granulation process is rolling blending with a granulator until the granules are dried to obtain a plurality of soft beads, or breaking up and sieving after the mixture is dried to obtain a plurality of soft beads. In other embodiments, the granulation method is drying the mixture by using an oven, and sieving the mixture after crushing to obtain a plurality of soft beads, wherein the drying temperature of the oven can be 25 ℃ to 60 ℃.

In an embodiment of step S170, referring to fig. 6, after step S150 is performed to obtain a mixture of the first particles and the liquid, the mixture and the second particles are mixed by rolling to obtain a plurality of scale beads (step S171). For example (but not limited thereto), the particle size of the plurality of first particles is between 100 and 500 micrometers, and the particle size of the second particles is between 1 and 100 micrometers. The second particles are biological materials, such as particles obtained by pulverizing purified flake materials, or particles of any one of shrimp shell powder, crab shell powder, or chitin powder. Wherein, the rolling mixing mode is carried out by a granulator. In one embodiment, the weight ratio of the first plurality of particles to the second plurality of particles is 1: 2. in one embodiment, the particle size of the scale soft beads is between 100 and 700 microns. In one example, after placing the second plurality of granules in a pelletizer (spherical pelletizer, model QJ-230T), the mixture was added and tumble mixed at room temperature until the granules were dried to obtain a plurality of flaky soft beads, wherein the weight ratio of the first plurality of granules to the second plurality of granules was 1: 2, and the ratio of the weight of the plurality of first particles to the volume of liquid in the mixture is 1: 4.

in another embodiment of step S170, referring to fig. 1 and 7, after step S150 to obtain a mixture of the first particles and the liquid, the mixture is roll-mixed with the second particles to obtain a plurality of scale particles (step S173), the scale particles are broken (step S174), and the broken scale particles are screened to obtain a plurality of scale soft beads (step S175). For example (but not limited thereto), the particle size of the plurality of first particles is between 100 and 500 micrometers, and the particle size of the second particles is between 1 and 100 micrometers. The second particles are biological materials, such as particles obtained by pulverizing purified flake materials, or particles of any one of shrimp shell powder, crab shell powder, or chitin powder. Wherein, the rolling mixing mode is carried out by a granulator. The crushing may be performed by crushing with a tool (e.g., a mortar), breaking, or the like. Wherein, the screening mode is that a plurality of broken scale particles are screened by screens with different aperture sizes. In one embodiment, the weight ratio of the first plurality of particles to the second plurality of particles is 1: 2. in one embodiment, the particle size of the scale soft beads is between 100 and 700 microns. In one example, after the second granules are placed in the granulator, the mixture is added and mixed at room temperature until the granules are dried to obtain several scale granules, and then the granules are sieved by sieves with different pore sizes to obtain several scale soft beads with the particle size of 100-700 microns. Wherein the weight ratio of the plurality of first particles to the plurality of second particles is 1: 2, and the ratio of the weight of the plurality of first particles to the volume of liquid in the mixture is 1: 4.

in another embodiment of step S170, referring to fig. 2 and 8, after step S160 is performed to obtain a mixture of the first particles, the second particles and the liquid, the mixture is dried (step S176), the dried mixture is broken up to obtain a plurality of scale particles (step S177), and the plurality of scale particles are sieved to obtain a plurality of scale soft beads (step S178). Wherein, the drying mode can be that the drying is carried out by utilizing an oven to set the temperature of 25 ℃ to 60 ℃ until the particles are dried. The crushing may be performed by crushing with a tool (e.g., a mortar), breaking, or the like. Wherein, the screening mode is that the smashed mixture is screened by screens with different aperture sizes. In one embodiment, the particle size of the scale soft beads is between 100 and 700 microns. In one example, the mixture is placed in an oven, the mixture is dried at 37 ℃, after the mixture is dried, the mixture is crushed by a mortar, and a plurality of scale soft beads with the particle size of between 100 and 700 microns are screened out by a screen.

In some embodiments, the scale-shaped beads prepared as described above have a particle size of between 100 microns and 700 microns. In some embodiments, the foregoing scale beadlets produced have a particle size of mostly less than 500 microns. In one embodiment, the scale beads are irregular or spherical in shape and are light yellow in color (as shown in fig. 15).

In one embodiment, the scale-shaped soft beads prepared as described above can be mixed with a solvent composition to be used as a cleaning agent. Wherein, the scale soft beads are uniformly distributed in the solvent composition. In some embodiments, the solvent composition comprises glycerin, vegetable oil, an antimicrobial agent, an antioxidant, a humectant, a natural preservative, essential oil, and the like. In some embodiments, the water content of the detergent is 0.05% to 90%. In some embodiments, other kinds of particles may be added to the detergent to increase the cleaning ability of the detergent, and the particles may be shrimp or crab shell powder, coarse salt, jojoba particles, minerals, etc.

In other embodiments, the degradable scale suction pipe can be made of scales. Referring to fig. 9, a plurality of scales are taken first (step S200) to remove impurities on the scales, such as: fish meat, fish skin, tissue fluid, blood, etc. In one embodiment of step S200, after the scales are scraped from the biological object, tap water is used to clean impurities on the scales. In some embodiments, the plurality of scales can be fish scales. Wherein the fish may be fish species of round scales.

After step S200, the plurality of scales are treated with an alkali solution to form a plurality of first scale materials (step S210) to remove cells, such as tissues and membranes, on the scales. The alkaline solution is a strong alkaline solution, such as sodium hydroxide (NaOH). The scale after being treated by alkali liquor to remove cells is taken as a first scale material, and the first scale material mainly comprises collagen and hydroxyl apatite. For example, but not limited to, the lye may be 0.1 to 1N sodium hydroxide. By way of example, but not limitation, the steps of the process may be performed at room temperature (e.g., 25 ℃) or in a refrigerated cabinet (e.g., 4 ℃). For example, but not limited thereto, the treatment time may be 3 to 18 hours. In some embodiments, the time of the alkali treatment is varied at different temperatures, for example, by soaking the plurality of scales in the alkali solution at room temperature (e.g., 25 ℃) for 3 to 6 hours, or soaking the plurality of scales in the alkali solution (hereinafter referred to as scale solution) and then placing the scale solution in a freezer (e.g., 4 ℃) to react the alkali solution with the scales for 6 to 18 hours. In some embodiments, the alkali treatment is performed at a ratio of 1 to 20 grams of flakes to 50 milliliters of lye. In some embodiments, the alkaline treatment process may be assisted by a stirrer at 250 ± 25 rpm. In one example, 10 g of fish scales are reacted with 50 ml of 1N sodium hydroxide solution at room temperature for 5 hours to obtain a first scale material. In another example, 10 g of fish scales are reacted with 50 ml of 0.3N NaOH solution at 4 ℃ for 18 hours to obtain a first scale material.

After step S210, the plurality of first scale materials are washed (step S220). The pH value of the first flake materials is adjusted to be neutral by washing. In some embodiments, the cleaning solution may be pure water, deionized water, secondary deionized water, phosphate buffered solution, or phosphate buffered solution (ph 6.8-7.0). In some embodiments, the cleaning process may be assisted by a blender at 250 ± 25 rpm. For example, but not limited thereto, the number of times of washing may not be limited to one, and may be two or more. In some embodiments, the completion of the cleaning step is determined by adjusting the pH to neutral. In one embodiment, the alkali-treated first flake material (step S220) can be adjusted to ph7.0 to ph7.5 by washing.

After step S220, the cleaned first scale materials are treated with a first acid solution to form a plurality of purified scale materials (step S230), so as to remove inorganic substances, such as hydroxyapatite, on the scales and/or soften the scales. In some embodiments, the first acid solution may be a strong acid solution, such as a hydrochloric acid solution, or a composition of a strong acid and a weak acid, such as a hydrochloric acid solution mixed with an acetic acid solution. Here, the strong acid serves to remove inorganic substances in the scale, for example, hydroxyapatite in the scale. The weak acid serves to soften the flakes to facilitate subsequent manufacturing steps. In some embodiments, the binding strength of collagen in the flakes can be adjusted by adjusting the acid solution with different concentration composition and treatment time, thereby changing the hardness of the flakes. In some embodiments, the first acid solution is a 0.1 to 0.5N hydrochloric acid solution. In other embodiments, the first acid solution is a 0.3 to 1M solution of acetic acid mixed with a 0.1 to 0.5N solution of hydrochloric acid. For example, but not limited to, the step of acid treatment of the first acid solution may be performed at room temperature (e.g., 25 ℃), in a refrigerated cabinet (e.g., 4 ℃), or at 50 ℃. And the composition and temperature of the first acid solution can affect the treatment time of the first acid solution. In some embodiments, the first acid solution is a 0.1 to 0.5N hydrochloric acid solution and the acid treatment is performed at 4 ℃ for a treatment time of 0.5 to 1 hour. In other embodiments, the first acid solution is a 0.3 to 1M solution of acetic acid mixed with a 0.1 to 0.5N solution of hydrochloric acid, and the acid treatment is carried out at room temperature (e.g., 25 ℃) for 12 to 48 hours. In still other embodiments, the first acid solution is a 0.3 to 1M solution of acetic acid mixed with a 0.1 to 0.5N solution of hydrochloric acid, and the acid treatment is performed at 50 ℃ for 2 to 12 hours. In some embodiments, the acid treatment process may be assisted by a stirrer at 250 ± 25 rpm.

In an embodiment of the step S230, referring to fig. 10, after the step S220 is performed to clean the first scale materials, the cleaned first scale materials are treated with a first acid solution to form a plurality of purified scale materials (step S231). In one embodiment of step S231, the first acid solution is a mixture of 0.3 to 1M acetic acid solution and 0.1 to 0.5N hydrochloric acid solution, wherein the hydrochloric acid is used to remove hydroxyapatite in the flakes, and the weak acid is used to soften the flakes, thereby facilitating the subsequent manufacturing steps. In one example, after the first scale material is washed, a first acid solution of 0.5M acetic acid solution and 0.3N hydrochloric acid solution is mixed at room temperature for 24 hours to obtain a plurality of purified scale materials. In one example, after the first flake material is washed, a first acid solution of 0.7M acetic acid and 0.5N hydrochloric acid is mixed at 50 ℃ for 4 hours to obtain a plurality of purified flake materials.

In another embodiment of step S230, please refer to fig. 11, and step S220 is continued to wash the first scale materials, the plurality of first scale materials after being washed are treated with a first acid solution to form a plurality of second scale materials (step S233), and the plurality of second scale materials after being washed are treated with a second acid solution to form a plurality of purified scale materials (step S235) (step S234). In one embodiment of step S233, the first acid solution is 0.1 to 0.5N hydrochloric acid solution, and the acid treatment is performed at 4 ℃ for 0.5 to 1 hour twice. In one embodiment of step S234, the second scale materials are washed with pure water and adjusted to neutral ph. In one embodiment of step S235, the second acid solution is a 0.3 to 1M acetic acid solution mixed with a 0.1 to 0.5N hydrochloric acid solution, and the acid treatment is performed at 37 ℃ for 8 to 72 hours or at 60 ℃ for 0.5 to 2 hours. In one example, the flakes are first flake materials after being alkali-treated with 0.3N sodium hydroxide at a temperature of 18 hours, and after being washed, the flakes are acid-treated twice with a first acid solution of 0.3N hydrochloric acid solution to obtain a plurality of second flake materials, and after being washed, the flakes are acid-treated with a second acid solution of 0.5M acetic acid solution mixed with a 0.3N hydrochloric acid solution at a temperature of 37 ℃ for 24 hours to obtain a plurality of purified flake materials. In another example, the flakes are first flake materials after being alkali-treated with 0.3N sodium hydroxide at a temperature of 18 hours, and after being washed, the flakes are acid-treated twice with a first acid solution of 0.3N hydrochloric acid solution to obtain a plurality of second flake materials, and after being washed, the flakes are acid-treated with a second acid solution of 0.5M acetic acid solution mixed with a 0.3N hydrochloric acid solution at a temperature of 60 ℃ for 2 hours to obtain a plurality of purified flake materials.

After step S230, the plurality of purified scale materials are washed (step S240). And (3) adjusting the pH value of the purified scale materials to be neutral by washing, wherein the washing solution can be pure water, deionized water, secondary deionized water (DDW), Phosphate Buffer Solution (PBS) or phosphate buffer solution (PB, pH 6.8-7.0). In some embodiments, the cleaning process may be assisted by a blender at 250 ± 25 rpm. For example, but not limited thereto, the number of times of cleaning may be not limited to one, and may be two or more, and whether the ph is adjusted to neutral is used as a basis for determining. In one embodiment, the acid-treated purified flake material (step S240) can be adjusted to ph7.0 to ph7.5 by washing.

After step S240, the plurality of purified scale materials after the cleaning is treated with an edible bleaching agent to be a plurality of scale materials (step S250). Sterilizing and deodorizing by edible bleaching agent. Wherein the edible bleaching agent can be but is not limited to a food grade sodium hypochlorite solution or a food grade calcium hypochlorite solution. In some embodiments, the concentration of the edible bleaching agent is from 1 to 200 parts per million (ppm). In some embodiments, the treatment time for the edible bleaching agent is from 0.2 to 1 hour. In one embodiment, the washed purified flake materials are mixed with 50 ml of edible bleaching agent per 10 to 50 g of the washed purified flake materials, and the concentration of the edible bleaching agent is 1 to 200 ppm. In one example, a plurality of cleaned purified flake materials are sterilized and deodorized by treating 10 grams of purified flake materials with 50 milliliters of a 50ppm food grade sodium hypochlorite solution for 0.5 hour.

After step S250, a plurality of scale materials are made to obtain a scale straw (step S260). The scale suction pipe can be made by sticking on a mould, a paper suction pipe machine or a suction pipe making machine (such as a RHXG type paper suction pipe machine), wherein the mould can be a stainless steel bar with a suitable specification or a tubular mould in the machine. In some embodiments, the scale material may be broken without treatment, after removing excess water, or may be dried and then broken to form different shapes of scale material to make the scale straw.

In an embodiment of step S260, referring to fig. 12, a scale material is attached to a mold and dried to form a scale straw (step 261). Wherein the plurality of scale materials are not treated. In one embodiment, the sheet material is dried at 37-40 ℃ against a mold. For example, the drying method may be oven drying, air drying, or the like. In one example, a plurality of scale materials are attached to a mold and air-dried at a low temperature of 37-40 ℃ for forming, and then the mold is taken out to obtain the scale straw.

In another embodiment of step S260, referring to fig. 13, after the plurality of scale materials are smashed to obtain a plurality of chip materials with a diameter of 2 to 10 mm (step 263), the plurality of chip materials are hot pressed into a sheet material with a thickness of 0.20 to 0.35 mm (step 264), and the sheet material is made into a scale straw by a mold (step 265). Wherein the plurality of scale materials are broken into a plurality of pieces of materials with the sizes of 2 to 10 mm or 3 to 8 mm after excessive water is drained off. For example, the crushing method may be crushing, breaking, crushing, etc. In one embodiment, the hardness of the flake straw can be increased by adding shrimp shell powder and crab shell powder into the fragment material, wherein the weight ratio of the fragment material to the shrimp shell powder or crab shell powder is 1: 0.05 to 1: 0.5. in another embodiment, the formation of the scale straw is facilitated by adding pulp to the chip material, wherein the weight ratio of chip material to pulp is 1: 0.05 to 1: 0.2. in yet another embodiment, any one of sodium alginate, corn starch or cellulose (i.e., carboxymethyl cellulose) is added to the chip material to aid in shaping the flake straw or/and to increase the hardness of the flake straw, wherein the sodium alginate, corn starch and cellulose are added in an amount of 0.5% to 2%. In one embodiment, the scrap material or scrap material mixed with additives is hot-pressed into a sheet of material of 0.20-0.35 mm.

In one example, the flake material is hot pressed into 0.25 mm sheet material, and after a plurality of flake materials are continuously pressed into a roll, the flake straw is manufactured by a paper straw machine. In one example, a flake material containing shrimp shell powder or crab shell powder is hot pressed into a 0.25 mm sheet material, and after a plurality of flake materials are continuously pressed into a material roll, a flake straw is manufactured by a paper straw machine, wherein the weight ratio of the flake materials to the shrimp shell powder or crab shell powder is 1: 0.1, and the shrimp shell powder or the crab shell powder is helpful to increase the hardness of the scale straw. In one example, a flake straw is manufactured by a paper straw machine after a flake material containing paper pulp is hot-pressed into a 0.25 mm sheet material and a plurality of flake materials are continuously pressed into a roll, wherein the weight ratio of the flake materials to the paper pulp is 1: 0.05, and the pulp contributes to the formation of the scale straw. In one example, a flake straw is made by a paper straw machine after hot pressing a flake material containing 1% sodium alginate into a 0.25 mm sheet material and continuously pressing a plurality of flakes into a roll, wherein sodium alginate aids in shaping the flake straw and increases the stiffness of the flake straw. In one example, a flake straw is formed by a paper straw machine after hot pressing a flake material containing 1% corn starch into a 0.25 mm sheet material and continuously pressing a plurality of the flake materials into a roll, wherein the corn starch facilitates the formation of the flake straw. In one example, a flake material containing 1% cornstarch is hot pressed into a 0.25 mm sheet material and a plurality of rolls of the flake material are continuously pressed and then a flake straw is formed by a paper straw machine after the rolls are coated with edible wax, wherein the cornstarch aids in the formation of the flake straw. In one example, a flake straw is made by a paper straw machine after hot pressing a flake material containing 1% cellulose to a 0.25 mm sheet material and continuously pressing a plurality of flake materials into a roll, wherein the cellulose aids in the formation of the flake straw.

In yet another embodiment of step S260, referring to fig. 14, after drying the plurality of scale materials (step 267), the dried plurality of scale materials are crushed into a plurality of powder materials with a diameter of 0.5 to 1 mm (step 268), and the sheet-shaped materials are molded into a scale suction pipe (step 269). In some embodiments, the drying method may be air drying, low temperature baking, or the like. In one embodiment of step 267, the scale materials are dried at a low temperature of 30 ℃ to 37 ℃. In one embodiment of step 268, the scale materials are broken up into powder materials of 0.5 to 1 mm. Wherein the crushing method can be grinding and pulverizing. In one embodiment, the addition of shrimp shell powder or crab shell powder and polylactic acid (PLA) to the powdered material helps to increase the hardness of the scale straw and helps to form the scale straw, wherein the weight ratio of the powdered material to the shrimp shell powder or crab shell powder is 1: 0.1 to 1:1, and the addition amount of the polylactic acid is 1-30 percent. In another embodiment, polylactic acid is added into the powdery material to help the forming of the scale suction pipe and increase the hardness of the scale suction pipe, wherein the adding amount of the polylactic acid is 1-30%. In another embodiment, any one of sodium alginate, corn starch or cellulose is added into the powdery material, and polylactic acid is added to assist the forming of the scale straw and increase the hardness of the scale straw, wherein the adding content of any one of sodium alginate, corn starch or cellulose is 0.5% -2%, and the adding amount of polylactic acid is 1% -30%.

In one example, after adding shrimp shell powder or crab shell powder and 10% polylactic acid into a powdery material, a scale straw is manufactured by a straw manufacturing machine, wherein the weight ratio of the powdery material to the shrimp shell powder or crab shell powder is 1: 0.5. in one example, a scale straw is made by a straw making machine after 10% polylactic acid is added to the powder material, wherein the polylactic acid helps to shape and increase the hardness of the scale straw.

In one example, after adding 1% sodium alginate and 10% polylactic acid to the powdery material, the tube is manufactured by a straw manufacturing machine. In one example, 1% corn starch and 10% polylactic acid are added to the powdery material, and then the mixture is formed into a tube by a straw-making machine. In one example, a straw manufacturing machine is used to form a tube after adding 1% cellulose and 10% polylactic acid to the powder material.

In one embodiment, the scale suction pipe manufactured in the above way has a pipe diameter of 6 to 12 mm, a length of 18 to 24 cm and a thickness of 0.20 to 0.35 mm. In one embodiment, the scale straw made in the above way can be cylindrical or tubular. In one embodiment, the scale straw made as described above is transparent, hazy or opaque in appearance, or has a slightly yellowish color (as shown in fig. 16 to 19), and the scale-structured hairline is visible on the surface (as shown by the red arrows in fig. 20 to 22). In one embodiment, after the flake straw was spread out and air dried, the scale structure of the hairline was still observed on the surface (as shown in fig. 21).

In some embodiments, the scale material produced by the manufacturing method of steps S200 to S250 and the purified scale material (produced by steps S100 to S130) are treated with the same alkali solution, and the process flow and method are very similar, so the scale material and the purified scale material are similar in composition and property.

Experimental examples and analytical results are provided below to further illustrate the scale-derived articles of daily use according to the examples of the present invention.

First exemplary purification of Scale Material (i.e., Steps S100 to S130)

Scraping fish scales, cleaning with tap water for 3 times, and collecting the fish scales with the wet weight of 1000 g. 7.5 liters of 1N sodium hydroxide solution is prepared, and the purified scale material is obtained by alkali treatment according to the ratio of the wet weight of each 100 g of the scale to 750 ml of 1N sodium hydroxide. Adding fish scales into alkali liquor for treatment, and stirring at room temperature for 2 hours by using a high-torque stirrer (16 cm stirring blade) with the set rotation speed of 250 +/-25 rpm. The purified flake material was then washed three times for 10 minutes each with 7.5 liters of 0.02M phosphate buffer (pH6.8-7.0) and washed to neutral (pH 7.0-7.5). Subsequently, the purified scale material was washed three more times with 7.5 liters of pure water for 10 minutes each, and set to a rotation speed of 250. + -. 25 rpm. Finally, oven drying at 37 deg.C for more than 15 hr, and visually observing the purified scale material to be dry and free of discoloration.

(II) second exemplary purification of Scale Material (i.e., step S100 to step S130)

Scraping fish scales, cleaning with tap water for 3 times, and placing 200 g of fish scales in a 5L measuring cup for purification. 2 liters of 0.3N sodium hydroxide solution was poured into a 5 liter measuring cup containing fish scales to alkali treat the fish scales into a first scale material. The 5 liter measuring cup containing the fish scale was placed in a freezer (4 ℃ C.) and stirred for 18 hours. + -. 30 minutes at a set rotation speed of 250. + -. 25rpm using a digital electric stirrer to carry out the alkali treatment. Then, the solution in the 5 liter measuring cup is removed and 2 liters of 0.1M phosphate buffer solution (i.e., 1XPBS) is poured to clean the first scale material, and the purified scale material is cleaned in a refrigerated cabinet by using a digital electric stirrer with a constant rotation speed of 250 + -25 rpm and stirring for 30 minutes, and the above cleaning steps are repeated for 2 times. The washing solution in the 5 liter measuring cup was removed, and 2 liters of a 0.3N hydrochloric acid solution was poured into the 5 liter measuring cup containing the first scale material to perform acid treatment. The measuring cup was placed in a freezer and stirred for 1 hour using a digital electric stirrer set at 250 + -25 rpm for acid treatment. The acid treatment step was repeated for a total of 2 times. Next, the acid treatment solution in the 5 liter measuring cup was removed, and 2 liters of 0.1M phosphate buffer solution was poured and placed in a refrigerated cabinet. The above washing steps were repeated for a total of five times by stirring for 30 minutes at a set rotation speed of 250. + -. 25rpm using a digital electric stirrer. After cleaning, the fish scales are laid on an iron plate and dried for more than 15 hours at the temperature of 30 ℃.

Mohs hardness test

The test method comprises the following steps: the purified scale material prepared in the first example is scribed by Mohs hardness pens of different grades to observe the scribing situation, if no nick exists, the hardness of the purified scale material is larger than the grade; if slight nicks are generated, the hardness of the purified scale material is equivalent to the hardness of the grade; if significant scoring occurs, the hardness of the material representing the purified scale is less than this grade.

And (3) testing results: the first exemplary purified flake material has a mohs hardness of between 1 and 4, wherein the mohs hardness of 1 corresponds to the hardness of talc and the mohs hardness of 4 corresponds to the hardness of fluorite.

And (3) test evaluation: the soft ball with certain hardness can be made into scale soft balls with certain cleaning power.

(IV) cytotoxicity test

The test method comprises the following steps: after culturing L929 cells (mouse connective tissue, cell line L) for 24 hours together with the extract of the purified scale material prepared in the second example, the cell survival rate was observed. The negative control group cultures cells in pure medium without soaking in purified scale material. The positive control cultured cells with medium plus 5% dimethyl sulfoxide (DMSO), without soaking purified scale material. Experimental groups 1 to 3 are cultured cells after the purified scale material prepared in the second example was soaked in a pure culture medium, respectively. After 24 hours of culture, the culture medium of each group was removed, a culture medium containing thiazole blue (MTT) was added and the cells were cultured for 3 hours in the dark to obtain cell metabolites (purple crystals), the culture medium containing MTT was removed and DMSO was added to dissolve out the purple crystals, and the crystal concentration was analyzed by a spectrophotometer (OD570nm) to estimate the cell death rate and the cell survival rate.

And (3) testing results: as in table 1.

TABLE 1

And (3) test evaluation: the cell survival rate is more than 90%, and the cytotoxicity is low.

(V) measurement of cell residual amount

The test method comprises the following steps: after the purified scale material prepared in the second example was cut with scissors, DNA extraction was performed using a DNA extraction Kit (QIAamp DNA Mini Kit, QIAGEN), the amount of DNA contained in the sample was determined by the degree of chemical color development using a spectrophotometer after extraction, and based on this value, the amount of DNA contained in each purified scale was estimated again, and thus it was determined whether or not biological cells remained.

And (3) testing results: as in table 2.

TABLE 2

And (3) test evaluation: as can be seen from Table 2, the DNA residue of the purified scale material (experimental group) was very low and close to that of the negative control group of pure water, so it can be inferred that the purified scale material had no residual cells.

(VI) first example of scale-like Flexible beads (step S150 and step S170)

Taking purified scale material, pouring 500 +/-5 g of purified scale material into a rolling type pulverizer groove, and uniformly dispersing the purified scale material. And the polishing was carried out for 5 minutes while setting the current to 11. + -. 1A. Then, the particles to be shaped with different particle sizes are sequentially screened out by using 1 mm, 0.5 mm, 0.25 mm, 0.1 mm, 0.045 mm and 0.025 mm screens. Then 100 to 500 microns of the particles to be shaped are selected as the first particles and 1 to 100 microns are selected as the second particles. The first particles were mixed with pure water to a mixture, wherein the weight of the first particles to the volume of pure water was 1: 4. And rolling the second granules in a granulator, adding the mixture, rolling and mixing at room temperature to obtain a plurality of scale granules, rolling and mixing until the second granules are visually confirmed to be dry, and taking out. And the scale particles were crushed and sieved to select scale soft beads having a particle size of 100 to 700 μm, and a plurality of scale soft beads manufactured by the first example are shown in fig. 15.

Seventh example of scale Flexible beads (step S160 to step S170)

Taking purified scale material, pouring 500 +/-5 g of purified scale material into a rolling type pulverizer groove, and uniformly dispersing the purified scale material. And the polishing was carried out for 5 minutes while setting the current to 11. + -. 1A. Then, the particles to be shaped with different particle sizes are sequentially screened out by using 1 mm, 0.5 mm, 0.25 mm, 0.1 mm, 0.045 mm and 0.025 mm screens. And then mixing and stirring the shrimp shell powder, the particles to be shaped and the pure water containing sodium alginate uniformly according to the ratio of 2:1:10, putting the mixture into an oven, and drying the mixture at 37 ℃. After drying, crushing the mixture by a mortar, and screening the scale soft beads with the particle size of 100 to 700 microns.

(eight) multiple scale mollisol pH test (pH test)

The test method comprises the following steps: the pH values of the solutions to which the first exemplary scale beads were added were measured, and the pH values of the solutions to which the first exemplary scale beads were not added were measured, and the difference in pH values between the two was observed.

And (3) testing results: the presence or absence of the scale beads prepared in the first example did not affect the pH of the solution, the pH of the tested solutions did not differ significantly, and the error of the pH was ± 0.5.

(nine) acid and alkali resistance test

The test method comprises the following steps: the scale-shaped flexible beads prepared in the first example were placed in pure water, a ph5.5 solution, and a ph7.4 solution, respectively, and then soaked for 24 hours, whether the solutions were turbid or not was observed, and the change in particle size of the scale-shaped flexible beads prepared in the first example before and after soaking was observed under a microscope at 4-fold magnification (see fig. 23).

And (3) testing results: the particle size appearance of the scale soft beads soaked at different pH values is observed by a microscope, the particle size structures of the three groups are maintained to be 0.5-1.0 micron, no obvious size change occurs before and after soaking, and the soaked solution has no turbid discoloration phenomenon.

(Ten) biodegradability test

The test method comprises the following steps: the scale soft beads produced in the first example and the scale soft beads produced in the second example were placed in soil to observe the decomposition state.

And (3) testing results: in the soil, the scale soft beads made in the first example were decomposed within 10 days, and the scale soft beads made in the second example containing sodium alginate were decomposed within 8 days.

And (3) test evaluation: compared with the original fish scales (such as the fish scales scraped in step S100) which take 30 days to decompose in the soil, the biodegradability of the two sets of scale soft beads is stronger.

(eleven) experimental results of scale softening

As can be seen from the above test, the purified flake material processed in steps S100 to S130 has no cytotoxicity, and thus meets the evaluation of safety of human body, and the purified flake material has a certain hardness, and after being manufactured into a plurality of flake soft beads, the purified flake material can be applied to a cleaning product and provides a certain cleaning power. As can be seen from the pH test, the acid-base value of the solution is not affected by the scale soft beads, which is beneficial to the application of the scale soft beads in cleaning products or cosmetics. Moreover, the scale soft beads have biodegradability and do not cause environmental burden.

First exemplary (twelve) Scale Material (i.e., step S200 to step S250)

Scraping fish scales, washing with tap water for 3 times, reacting 10 g of the washed fish scales with 50 ml of 1N sodium hydroxide solution at room temperature for 5 hours to obtain a first scale material, wherein the rotation speed of a stirrer is set to be 250 +/-25 rpm to assist the reaction. After washing the first scale material with pure water, acid treatment was then performed with a 0.5M acetic acid solution and a 0.5N hydrochloric acid solution at room temperature for 24 hours to obtain a plurality of purified scale materials. A plurality of purified scale materials after washing were treated with 50 ml of 50ppm food grade sodium hypochlorite solution for 0.5 hour per 10 g of the purified scale materials to sterilize and deodorize the purified scale materials into scale materials, and a scale straw manufactured by the first example is shown in fig. 16.

(thirteen) second example of scale material (i.e., step S200 to step S250)

Scraping fish scales, washing with tap water for 3 times, reacting 10 g of the washed fish scales with 50 ml of 1N sodium hydroxide solution at room temperature for 5 hours to obtain a first scale material, wherein the rotation speed of a stirrer is set to be 250 +/-25 rpm to assist the reaction. The first scale material was washed with pure water, followed by acid treatment with 0.7M acetic acid solution and 0.5N hydrochloric acid solution at 50 ℃ for 4 hours to obtain a plurality of purified scale materials. And treating the cleaned purified scale materials with 50 ml of 50ppm food grade sodium hypochlorite solution for 0.5 hour every 10 grams of the purified scale materials so as to sterilize and deodorize the purified scale materials into scale materials.

Third exemplary (fourteen) scale material (i.e., step S200 to step S250)

Scraping fish scales, washing with tap water for 3 times, reacting 10 g of the washed fish scales with 50 ml of 0.3N sodium hydroxide solution at 4 ℃ for 18 hours to obtain a first scale material, wherein the rotation speed of a stirrer is set to be 250 +/-25 rpm to assist the reaction. The first scale material is washed with pure water. Next, acid treatment was performed with a 0.3N hydrochloric acid solution at 4 ℃ for 1 hour twice in total to obtain a plurality of second flake materials. The second scale material is washed with pure water. And then acid-treated with 0.5M acetic acid solution and 0.3N hydrochloric acid solution at 37 ℃ for 24 hours to obtain a plurality of purified flake materials. And treating the cleaned purified scale materials with 50 ml of 50ppm food grade sodium hypochlorite solution for 0.5 hour every 10 grams of the purified scale materials so as to sterilize and deodorize the purified scale materials into scale materials.

(fifteen) fourth exemplary scale material (i.e., step S200 to step S250)

Scraping fish scales, washing with tap water for 3 times, reacting 10 g of the washed fish scales with 50 ml of 0.3N sodium hydroxide solution at 4 ℃ for 18 hours to obtain a first scale material, wherein the rotation speed of a stirrer is set to be 250 +/-25 rpm to assist the reaction. The first scale material is purified water. Next, acid treatment was performed with a 0.3N hydrochloric acid solution at 4 ℃ for 1 hour twice in total to obtain a plurality of second flake materials. The second scale material is washed with pure water. And then acid-treated with 0.5M acetic acid solution and 0.3N hydrochloric acid solution at 60 ℃ for 1.5 hours to obtain a plurality of purified flake materials. And treating the cleaned purified scale materials with 50 ml of 50ppm food grade sodium hypochlorite solution for 0.5 hour every 10 grams of the purified scale materials so as to sterilize and deodorize the purified scale materials into scale materials.

First exemplary (sixteen) scale suction pipe (step S260)

And (3) attaching the scale material to a mould (a stainless steel bar with a proper specification), drying at a low temperature of 37-40 ℃, and taking out the mould to obtain the scale straw.

Second exemplary (seventeen) Scale straw (i.e., step S260)

The scale material is crushed into a plurality of pieces of 3-8 mm after excessive water is drained, then the pieces of the scale material are poured into a mould to be hot-pressed into a sheet material with the thickness of about 0.25 mm, a plurality of sheets of the sheet material are continuously pressed to be made into a large material roll, and the large material roll is made into a scale suction pipe by a paper suction pipe machine.

(eighteen) third exemplary embodiment of the scale suction pipe (i.e., step S260)

And (3) draining the scale materials to remove excessive water, crushing the scale materials into a plurality of pieces of 3-8 mm, and pouring the pieces of materials into a straw manufacturing machine to extrude the pieces of materials into a straw mold to be molded into the scale straw.

(nineteenth) fourth exemplary scale suction pipe (i.e., step S260)

The scale material is broken into a plurality of pieces of 3-8 mm after excessive water is drained, and then shrimp shell powder is added to increase the hardness of the scale straw, wherein the weight ratio of the pieces of material to the shrimp shell powder is 1: 0.1. the fragment material of the mixed shrimp shell powder is poured into a mould and is hot-pressed into a sheet material with the thickness of about 0.25 mm to be made into a material roll, and the material roll is made into a scale straw by a paper straw machine.

(twenty) fifth exemplary embodiment of the scale suction pipe (i.e., step S260)

The method comprises the following steps of (1) draining excessive water from the scale materials, smashing the scale materials into a plurality of scale materials of 3-8 mm, and adding paper pulp to help the scale straw to form, wherein the weight ratio of the scale materials to the paper pulp is 1: 0.05. the chip material of the mixed pulp is poured into a mould and is hot-pressed into a sheet material with the thickness of about 0.25 mm to form a material roll, and the material roll is made into a scale straw by a straw machine.

Sixth exemplary (twenty-one) flake suction pipe (step S260)

And (3) draining the scale materials to remove excessive water, crushing the scale materials into a plurality of pieces of 3-8 mm, adding 1% sodium alginate to help the scale straw to be shaped, and increasing the hardness of the scale straw. Then, the fragment material containing 1% sodium alginate is poured into a mould to be hot-pressed into a sheet material with the thickness of about 0.25 mm to be made into a material roll, and the material roll is made into a scale straw by a paper straw machine.

(twenty-two) seventh exemplary embodiment of the scale suction pipe (i.e., step S260)

The flake material was drained and broken into pieces of 3 to 8 mm, and 1% corn starch was added to aid in the formation of the flake straw. Then, the chip material containing 1% of corn starch is poured into a mould to be hot-pressed into a sheet material with the thickness of about 0.25 mm to be made into a material roll, and then after edible wax is coated on the material roll, the flake straw is made by a paper straw machine.

(twenty-third) eighth exemplary scale suction pipe (step S260)

The scale material is broken into pieces of 3-8 mm after excess water is drained off, and 1% cellulose (CMC, carboxymethyl cellulose) is added to help the formation of the scale straw and increase the hardness of the scale straw. Then, the chip material containing 1% cellulose was poured into a mold and hot-pressed into a sheet material having a thickness of about 0.25 mm to make a roll, and a scale straw was manufactured by a paper straw machine.

Ninth exemplary (twenty-four) scale suction pipe (step S260)

Drying the scale material at a low temperature of 30-37 ℃, grinding the dried scale material into a powdery material with the diameter of 0.5-1 mm, and then adding shrimp shell powder and 10% polylactic acid, wherein the weight ratio of the fragment material to the shrimp shell powder is 1: 0.5. pouring the powdery material containing the shrimp shell powder and the polylactic acid into a straw manufacturing machine to manufacture the scale straw.

(twenty-five) tenth example of a scale suction pipe (i.e., step S260)

Drying the scale material at a low temperature of 30-37 ℃, grinding the dried scale material into a powdery material with a diameter of 0.5-1 mm, adding 10% of polylactic acid, and pouring the powdery material containing the polylactic acid into a straw manufacturing machine to manufacture the scale straw.

Eleventh exemplary (twenty-sixth) Scale pipette (i.e., step S260)

Drying the scale material at a low temperature of 30-37 ℃, grinding the dried scale material into a powder material with a diameter of 0.5-1 mm, adding 1% of sodium alginate and 10% of polylactic acid, and pouring the powder material containing the sodium alginate and the polylactic acid into a straw manufacturing machine to manufacture the scale straw.

Twelfth exemplary (twenty-seventh) Scale straw (i.e., step S260)

Drying the scale material at a low temperature of 30-37 ℃, grinding the dried scale material into a powdery material with a diameter of 0.5-1 mm, adding 1% of corn starch and 10% of polylactic acid, and pouring the powdery material containing the corn starch and the polylactic acid into a straw manufacturing machine to manufacture the scale straw.

Thirteenth exemplary embodiment of the scale suction pipe (step S260)

Drying the scale material at a low temperature of 30-37 ℃, grinding the dried scale material into a powder material with a diameter of 0.5-1 mm, adding 1% of cellulose and 10% of polylactic acid, and pouring the powder material containing the cellulose and the polylactic acid into a straw manufacturing machine to manufacture the scale straw.

(twenty-eight) mechanical Property testing

Defining: when the deformation quantity does not exceed the elastic limit of the corresponding material, the ratio of the positive stress to the positive strain is defined, namely the Young modulus of the material, and the maximum value of the positive stress is the maximum load.

Tensile test results: the flake straw made by the first example had a Young's modulus of 100 to 250 million pascals (MPa) and a maximum load of 5000 to 6000 grams force (gf).

(twenty nine) usability test

The test method comprises the following steps: the scale straw made in the first example was placed in water and observed for disintegration.

And (3) testing results: the scale straw made in the first example does not collapse when soaked in water for 18 days and still maintains the tubular structure.

(thirty) acid and base resistance test

The test method comprises the following steps: the scale pipette manufactured in the first example was immersed in pure water, a neutral solution (pH6-8), and an acidic solution (< pH4), respectively, and was observed to be disintegrated.

And (3) testing results: the scale suction pipe is not disintegrated after being soaked in pure water for 18 days, and the pipe-shaped structure is still maintained; soaking the scale sucker in a neutral solution (pH6-8) for 24 hours without disintegration; the scale pipette did not break down when soaked in acidic solution (< pH4) for 1 hour.

(thirty-one) Heat resistance test

The test method comprises the following steps: the first exemplary scale-formed straw was immersed in hot water at 60 ℃ and observed for disintegration.

And (3) testing results: the flake straw is not disintegrated after being soaked in hot water at 60 ℃ for 2 hours.

(thirty-two) biodegradability test

The test method comprises the following steps: the scale-shaped straws manufactured in the first and sixth examples were placed in soil to observe their decomposition states.

And (3) testing results: in the soil, the scale straw made in the first example was decomposed within 10 days, while the scale straw made in the sixth example containing sodium alginate was decomposed within 8 days.

And (3) test evaluation: compared with the original fish scales (such as the scales scraped in the step 100) which take 30 days to decompose in the soil, the two groups of scale suction pipes have stronger biodegradability.

(thirty-three) scale pipette test results

From the above tests, it can be concluded that the flake straw has a certain heat resistance, acid and alkali resistance and usability, and thus has a very high potential as a substitute for plastic straws. Moreover, the flake straw has better degradability (compared with the original flake material) and does not cause environmental burden.

In summary, the scale-derived articles of daily use and the manufacturing method thereof according to the embodiments of the present invention are suitable for providing an environmentally friendly article of daily use, and the scale-derived articles of daily use have biodegradable properties, and can also be used as a substitute for the same type of plastic products, such as plastic soft beads and plastic straws. The scale-derived daily necessities which are low in pollution, environment-friendly and low in harm to marine organisms are provided for consumers, so that the green and continuous purpose can be achieved, and the convenience in use for the consumers is provided.

Although the present invention has been described with reference to the preferred embodiments, it is to be understood that the invention is not limited thereto, and that various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (28)

1. A method of making a scale-derived household item, comprising:

obtaining a plurality of scales;

treating the flakes with a lye to obtain a plurality of purified flake material;

washing the purified scale material;

drying the washed purified flake material, wherein the purified flake material comprises 50% to 90% collagen;

pulverizing the dried purified flake material into a plurality of particles to be shaped, wherein the particles to be shaped comprise a first plurality of particles;

mixing the first particles with a liquid to form a mixture, wherein the ratio of the weight of the first particles to the volume of the liquid is 1:1 to 1: 12, and the weight of the first particles is in grams and the volume of the liquid is in milliliters; and

and granulating the mixture to obtain a plurality of scale flexible bead microbeads.

2. The method of making scale-derived household items of claim 1, wherein said step of treating said scale with lye to obtain a plurality of purified scale materials comprises:

and treating the scales with the alkali liquor to obtain the purified scale material.

3. A method of making scale-derived household items as in claim 2, wherein said step of treating said scale with lye to obtain a plurality of purified scale materials comprises:

alkali treating the scale with the alkaline solution into a plurality of first scale materials;

washing the first scale material; and

and the first scale material after acid-acid treatment and cleaning is taken as the purified scale material.

4. The method of making scale-derived living goods according to claim 1, wherein the step of granulating with said mixture comprises:

rolling and mixing the mixed solution and a plurality of second particles to obtain the scale soft beads, wherein the second particles are biological substances, each second particle is smaller than each first particle, and the weight ratio of the first particles to the second particles is 1: 2.

5. the method of making scale-derived living goods according to claim 1, wherein the step of granulating with said mixture comprises:

rolling and mixing said mixture with said second particles to obtain a plurality of scale particles, wherein said second particles are biological matter, each of said second particles being smaller than each of said first particles, wherein the weight ratio of said first particles to said second particles is 1: 2;

breaking the scale particles; and

sieving the smashed scale particles to obtain the scale soft beads.

6. A method of making scale-derived articles of daily use as claimed in claim 1 wherein the step of mixing said first particles with a liquid into a mixture comprises:

mixing said first particles, said second particles and said liquid to form said mixture, wherein each of said second particles is smaller than each of said first particles, and wherein the ratio of the weight of said first particles, the weight of said second particles and the volume of said liquid is 1: 2:1 to 1: 2: 10, or wherein the ratio of the combined weight of the first particles and the second particles to the volume of the liquid is 1:1 to 1: 10.

7. the method of making scale-derived living goods according to claim 6, wherein the step of granulating with said mixture comprises:

drying the mixture;

breaking up the dried mixture to obtain the scale particles; and

sieving the scale particles to obtain the scale soft beads.

8. A method of making scale-derived household items as recited in claim 1, wherein the step of pulverizing the dried purified scale material into a plurality of particles to be molded comprises:

crushing the dried purified scale material into a plurality of particles to be molded; and

sieving the particles to be shaped to obtain the first particles and the second particles, wherein each of the second particles is smaller than each of the first particles.

9. The method of manufacturing scale-derived living goods according to any one of claims 4 to 6, wherein the second granule is any one of shrimp shell powder, crab shell powder, or chitin powder.

10. A method of manufacturing scale-derived household goods as claimed in any one of claims 1 to 5, wherein said liquid is pure water and the ratio of the weight of said first particles to the volume of said pure water is 1:1 to 1: 10.

11. the method of making scale-derived living goods according to any one of claims 1 to 8, wherein the liquid comprises the purified water and a binder.

12. A method of making a scale-derived household item, comprising:

obtaining a plurality of scales;

treating the scales with alkali liquor to form a plurality of first scale materials;

washing the first scale material;

the first scale material after being cleaned by first acid liquid is taken as a plurality of purified scale materials;

washing the purified scale material;

the purified scale material after being cleaned by edible bleaching agent is a plurality of scale materials, wherein the scale material after being cleaned again contains 50-90% of collagen; and

and manufacturing the scale material to obtain the scale suction pipe.

13. The method of making scale-derived household items of claim 12, wherein the step of treating the washed first scale material with the first acid solution as the purified scale material comprises:

and the first scale material after being acid-treated and cleaned by the first acid solution is a plurality of purified scale materials.

14. The method of making scale-derived household items of claim 12, wherein the step of treating the washed first scale material with the first acid solution as the purified scale material comprises:

the first scale material after being acid-treated and cleaned by the first acid solution is a plurality of second scale materials;

washing the second scale material; and

and the second scale material after being treated and cleaned by second acid liquid acid is the purified scale material.

15. The method of making scale-derived articles of daily use of claim 12, wherein the step of making with said scale material to obtain scale straws comprises:

and (3) attaching the scale material on a mould and drying to obtain the scale straw.

16. The method of making scale-derived articles of daily use of claim 12, wherein the step of making with said scale material to obtain scale straws comprises:

breaking up the scale material to obtain a plurality of pieces of material having a diameter of 2 to 10 mm;

hot pressing the scrap material into a sheet of material having a thickness of 0.20 to 0.35 mm; and

the flake straw is made of the sheet material by a mould.

17. The method of making scale-derived articles of daily use of claim 12, wherein the step of making with said scale material to obtain scale straws comprises:

drying the scale material;

breaking up the dried scale material to obtain a plurality of powdery materials with a diameter of 0.5 to 1 mm; and

and (3) using a mould to make the powdery material into the scale suction pipe.

18. A method of manufacturing scale-derived articles of daily use according to claim 16 or 17, wherein the step of making with the scale material to obtain scale straws comprises:

and mixing an additive with the scale material, and manufacturing to obtain the scale straw.

19. A flake-derived household item comprising:

a plurality of degradable scale beads comprising:

a plurality of first particles made of at least one flake, wherein the first particles comprise 50% to 90% collagen; and

a plurality of second particles associated with the first particles, wherein the plurality of second particles are biological matter and each of the second particles is smaller than each of the first particles.

20. The scale-derived household item of claim 19, wherein said degradable scale beadlets further comprise a binder to bind said first particles to said second particles into said degradable scale beadlets.

21. The scale-derived household item of claim 19 or 20, wherein said second particles are made from said at least one scale.

22. The scale-derived commodity of claim 19 or 20, wherein the second particle is any one of shrimp shell meal, crab shell meal, or chitin meal.

23. Scale-derived household item according to claim 19 or 20, wherein the weight ratio of said second particles to said first particles is 2: 1.

24. the scale-derived household item of claim 19 or 20, wherein said at least one scale is a fish scale, a terrestrial animal scale, or a combination thereof.

25. A flake-derived household item comprising:

a degradable scale straw is made of a plurality of scales and comprises 50-90% of collagen.

26. The scale-derived commodity of claim 25, wherein the degradable scale straw further comprises an additive, and the additive is shrimp shell meal, crab shell meal, paper pulp, sodium alginate, corn starch, polylactic acid, cellulose, or a combination thereof.

27. The scale-derived household item of claim 25 or 26, wherein the degradable scale straw has a hairline of the scale structure of said scales.

28. The scale-derived commodity of claim 25 or 26, wherein said scale is a fish scale.

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