RO138007A2 - Composition for 3d printing of biodegradable artificial baits for sport fishing and process for preparing said composition - Google Patents

Abstract

The invention relates to a composition for 3D printing of biodegradable artificial baits for sport fishing, to a process for preparing the same and to a process for using said composition. According to the invention, the composition consists of the following components: 1...6% sodium alginate, 0.1...9% tetrasodium pyrophosphate, 0.1...4.5% sodium sulphate and, for the remainder, water, the percentage being expressed by mass. The claimed preparation process consists in preparing a component A by mixing the sodium alginate with 1/2 of the total amount of water, at a temperature of 20...30°C, with a rotational speed of 150...500 rpm until a homogeneous paste results, to which the tetrasodium pyrophosphate is added while continuing to stir at the same speed for 1...4 hours, followed by stirring until the calcium sulphate and the food colouring is homogenized with the remaining 1/2 of the total amount of water, to result in a component B which is added at variable flow rate into the component A for 1...60 min and stirring the components for 2...3 hours, at a rotational speed of 50...300 rpm, until the 3D printing composition is obtained. The claimed process of use consists in feeding the tank of an extruder-type 3D printer having a nozzle of 0.2...2 mm, with the above-mentioned bait composition, loading the desired 3D model and printing at a speed ranging between 10...100 mm/min, then the 3D-printed bait is removed from the printer platform and it is immersed into the curing solution consisting of 50...700 g/l of calcium chloride in water, for 0.5 to 8 hours, while keeping it immersed in the preservation solution consisting of calcium chloride solution 10...600 g/l up to its use.

Description

COMPOSITION FOR 3D PRINTING OF BIODEGRADABLE ARTIFICIAL BAITS AND PROCEDURE FOR OBTAINING IT

The present invention relates to a composition for 3D printing of biodegradable artificial baits intended for sport fishing and to a method of obtaining this composition.

Biodegradable compositions intended for obtaining biodegradable artificial baits intended for sport fishing of predatory fish are known. Artificial fishing lures for predatory fish, commonly referred to as lures, were introduced to avoid the unnecessary and torturous slaughter of nada fish. Another advantage of using artificial baits is that they are much more durable than live baits, which allows for more catches with the same bait. This durability is a result of the fact that most lures are composed of non-biodegradable synthetic plastics. However, the fact that fishing baits are made of non-biodegradable plastic materials has a negative impact on both the environment and predatory fish. These artificial baits, commonly referred to as lures, were developed to counteract the negative effects of plastic predatory artificial baits. It is estimated that around 500 tons of plastic baits are lost annually in Canada alone (Franson, Hansen et al. 2003), having a harmful effect on aquatic habitats (Raison, Nagrodski et al. 2014) and being a source of pollution microplastic (Iverson 2019). The ingestion of lost baits by predatory fish generates a series of conditions that debilitate and unnecessarily torment the animals (Raison, Nagrodski et al. 2014, Sanft, Porreca et al. 2018). Such consequences are contrary to the ethics of sport fishing, the requirement for biodegradable baits being high.

Biodegradable compositions protected by patents/utility models and/or patent/utility model applications generally consist of water, gelling agents, predatory fish attractants.

Utility model application AU2018201839 relates to a biodegradable composition based on sugar, glucose syrup, starch, flavor, food coloring, citric acid, fish oil, fish meal, shrimp meal, squid flavor compounds, natural flavor identical fish, anise oil, agar-agar, fumaric acid, gelatin, iridescent compounds in the form of powder or granules.

Utility model application ES1253314U claims a composition consisting of 50-60% water, 5-35% fish oil or cephalopod oil or crustacean oil and between 10% and 45% gelling agents.

Patent CN101268812B describes a composition consisting of polyvinyl alcohol, hydroxypropylmethylcellulose, sodium carboxymethylcellulose, microcrystalline cellulose, carbomer, sugar, gluten, fish meal, shrimp meal, betaine, food coloring.

Patent US6753004B2 relates to a biodegradable composition for the manufacture of artificial baits intended for sport fishing of predatory fish, which also includes fish attractants. The attractants are selected from the following products: fish protein hydrolyzate, fish oil, fish meal, ground crustaceans, ground clams, fruits, spices, garlic, garlic oil, neutral L-amino acids, betaine, nucleotides, inosine and inosine -5-monophosphate, sulfonium compounds, dimethyltin / sulfobetaine, dimethylpropiothetin / S,S-dimethyl-beta-propiothetin, powders with iridescent effect and / or food dyes. The compositions claimed by this patent are water-based and include between 5-15% sucrose, 10-30% gelatin, 1-5% sodium alginate, 1-5% gum acacia, 0.1-1% calcium chloride, 1 -5% starch, 30-50% corn syrup, 1-5% glycerin, 1-3% sodium benzoate and 1-3% sodium metaphosphate.

Patent US6174525B1 protects a composition consisting of 1-24% polyvinyl alcohol with a molecular weight of at least 195,000 and a degree of polymerization of at least 2500.0-4% glucomannan from Amorphophallus konjac, 0-10% water-soluble polymer gum, 0.1% - 2% of an aromatic hydroxyl compound that accelerates the formation of hydrogen bonds, 1-30% fish attractant, 1% - 15% plasticizer glycerin or propylene glycol, 63-93% water. The water-soluble polymeric gum is selected from the group represented by iota carrageenan gum and xanthan gum. Aromatic hydroxyl compounds that favor the formation of hydrogen bonds are selected from the group catechol, nordihydroguaiaretic acid, hydroquinone, anthraquinone, resorcinol, gallic acid, pyrogallol, phloroglucinol, propylgallate, glutaric acid. The fish attractant is selected from Berkley-type attractants (a water-in-oil emulsion containing protein hydrolysates, petroleum jelly, glycerin, propylene glycol, co-methacrylates), garlic oil, soluble compounds from menhaden fish, small fish of the order Clupeiformes , menhaden hydrolyzate and menhaden oil. The composition is subjected to a freeze-thaw cycle before use.

Patent CN112661983A describes a method of preparing a hydrogel material for 3D printing, which comprises mixing the solution of sodium alginate and methacrylic anhydride preferably in an ice water bath and then mixing with a photocrosslinking agent and a photoinitiator. curing is done by exposing the composition to an ultraviolet lamp.

The main disadvantage of these biodegradable compositions is their high microbiological instability, which requires special storage conditions for ^^extjhfiie storage period. In order to extend the shelf life, the specific composition of patent US6753004B2 includes preservatives of the sodium benzoate type. The toxicity of benzoate preservatives to fish has recently been proven (Gaur, Purushothaman et al. 2018). There is also the risk of the accumulation of these types of preservatives in the food chain and of their metabolism into benzene, a carcinogenic compound (Azuma, Quartey et al. 2020). The proven ecological risks go against the ethics of sport fishing, the acceptance of biodegradable artificial baits containing benzoate class preservatives being reduced among end users.

Biodegradable compositions to be 3D printed for a customization of different types of sport fishing lures have not yet been described. The market demands such customized baits, which attract the spectacular attack of the predators on them. US patent 10130082B2 claims a kit of non-biodegradable components to allow for custom made lures.

The technical problem that the invention solves is to make a biodegradable composition with a shelf life of up to one month, which does not include preservatives and which can be 3D printed in a limited series, for immediate use.

The composition according to the invention consists of: 1...6% sodium alginate, 0.1...9% tetrasodium pyrophosphate, 0.1...4.5% calcium sulfate, 0...1% dye food and the rest up to 100% water, the proportions being expressed in gravimetric percentages.

The process of obtaining, according to the invention, the composition for artificial baits consists in mixing sodium alginate and water from the total amount at a temperature of 2O...3O°C with a rotation speed of 150...500rot/min of water until a homogeneous paste is obtained to which a quantity of tetrasodium pyrophosphate is added, continuing mixing with a rotation speed of 150..500rot/min until a homogeneous paste is obtained and maintaining the mixing for 1... 4 hours creating a homogenous paste resulting in component A, mix calcium sulfate and food coloring with the amount of water until homogenized resulting in component B. add component A over a period of 1...60min with variable flow rate component B further mixing for 2...3 hours at a rotation speed of 50...300rot/min resulting in the composition for 3D printing of biodegradable artificial baits which can be used as such in 3D printing of baits or put in a hermetically sealed container for storage until use.

Using composition for 3D printing:

A 3D printer of extra malleable materials, with a nozzle of 0.2...2mm and a support platform, is used for printing artificial baits. You have it

the malleable material tank of the printer with the composition for 3D printing of biodegradable artificial baits, load the desired bait 3D model into the printer and print at a speed of 10...100mm/min. The bait made by printing is detached from the printer platform and immersed in the curing solution consisting of a calcium chloride solution 50...700g/l in water for 0.5...8 hours and preserved by immersion in the preservation solution consisting of calcium chloride solution 10...600g/l in water, until use.

The invention presents the following advantages:

- It allows 3D printing in limited series due to the non-Newtonian rheological behavior of the composition, namely fluidization when applying pressure for printing and gelling in the absence of the application of mechanical forces;

- It has the possibility of high customization of the artificial bait, according to the requirements of every amateur fisherman, thanks to 3D printing;

- The bait obtained from the composition according to the invention is biodegradable;

- The obtaining process is carried out at room temperature in the range of 20...30°C;

- It has a high attractive effect for fish due to the food coloring content;

- It is easily made with little consumption of materials and resources.

Example 1. a volume of 100ml of water is introduced into a 300ml Berzelius vessel, 3g of sodium alginate are added and mixed with a rotating mechanical stirrer at a speed of 300rot/min for 2 hours at room temperature 21...24° C until a homogeneous paste is obtained, add a quantity of 6g of tetrasodium pyrophosphate and continue mixing for 2 hours until homogenization (component A). in a 200ml Berzelius vessel, mix 100ml of water with 3g of calcium sulfate with a mechanical stirrer at a speed of 100rot/min for 30min and 0.5g of food coloring - betaine (component B). The stirring of component A is continued and component B is added at a flow rate of 10ml/min and further mixed for 2 hours at 300rot/min obtaining the composition for 3D printing which is placed in a 250ml glass vessel with a lid.

Example 2, in a 300ml Berzelius vessel, a volume of 100ml of water is introduced, 4g of sodium alginate are added and mixed with a rotating mechanical stirrer at a speed of 300 rpm for 2 hours at room temperature 21... 24°C until a homogeneous paste is obtained, add a quantity of 5.5 g of tetrasodium pyrophosphate and continue mixing for 2 hours until homogenization (component A). in a 200ml beaker, mix 100ml of water with 0.5g of calcium sulfate with a mechanical stirrer at 100 rpm for 30min and 0.1g of food coloring - curcumin (component B). Continue stirring component A and add component B at a flow rate of 50ml/min and further mix for 2 hours at 200rot/min to obtain the composition for 3D printing which is placed in a 250ml glass vessel with a lid .

Bibliographic sheet

Azuma, S. L, N. K. A. Quartey and I. W. Ofosu (2020). Sodium benzoate in nonalcoholic carbonated (soft) drinks: Exposure and health risks. Scientific Africani0: e00611.

Franson, J.C., S.E. Hansen, T.E. Creekmore, C.J. Brand, D.C. Evers, A.E. Duerr and S. DeStephano (2003). Lead Fishing Weights and Other Fishing Tackle in Selected Waterbirds. National Wildlife Health Center12: 27-42.

Gaur, H., S. Purushothaman, N. Pullaguri, Y. Bhargava and A. Bhargava (2018). Sodiumbenzoate induced developmental defects, oxidative stress and anxiety-like behavior in zebrafish larvae. Biochemical and Biophysical Research Communications502(3): 364-369.

Iverson, A. R. (2019). The United States requires effective federal policy to reduce marine plastic pollution. Conservation Science and Practices (6): e45.

Raison, T., A. Nagrodski, C. D. Suski and S. J. Cooke (2014). Exploring the Potential Effects of Lost or Discarded Soft Plastic FishingLures on Fish and the Environment. Water, Air, & Soil Pollution 225(2): 1869.

Sanft, E. J„ A. P. Porreca, J. J. Parkos III, T. M. Detmer and D. H. Wahl (2018). Effects of Ingestion of Soft Plastic Fishing Lures on Largemouth Bass. North American Journal of Fisheries Management38(3): 718-724.

Claims (3)

1. Composition for 3D printing of biodegradable artificial baits characterized by the fact that it consists of 1...6% sodium alginate, 0.1...9% tetrasodium pyrophosphate, 0.1...4.5% sulfate of sodium and the rest water, the proportions being expressed in gravimetric percentages. 2. Process for obtaining the composition for 3D printing of biodegradable artificial baits, according to claim 1, characterized by making component A by mixing at a temperature of 2O...3O°C with a rotation speed of 150...500rot/min of sodium alginate and water from the total amount of water until a homogeneous paste is obtained to which a quantity of tetrasodium pyrophosphate is added, continuing mixing with a rotation speed of 150...500rot/min until a paste is obtained homogenous and maintaining mixing for 1...4 hours, mixing calcium sulfate and food coloring with % of the amount of water, until homogenization resulting in component B, adding component B during 1...60min with variable flow in component A, mixing the components for 2...3 hours with a rotation speed of 50...300rot/min resulting in the composition for 3D printing of biodegradable artificial baits 3. Method of using the composition for 3D printing of biodegradable artificial baits, according to claim 1, characterized by a nozzle having a feed size of 0.2...2mm, a printing speed of 10...100mm/min, immersion the bait thus made in the hardening solution consisting of a 5O-5-7OOg/l calcium chloride solution in water, for 0.5...8 hours and keeping it by immersion in the conservation solution consisting of a calcium chloride solution calcium 10...600 g/l in water, until use.