KR102393864B1 - Composition for manufacturing biodegradable plastic seaweed farming nets containing seaweed fertilizer ingredients - Google Patents

Abstract

The present invention relates to a composition for manufacturing biodegradable plastic seaweed farming nets containing seaweed fertilizer ingredients and a method for manufacturing the same and, more specifically, to a composition for manufacturing biodegradable plastic seaweed farming nets containing seaweed fertilizer ingredients that can naturally decompose in seawater while ensuring performance equivalent to that of conventional non-degradable seaweed farming nets, thereby minimizing contamination by waste aquaculture nets and consequent damage, and a method for manufacturing the composition for manufacturing seaweed farming nets.

Description

Composition for manufacturing biodegradable plastic seaweed nets containing seaweed fertilizer ingredients

The present invention relates to a composition for producing a biodegradable plastic seaweed culture net containing seaweed fertilizer ingredients and a method for producing the same, and more particularly, to a natural biodegradable seaweed culture net in seawater while securing performance comparable to that of a conventional hard-to-degradable seaweed culture net. The present invention relates to a composition for manufacturing a biodegradable plastic seaweed net containing seaweed fertilizer, which can be decomposed to minimize contamination by waste culture nets and consequent damage, and a method for preparing the composition for preparing the seaweed culture nets.

In general, in order to culture seaweeds such as brown algae, red algae, and green algae in the sea, a structure is installed in the sea and spores of the seaweed are attached to the structure and then grown. Traditionally, structures for growing these seaweeds are made by weaving them with bamboo, sap, and sari, but recently, there is a trend to use aquaculture nets made of nets.

Such a culture net is mainly composed of a net woven with a plurality of strands of netting thread inside the main rope having a square rim made of a rope made of synthetic fiber, or inside the main rope with a square rim made of a rope made of synthetic fiber material. A plurality of mesh support ropes are installed at regular intervals, and a plurality of unit meshes interwoven with a single or a plurality of mesh threads are provided between the plurality of mesh support ropes to be installed at regular intervals.

Since the conventional aquaculture net is retrieved after a certain period of time has elapsed after being installed at the sea level or the seabed, it is frequently lost due to rough sea conditions or when the net is cut by other fishing boats operating while dragging fishing gear.

In addition, since the composition for producing the aquaculture net is mainly composed of a difficult-to-decomposable polymer synthetic resin or an organic tin compound that is not biodegradable, aquaculture in which aquatic organisms are entangled or captured in the lost aquaculture net is continuously repeated while aquaculture There is a significant loss of resources, and fishing gear accumulated on the seafloor can contaminate the spawning grounds and habitats of aquatic organisms. In addition, there was a problem that it is a major cause of marine pollution that continuously releases environmental hormones and destroys the marine ecosystem.

Republic of Korea Patent Publication No. 10-1749343

The present invention is to solve the above problems, and it is possible to secure sufficient strength and flexibility necessary for aquaculture networks, and to enable natural decomposition in seawater, biodegradable plastic seaweed culture containing seaweed fertilizer ingredients An object of the present invention is to provide a composition for manufacturing a net and a method for manufacturing the same.

These and other objects and advantages of the present invention will become apparent from the following description of preferred embodiments.

The above object is a liquid fertilizer containing seaweed powder; biodegradable polymers; and an organic solvent.

Specifically, the liquid fertilizer is prepared by mixing seaweed powder containing at least one selected from the group consisting of blue-green algae, brown algae, red algae, and combinations thereof, mineral concentrated water, and a proteolytic enzyme. can

Specifically, the biodegradable polymer is, poly-L-lactic acid, poly-D, L-lactic acid, polyglycolic acid, polycaprolactone, polylactic acid-co-glycolic acid, polytrimethylene carbonate, polybutylene adipate terre It may include one or more selected from the group consisting of phthalates, polyphosphazines, and combinations thereof.

According to the present invention, as a material that can be naturally decomposed in seawater is applied, it is decomposed after use and prevents contamination of coastal waters by waste aquaculture nets, protects marine ecosystems, and prevents ghost fishing to minimize damage. .

In addition, the composition for producing a seaweed culture net according to the present invention has mechanical strength, flexibility, and elasticity equivalent to those of conventionally used recalcitrant seaweed culture nets, so that it is possible to not only improve the catch, but also to increase the amount of fish caught in the rapid environment and temperature It has the advantage of being able to prevent denaturation problems due to changes.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings of the present invention. It will be apparent to those of ordinary skill in the art that these examples are merely presented by way of example to explain the present invention in more detail, and that the scope of the present invention is not limited by these examples. .

Further, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in case of conflict, this specification, including definitions will take precedence.

In order to clearly explain the invention proposed in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are assigned to similar parts throughout the specification. And, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated. In addition, "unit" described in the specification means one unit or block that performs a specific function.

In each step, identification numbers (first, second, etc.) are used for convenience of description, and identification numbers do not describe the order of each step, and each step does not clearly describe a specific order in context. It may be performed differently from the order specified above. That is, each step may be performed in the same order as the specified order, may be performed substantially simultaneously, or may be performed in the reverse order.

Hereinafter, embodiments and examples of the present application will be described in detail with reference to the accompanying drawings. However, it may not be limited to these embodiments and examples and drawings of the present application.

One aspect of the present application is a liquid fertilizer comprising seaweed powder; biodegradable polymers; and an organic solvent.

The composition for manufacturing seaweed aquaculture nets according to the present invention contains biodegradable polymers that can be naturally decomposed in seawater, so it is decomposed after use to prevent contamination of coastal waters by waste aquaculture nets, protect marine ecosystems, and promote ghost fishing damage can be minimized. In addition, it has mechanical strength, flexibility, and elasticity equivalent to those of conventionally used recalcitrant seaweed aquaculture nets, so it can not only improve the catch, but also prevent denaturation problems caused by rapid environmental and temperature changes. has

In one embodiment, the composition for producing a seaweed aquaculture network can exhibit high natural compatibility by using a liquid fertilizer containing discardable seaweed as a component, and can be decomposed by microorganisms contained in seawater. It can exhibit biodegradability and can have the effect of improving the viscosity and flexibility of the composition for producing a seaweed aquaculture net.

In one embodiment, the liquid fertilizer may be included in about 1 to 10% by weight. If the liquid fertilizer is included in an amount of less than about 1% by weight, the effect of improving viscosity and flexibility resulting from the inclusion of the liquid fertilizer may not be sufficiently exhibited, and if it exceeds about 10% by weight, miscibility with other components this may be hindered.

In one embodiment, the liquid fertilizer comprises the steps of preparing seaweed and drying; pulverizing the dried seaweed into a size range of about 40 to about 70 mesh using a grinder; mixing the powdered seaweed with concentrated mineral water and proteolytic enzyme; and obtaining a liquid fertilizer by fermenting the mixture. Specifically, the fermentation may be performed for about 10 days to about 30 days at a temperature range of about 20°C to about 37°C, and if fermentation is not performed during the temperature range and period range, the seaweed contains The effects of liquid fertilizers indicated by pharmacological components may not be fully exhibited.

In one embodiment, the liquid fertilizer comprises about 35% by weight of seaweed powder comprising at least one selected from the group consisting of blue-green algae, brown algae, red algae, and combinations thereof, based on the total weight of the liquid fertilizer, and mineral concentrate It may be characterized in that it is prepared by mixing 60% by weight, and about 5% by weight of a protease.

In one embodiment, the seaweed may include red algae, and preferably, may include red algae, agarfish, or agaric algae.

In one embodiment, the seaweed powder may be included in about 20 to about 40 wt% of the liquid fertilizer, and if the seaweed powder is included in less than about 20 wt%, the effect of improving viscosity and flexibility may not be sufficiently exhibited. And, if it exceeds about 40% by weight, the mechanical strength of the aquaculture net to be manufactured later may decrease.

In one embodiment, the mineral concentrated water is obtained by concentrating seawater or brine using sea salt, or obtained as a mixture of seawater concentrated water and concentrated seawater salt water, the concentration of salt is reduced from about 30 to about 40 It may mean concentrated water of Brix. Specifically, the mineral concentrated water can be used as the mineral concentrated water, or seawater concentrated water with a reduced NaCl concentration of about 30 to about 40 Brix obtained by concentrating seawater while removing sodium by a conventional method, or sea salt in water Concentrated water of an aqueous solution of sea salt with reduced NaCl concentration of about 30 to about 40 Brix obtained by concentration while removing salt after dissolving may be used.

In one embodiment, the concentrated mineral water may be included in an amount of about 50 to about 60% by weight of the liquid fertilizer, and if the concentrated mineral water is included in an amount of less than about 50% by weight, the liquid fertilizer may not be easily manufactured , If it exceeds about 60% by weight, the mechanical strength of the aquaculture net to be manufactured later may decrease.

In one embodiment, the proteolytic enzyme may include Alcalase or Esperase, specifically, it may include Esperase.

As a component of the composition for producing the seaweed aquaculture net, the biodegradable polymer imparts biodegradability to the aquaculture net, so that if the aquaculture net is lost after use or during use, the microorganisms or enzymes present in nature such as soil or the sea to be decomposed by For example, the biodegradable polymer is poly-L-lactic acid, poly-D, L-lactic acid, polyglycolic acid, polycaprolactone, polylactic acid-co-glycolic acid, polytrimethylene carbonate, polybutylene adipate terre It may include one or more selected from the group consisting of phthalates, polyphosphazines, and combinations thereof.

Poly lactic acid has excellent heat resistance and strength among biodegradable polymers, and excellent transparency after molding. Polylactic acid is a polyester synthesized by polycondensation of lactic acid or ring-opening polymerization of lactide. It has intermediate physical properties between polyamide and polyethylene terephthalate (PET), and mainly Since it is made from natural vegetable sugars obtained from potatoes and corn, the biodegradability is high and the hardness is generally high. Polylactic acid is used for various purposes such as films, packaging containers, sheets, packaging materials, coatings, and medical materials.

Since poly glycolic acid (PGA) contains an aliphatic ester bond in its molecular chain, it is decomposed by microorganisms or enzymes that exist in nature such as soil or sea, It can be produced by dealcoholization polycondensation of an acid alkyl ester, desalting polycondensation of glycolate, or the like. Polyglycolic acid has superior heat resistance, gas barrier properties, and mechanical strength compared to other biodegradable polymer materials such as aliphatic polyesters, and thus is widely used as a sheet, film, container, injection molded article, and medical material.

Polycaprolactone (PCL) is a type of linear aliphatic polyester produced by ring-opening polymerization of ε-caprolactone. In general, it has relatively excellent mechanical strength at molecular weights of 50,000 or more and has a low melting point of 60°C, making it easy to handle. It is a biodegradable polymer. In addition, compared to other biodegradable polymers, it is relatively economical and non-toxic, so it is widely used in various fields. In particular, since the compatibility with other polymers is excellent, the degradability can be controlled through polymerization or synthesis with various other polymers, and for example, the biodegradability can be improved by forming copolymerization with lactide and glycolide, It can also be mixed with silica to improve strength.

Polytrimethylene carbonate (PTMC) is a biodegradable polymer with a hydrophobic polymer block, and has excellent flexibility compared to other biodegradable polymers due to its low glass transition temperature. , the hardness can be adjusted.

Polylactic-co-glycolic acid (PLGA) has high mechanical properties and biostability, and can be processed by mixing with other biodegradable polymers because the biodegradability period can be controlled by controlling the amount of monomers. there is.

Since polybutylene adipate-co-terephthalate (PBAT) has a slow cooling rate and high flexibility, it can be mixed with the biodegradable polymer to improve the flexibility of the composition.

In one embodiment, the biodegradable polymer may include two or more biodegradable polymers, for example, may include polytrimethylene carbonate and polylactic acid-co-glycolic acid.

Specifically, the composition for preparing the seaweed aquaculture network may include about 10 to about 35 wt% of the polytrimethylene carbonate and about 10 to about 35 wt% of polylactic acid-co-glycolic acid. If, in the composition for producing a seaweed aquaculture net, the polytrimethylene carbonate is included in an amount of less than about 10% by weight or the polylactic acid-co-glycolic acid is included in an amount of more than about 35% by weight, the flexibility compared to the mechanical strength of the aquaculture net to be manufactured later And the elastic strength is low and can be easily broken, and when the polytrimethylene carbonate is included in excess of about 35% by weight or the polylactic acid-co-glycolic acid is included in less than about 10% by weight, the mechanical properties are low, and the function as a culture net may not be able to perform.

In one embodiment, the composition for preparing a seaweed culture net may further include a compatibilizer so that the biodegradable polymer polytrimethylene carbonate and polylactic acid-co-glycolic acid can be easily mixed with each other. The compatibilizer may be a blend in which the biodegradable polymer is chain-exchanged with amino alcohol. Chain exchange means at least one selected from a transesterification reaction and a transamidation reaction.

At this time, the amino alcohol may be at least one selected from the group consisting of C ₁ to C ₈ amino alcohol. Specifically, amino alcohol is C ₁ of methanolamine (Methanolamine), C ₂ of ethanolamine (Ethanolamine, Monoethanolamine, 2-Aminoethanol, hereinafter referred to as MEA), C ₃ of methylethanolamine (N-methylethanolamine) and 1-amino -2-propanol (1-amino-2-propanol), and C ₄ 4-amino-1-butanol (4-Amino-1-butanol), C ₅ 5-amino-1-pentanol (5-Amino -1-Pentanol), C ₆ 6-amino-1-hexanol (6-Amino-1-hexanol), C ₇ 7-amino-1-heptanol (7-Amino-1-heptanol), C ₈ of 8-amino-1-octanol (8-amino-1-octanol) and at least one selected from the group consisting of heptaminol (Heptaminol) may be used.

In one embodiment, the compatibilizer may be included in an amount of about 1 to about 10% by weight. If the compatibilizer is included in an amount of less than about 1% by weight, the effect of improving the compatibility between the biodegradable polymers may not be sufficiently exhibited. .

In one embodiment, as a component of the composition for preparing the seaweed aquaculture network, the organic solvent may be used without limitation as long as it can dissolve the biodegradable polymer. For example, the organic solvent is methanol, ethanol, propanol, isopropanol, butanol, methylene chloride, acetone, methyl ethyl ketone, toluene, benzene, xylene, naphtha. It may include one or more selected from the group consisting of cyclic polysiloxane, and combinations thereof, and specifically may include methylene chloride.

In one embodiment, the organic solvent may be included in an amount of about 10 to about 65% by weight. If the organic solvent is included in an amount of less than about 10% by weight, it may not be possible to sufficiently dissolve and mix the components included in the composition for preparing the seaweed aquaculture net, and if it exceeds about 65% by weight, it may function as a culture net. It may not be able to show the mechanical strength to that extent.

In one embodiment, the composition for producing a seaweed culture net may further include sodium caseinate (sodium caseinate). The sodium caseinate (sodium caseinate) is a compound in which sodium is bound to increase water solubility in casein protein obtained through alkali treatment from crude oil. The sodium caseinate is manufactured from a natural material and is not only environmentally friendly, but also can exhibit biodegradability, and can control the biodegradation period by giving flexibility.

In one embodiment, the sodium caseinate may be included in about 0.1 to about 3% by weight. If the sodium caseinate is included in less than about 0.1% by weight, the effect that appears according to the inclusion of sodium caseinate may not be sufficiently exhibited, and if it exceeds about 3% by weight, enough to function as a culture net may not show the mechanical strength of

In one embodiment, the composition for producing a seaweed aquaculture network may further include talc. The talc is a rock of brittle nature containing magnesium as a main component, and may be included to improve the mechanical properties of the produced aquaculture net to improve durability and chemical resistance. In one embodiment, it is preferable to use talc powder having a particle size of about 150 to about 200 mesh for the talc to be mixed.

In one embodiment, the talc powder may be included in an amount of about 0.1 to about 3% by weight based on the total composition for preparing the seaweed aquaculture network. If the talc powder is included in an amount of less than about 0.1% by weight, durability and chemical resistance are improved The effect may be insignificant, and when it is included in excess of about 3% by weight, workability may decrease when manufacturing aquaculture nets using the composition.

In one embodiment, the composition for preparing a seaweed culture net may further include a mussel adhesive protein to improve the mixability between the components included in the composition. The mussel adhesion protein is a highly viscous adhesion protein derived from mussels, for example, Mytilus edulis, Mytilus galloprovincialis, or Mytilus corus. mussel adhesion protein derived from Mytilus coruscus or a variant thereof.

In one embodiment, the mussel adhesive protein may be included in an amount of about 0.1 to about 3% by weight. If the mussel adhesive protein is included in an amount of less than about 0.1% by weight, the effect of including the mussel adhesive protein may not be sufficiently exhibited, and if it exceeds about 3% by weight, miscibility with other components may be inhibited. there is.

In one embodiment, the composition for producing a seaweed culture net may exhibit excellent mechanical strength and deodorizing effect by additionally including tourmaline powder.

In one embodiment, the tourmaline powder may be pulverized to have a particle diameter of about 1,000 to about 3,000 mesh. When the particle diameter of the tourmaline powder is less than about 1,000 mesh, the deodorizing effect may be reduced, and if the particle diameter of the tourmaline powder exceeds about 3,000 mesh, miscibility with other components may be inhibited, so the tourmaline powder is about 1,000 It is preferred that the pulverized to have a particle size of about 3,000 mesh.

In one embodiment, the tourmaline powder may be included in an amount of about 0.01 to about 3 wt%. If the tourmaline powder is included in an amount of less than about 0.01 wt%, the mechanical strength improvement and deodorization effect caused by the inclusion of the tourmaline powder may not be sufficiently exhibited. Mixability may be impaired.

Hereinafter, the configuration of the present invention and its effects will be described in more detail through specific examples and comparative examples. However, these examples are for explaining the present invention in more detail, and the scope of the present invention is not limited to these examples.

[Examples 1 to 3]

A composition for producing a seaweed culture net was prepared by mixing the components shown in Table 1 below, and the seaweed culture net was prepared using a net obtained by putting the prepared composition into a spinning machine and spinning it. According to the weight ratio of each component of the composition for producing aquaculture nets, the prepared seaweed cultured nets were named Examples 1, 2, and 3, respectively.

Composition of composition for manufacturing seaweed aquaculture net (% by weight) Example 1 Example 2 Example 3 liquid fertilizer
(35% by weight of sagebrush powder, 60% by weight of mineral concentrated water, 5% by weight of proteolytic enzyme) 10.00 10.00 10.00 polytrimethylene carbonate 20.00 17.50 17.00 polylactic acid-co-glycolic acid 20.00 17.50 17.00 Ethanolamine (MEA) 2.50 2.50 2.50 methylene chloride 47.50 48.00 47.50 Sodium Caseinate - 2.00 1.75 Talc powder (200 mesh) - - 1.50 mussel adhesion protein - 2.50 2.50 Tourmaline powder (1200 mesh) - - 0.25 Sum 100.00 100.00 100.00

[Comparative example]

A seaweed culture net was prepared using commercially available polypropylene synthetic fibers, and this was named as a seaweed culture net of Comparative Example.

[Experimental Example 1: Measurement of mechanical properties]

For each of the seaweed culture nets using the compositions for preparing seaweed culture nets of Examples 1 to 3 and Comparative Examples, tensile strength was measured in accordance with ASTM D 683, and the results are shown in Table 2 below.

[Experimental Example 2: Flexibility Measurement]

For each of the seaweed culture nets using the compositions for preparing seaweed culture nets of Examples 1 to 3 and Comparative Examples, the flexural modulus (flexibility) was measured in accordance with ASTM D-790, and the results are shown in Table 2 below.

[Experimental Example 3: Measurement of biodegradability]

For each of the seaweed cultured nets using the composition for preparing seaweed cultured nets of Examples 1 to 3 and Comparative Examples, the weight reduction rate was measured by allowing them to stand for 90 days under standard conditions at a humidity of 65% and a temperature of 21°C. The measurement results are shown in Table 2 below.

tensile strength
(Kg/cm ² ) flexural modulus
(Kg/cm ² ) biodegradable
(weight reduction rate, %) Example 1 648 4,051 48.2 Example 2 658 4,862 52.8 Example 3 671 5,609 58.6 comparative example 651 1,201 21.9

As shown in Table 2, in the case of the comparative example, the tensile strength was similar to that of the example, but showed a very low flexural modulus result. This means the possibility of being easily separated or ruptured when using aquaculture nets due to a very low flexural modulus compared to tensile strength.

On the other hand, in the case of the composition for producing a seaweed culture net of Examples 1 to 3 according to the present invention, high tensile strength and a high flexural modulus were exhibited, which had high mechanical strength and high flexibility, even when used as a culture net. It does not break, which means that usability can be improved.

In addition to the physical property test, it was confirmed that the culture net using the composition for preparing a seaweed culture net according to the present invention exhibited a higher degree of biodegradation compared to the comparative example.

In summary, when the composition for manufacturing a seaweed aquaculture net according to the present invention is used, it has high mechanical strength, high flexural modulus compared to mechanical strength, and biodegradability, so that it can be used in aquaculture nets for fishing that require high modulus of elasticity in addition to mechanical strength, It means that even if it is lost after use or during use, it can be naturally decomposed and used in an environmentally friendly manner.

In this specification, only a few examples among the various embodiments performed by the present inventors will be described, but the technical spirit of the present invention is not limited or limited thereto, and it is of course that it may be modified and implemented in various ways by those skilled in the art.

Claims (3)

1 to 10% by weight of liquid fertilizer;
10 to 35% by weight of polytrimethylene carbonate;
10 to 35% by weight of polylactic acid-co-glycolic acid;
1 to 10% by weight of ethanolamine;
10 to 65% by weight of methylene chloride;
0.1 to 3% by weight of sodium caseinate; and
0.1 to 3% by weight of mussel adhesive protein;
A composition for preparing a seaweed culture net comprising:
The liquid fertilizer is
It is characterized in that it is prepared by mixing 35% by weight of sagebrush powder, 60% by weight of mineral concentrated water, and 5% by weight of proteolytic enzyme,
A composition for manufacturing a seaweed culture net. delete delete