KR101774266B1 - Biodegradable polymer compositions using a waste fishing net and fish trap produced therefrom - Google Patents

Abstract

The present invention relates to a naturally degradable polymer composition for fishes using a closed network, and a fish manufactured from the fish nets. The present invention relates to a naturally degradable polymer composition for fishing, The present invention relates to a naturally degradable polymer composition for fishes using a closed net that can control biodegradability within 6 months to 5 years as well as biodegradability and a fish prepared from the composition. The spontaneously decomposing polymer composition for fishing using a closed net includes 40 to 70% by weight of closed net pellets; 20 to 40% by weight of a polybutylene succinate or polybutylene succinate / polybutylene adipate terephthalate polymer as a novel biodegradable polymer; 1 to 15% by weight of a spontaneous decomposition catalyst; And 1 to 5% by weight of barium sulfate.

Description

TECHNICAL FIELD [0001] The present invention relates to a natural degradable polymer composition for fishes using a closed fish net, and a fish meal prepared from the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a spontaneous degradable polymer composition for fishing and a fishing goggle produced therefrom, and more particularly, to a fishing net pellet composition for fishing, which comprises a fish net pellet, a novel biodegradable polymer, a natural decomposition catalyst and barium sulfate, The present invention relates to a naturally degradable polymer composition for fishes using a closed network capable of controlling the biodegradability within a range of 6 months to 5 years based on excellent biodegradability in the environment and a fish prepared from the composition.

In recent years, problems have arisen with regard to loss of useful biological resources by ghost fishing caused by lost fishing nets, water pollution caused by dead fishes that are caught in a closed nose, and destruction of marine ecosystems.

In particular, among fish, fishing nets have a considerable amount to be lost in water. As the scale of fisheries in the world grows larger, the degradable synthetic polymer is used as a raw material for the purpose of improving durability. The damage caused by ghost fishing due to fishing loses due to the loss of anchor or other obstacles or due to competition with other fishing vessels is almost permanently occurring.

Although the government is working to collect fishing nets that have been neglected in the water, the number of fishing gears collected in comparison to the enormous budget is still insufficient, and the collected fishing net is also corrupted by various pollutants and decayed for a long time. Which can not be easily handled as it is accelerated.

Accordingly, there is a need for a method for recycling and processing the collected abandoned net while fundamentally solving the problem of the abandoned net. In order to solve such a problem, a biodegradable aliphatic polyester resin composition, Methods have been known.

However, since the above-mentioned invention does not disclose a resin composition capable of controlling the decomposition period, it has a disadvantage in that it is not applicable to various product groups, and does not completely solve the problems of conventional phrases which are disassembled in a relatively short period of time.

Patent Registration No. 10-0415812

The present invention aims to solve the environmental problem by establishing a method for recycling the collected closed net, and by using it as a raw material of the natural degradable fishing gear, it is possible to control the decomposition period of the fishing net within 6 to 5 years It is another object of the present invention to provide a natural decomposable polymer composition for fishes using a closed net that can be supplied at low cost to a wide variety of product groups and lead to generalization of distribution, and a fishfood manufactured therefrom.

According to a preferred embodiment of the present invention, a spontaneous degradable polymer composition for fishing using a closed network comprises: a) collecting and preparing a closed net; b) removing foreign matter from the closed network; c) removing the odor generated from the abandoned speech by a chemical treatment method; d) cutting and compressing the closed network; e) cleaning the closed network; f) drying the scourge; And g) pelleting the dried waste net using a pellet mill; 40 to 70% by weight of waste net pellets prepared from; 20 to 40% by weight of a polybutylene succinate or polybutylene succinate / polybutylene adipate terephthalate polymer as a novel biodegradable polymer; 1 to 15% by weight of a spontaneous decomposition catalyst; And 1 to 5% by weight of barium sulphate, wherein the natural decomposition catalyst comprises 10 to 30% by weight of the jute pellets powder; 0.05 to 0.6 wt% of wax; 1 to 2% by weight of a sodium-based plasticizer; 0.5 to 2% by weight of an organic oxidation initiator; 0.01 to 1% by weight peroxide; 1 to 5% by weight of a metal ion salt; 1 to 2% by weight of a thermal decomposition initiator; 0.5 to 2% by weight of organic acid; 40 to 82% by weight of a binder polymer; Wherein the sodium plasticizer is selected from the group consisting of sodium metasilicate (Na ₂ SiO ₃ ) and sodium borate decahydrate (Na ₂ B ₄ O ₇ .10H ₂ O); And the organic ionic initiator is at least one selected from the group consisting of C18-based alpha-linolenic acid (ALA), gamma -linolenic acid (GLA), and mixtures thereof, wherein the metal ion salt is at least one selected from the group consisting of Nickelous Acetate Manganic acetate, Manganous oxalate, Cobaltous acetate, Cobaltic acetate, Oxalic acid, Manganic acid, Manganese acetate, Manganese acetate, At least one selected from the group consisting of Cobaltous oxalate, Ferric formate and Ferrous lactate, and the pyrolysis initiator is at least one selected from the group consisting of azobenzene, methyl red, 2,2'-azobisisobutyronitrile , Bismarck Brown, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride, 1,1'-azobis (cyclohexane carbonate Azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (N, N-dimethylformamide) and 2,2'- And the organic acid is at least one selected from the group consisting of propionic acid, p-nitrilobenzoic acid, citric acid, malic acid and maleic acid, and the decomposition assist accelerator is a mixture of calcium carbonate and talc.

According to another preferred embodiment of the present invention, the spontaneously decomposing polymer composition for fishing using the closed network further comprises a redox initiator, and the redox initiator is selected from the group consisting of ammonium persulfate (APS), potassium persulfate (PPS) and cumene hydroperoxide ≪ / RTI >

According to another preferred embodiment of the present invention, the fish-spontaneously decomposing polymer composition for fishing using a closed net further comprises at least one selected from the group consisting of a primary antioxidant, a secondary antioxidant and a yellowing-preventing antioxidant as antioxidants, The primary antioxidant is tetraquismeethylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane, octadecyl 3- (3'5'-di- Ethylidenebis [4,6-di-t-butylphenol], 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6 Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -thione, triethylene glycol bis [3- -Methylphenyl) propionate] and N, N'-hexamethylenebis [3- (3,5-di-thi-butyl-4-hydroxyphenyl) propionamide] The antioxidant is tris (2,4-di-t-butyl ), And phosphite, an antioxidant for preventing yellowing is a thioester-thiodipropionate (thioester thiodipropionate).

According to another preferred embodiment of the present invention, the weight ratio of the polybutylene succinate / polybutylene adipate terephthalate polymer in the spontaneously decomposing polymer composition for fishing using the closed network is 99/1, 95/5 or 90/10 to be.

According to another preferred embodiment of the present invention, the fish according to the present invention is prepared from the natural degradable polymer composition for fishing using the fish net.

The natural decomposing polymer composition for fishes using the closed network according to the present invention solves the problems of odor and space utilization caused by the closed fishing net by using the collected closed net as a raw material, , And to make it possible to solve the environmental problems in the long term by establishing a continuous use network.

The natural decomposition catalyst contained in the natural decomposing polymer composition for fishing using the closed net according to the present invention shows superior oxidative biodegradability even in a small amount of use. Therefore, it is possible to control the physical properties of the biodegradable polymer which has been excessively used for imparting biodegradability And solve the problem of rising raw material costs.

The natural degradable polymer composition for fishes using the closed network according to the present invention has an advantage that it can be applied to various product groups since the oxidative biodegradation period can be controlled within a range of 6 months to 5 years.

The sodium-based plasticizer included in the natural decomposition catalyst according to the present invention can enhance the decomposition of the resin by substituting the lignin contained in the lignin, and mask the dark color due to lignin.

The thermal decomposition initiator included in the natural decomposition catalyst according to the present invention can easily control the biodegradability of the product according to the present invention at a specific temperature condition by using an azo compound.

The metal ion salt having iron divalent ions and iron trivalent ions contained in the natural decomposition catalyst according to the present invention may react with a redox initiator, an organic acid, and a hydroperoxide to promote a radical reaction, thereby improving biodegradability.

The crude saponin contained in the natural decomposition catalyst according to the present invention has the advantage of being capable of coping with international environmental regulations while promoting carbon reduction effect, carbon neutralization and decomposition of resin, thereby reducing environmental burden.

The barium sulphate contained in the natural degradable polymer composition for fishing using the abandoned net according to the present invention allows the fish manufactured by the high specific gravity property to be dropped into water in a short time, thereby facilitating the fishing operation.

The fish manufactured from the natural degradable polymer composition for fishing using the closed net according to the present invention can reduce the supply cost due to the reduction of the raw material cost by reducing the use of the new polymer according to the use of the closed network, So that it can be activated.

Closed speech  Process for producing pellets

The closed net pellet according to the present invention comprises:

a) collecting and preparing a closed network;

b) removing foreign matter from the closed network;

c) removing the odor generated from the abandoned speech by a chemical treatment method;

d) cutting and compressing the closed network;

e) cleaning the closed network;

f) drying the scourge; And

g) pelletizing the dried waste net using a pellet forming machine.

The step a) may be carried out after the disposal of the fishing nets or in the offshore waters or in the offshore waters to remove the sinking or drifting nets, thereby producing polybutylene succinate, polybutylene adipate terephthalate and polybutylene succinate / And a pale terephthalate polymer is classified and collected.

In the present invention, in order to solve the environmental problem due to the closed network, the closed net pellet is used for the production of a biodegradable fishing net, in order to reduce the cost of raw materials by using polybutylene succinate and polybutylene adipate terephthalate, The closed net collected in the present invention is not limited to the fishing net but includes at least one of polybutylene succinate, polybutylene adipate terephthalate and polybutylene succinate / polybutylene adipate terephthalate polymer It should be understood that the phrase or wastes involved may be applied.

The step b) is a step of removing a relatively large unit of foreign matter such as seaweeds, fish and shellfish, various marine litter, and municipal wastes, which are caught in a closed network.

The step c) is a step of deodorizing various seaweeds, fish and shellfish, etc. by a chemical treatment method to effectively remove odors generated from various causes such as decaying or leachate water generated from long-term wastes, It is preferable that the non-toxic inorganic minerals having strong basicity are applied to the closed network through a spraying system such as a high-pressure nozzle. Inorganic minerals applied to scarce nets emit strong far infrared rays and negative ions at room temperature, and they have antimicrobial and antiviral effects and major odor substances such as hydrogen sulfide, ammonia trimethylamine, Methyl mercaptan and so on to exhibit strong deodorizing effect.

The step d) is a step of cutting the closed speech network deactivated from the step c) to a predetermined size in order to increase the processing efficiency during loading, transportation and processing of the closed speech network. The deodorized closed network may be cut into a predetermined size by a cutter formed on an inner surface of the chamber or a discharge port in the process of being pushed into the inlet formed at the upper portion of the chamber and being pushed by the rotation of the screw in the chamber, By cutting to 30 mm, the treatment efficiency can be maximized.

The step (e) is a step of completely removing foreign substances in a small unit in order to improve the purity of the pellet produced in the pelletizing step of the closed network to be described later, and is performed by spraying air or washing water through a high-pressure nozzle .

The step (f) is a step of removing water remaining in the closed network. The step (e) is a step of extending the injection time of the high-pressure air in the step (e), or an additional drying method such as hot air drying or vacuum drying, Can be removed. It is preferable that the moisture content (%) of the dried scissors is 0 to 0.02%. However, since the moisture content in dried scissors due to moisture adsorption in the air may increase again, the moisture percentage (%) of dried scissors dried from step f) Is preferably 0 to 0.01%.

The step g) is a step of pelletizing the closed net that has been dried from the step f) by using a known pellet molding machine. The closed net is put into the chamber of the molding machine having a temperature condition of 125 to 140 캜, After the kneaded mixture is cooled, a pellet having a diameter of 15 mm or less and a length of 50 mm or less can be obtained through a cutting device.

I can not wait.  Used fishing gear Natural degradability  Polymer composition

The naturally degradable polymer composition for fishing use of the present invention,

From 40 to 70% by weight of closed net pellets prepared from steps a) to g);

20 to 40% by weight of a polybutylene succinate or polybutylene succinate / polybutylene adipate terephthalate polymer as a novel biodegradable polymer;

1 to 15% by weight of a spontaneous decomposition catalyst; And

And 1 to 5% by weight of barium sulfate.

Wherein the closed net pellet comprises at least one of polybutylene succinate, polybutylene adipate terephthalate, and polybutylene succinate / polybutylene adipate terephthalate polymer, wherein the ratio of the total weight of the spontaneous degradable polymer composition By using 40 to 70% by weight, the cost-saving effect of purchasing the expensive polybutylene succinate and the polybutylene adipate terephthalate can be reduced, and the continuous production of the naturally degradable polymer composition according to the present invention and the reasonable supply Thereby facilitating the distribution activation of the fish manufactured from the present invention.

The novel biodegradable polymer is a polymer of polybutylene succinate or polybutylene succinate / polybutylene adipate terephthalate, and is used in an amount of 20 to 40% by weight based on the total weight of the naturally degradable polymer composition, The control of biodegradation performance and the improvement of properties such as strength and elongation according to the content of polybutylene succinate, polybutylene adipate terephthalate, polybutylene succinate / polybutylene adipate terephthalate polymer or refractory synthetic polymer .

The natural decomposition catalyst is a catalyst for promoting oxidative biodegradation of a polymer, and is preferably used in an amount of 1 to 15% by weight based on the total weight of the natural decomposable polymer composition. If it is used out of the above range, it is difficult to realize the biodegradability suitable for the fishery by excessively lengthening or shortening the decomposition period of the polymer.

Due to the high specific gravity property of barium sulfate (BaSO ₄ ) of 4.5, the fish prepared from the naturally degradable polymer composition can sink at high speed in a seawater environment, thereby enabling a stable fishing operation. The barium sulfate is preferably used in an amount of 1 to 5 wt% based on the total weight of the naturally decomposable polymer composition.

Natural decomposition catalyst

The natural decomposition catalyst according to the present invention comprises

10 to 30% by weight of the haze powder;

0.05 to 0.6 wt% of wax;

1 to 2% by weight of a sodium-based plasticizer;

0.5 to 2% by weight of an organic oxidation initiator;

1 to 5% by weight of a metal ion salt;

0.01 to 1% by weight peroxide;

0.5 to 2% by weight of organic acid;

1 to 2% by weight of a thermal decomposition initiator;

40 to 82% by weight of a binder polymer;

1 to 30% by weight of a decomposition assist accelerator,

The sodium plasticizer is at least one selected from the group consisting of sodium metasilicate (Na ₂ SiO ₃ ) and sodium borate decahydrate (Na ₂ B ₄ O ₇ .10H ₂ O)

The metal ion salt may be at least one selected from the group consisting of nickel nickel acetate, nickel oxalate, manganous acetate, manganic acetate, manganous oxalate, cobaltous acetate ), At least one selected from the group consisting of Cobaltic acetate, Cobaltous oxalate, Ferric formate and Ferrous lactate,

The pyrolysis initiator may be azobenzene, methyl red, 2,2'-azobisisobutyronitrile, Bismarck Brown, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (Aminodipropane) dihydrochloride, 1,1'-azobis (cyclohexane carbonitrile), 1,1'-azobis (N, N-dimethylformamide) and 2,2'-azobis -Methoxy-2,4-dimethylvaleronitrile). ≪ / RTI >

The haze powder is used in an amount of 10 to 30% by weight based on the total weight of the natural decomposition catalyst. Pine nuts have the advantage of drying process by having the relatively low water content of 6.13% compared with other biomass. However, the drying process can be further performed in consideration of the increased moisture content of the papermaking due to external environmental factors, and the drying process is performed in a drying apparatus equipped with a temperature condition of 90 to 110 캜 for 30 minutes by a hot air drying method It is possible to obtain a seed having a water content of 6% or less which is advantageous for the processing process. The dried pellets are preferably milled at a particle size of 380 to 450 mesh so as to be uniformly blended with the raw materials constituting the natural decomposition catalyst and to improve the flowability and to be extruded into filaments for the production of a fishing net. The hazelnut powder which is dried in the invention and ground to a particle size of 380 to 450 mesh is referred to as hazelnut powder.

The wax may be used in such a manner that the surface of the cookie is coated with the wax in order to prevent the water from being absorbed by the bark powder of the dried sesame seed powder. Preferably, paraffin wax, liquid paraffin wax, beeswax, emulsion wax, candelilla wax , Polyethylene wax and polypropylene wax may be used. Further, wax can be advantageously used in the present invention because it can serve as an auxiliary agent for the lubricant, and has an advantage of easy biodegradation due to a low molecular weight structure. The wax is preferably used in an amount of 0.05 to 0.6% by weight based on the total weight of the natural decomposition catalyst for its role as a coating function and a lubricant assistant.

The plasticizer can be used for plasticizing the wax-coated hazelnut powder, and in addition, a sodium-based plasticizer can be used to mask the dark color caused by lignin while increasing the degradability by replacing the lignin of the wax. Sodium-based plasticizer sodium bisulfite (sodium hydrogensulfite, NaHSO _3), and sodium carbonate _{(sodium percarbonate, 2Na 2 CO 3} · 3H 2 O 2), bicarbonate (sodium bicarbonate, NaHCO _3), sodium chloride (sodium chloride, NaCl) , Sodium sulphate (Na ₂ SiO ₃ ), sodium borate sodium decahydrate (Na ₂ B ₄ O ₇ .10H ₂ O), and soda ash (Na ₂ CO ₃ ) (Na ₂ SiO ₃ ), sodium borate decahydrate (Na ₂ B ₄ O ₇ .10H ₂ O), or a mixture thereof (eg, a weight ratio of 3: 7 to 7: 3, more specifically 5: 5 By weight) is preferably used. The sodium-based plasticizer may be used in an amount of 1 to 2% by weight based on the total weight of the natural decomposition catalyst for the plasticization of the wax-coated Iztagis powder and the oxidizing effect of the polymer. If the amount exceeds 2% by weight, Carbonization or deterioration of physical properties may occur.

The organic oxidation initiator can be used to accelerate the decomposition reaction of the resin, and a natural polyunsaturated fatty acid having an active methylene group can be preferably used. The active methylene group formed on the polyunsaturated fatty acid can be oxidized automatically by catalytic action such as light or heat, and then cause degradation of the lipid, thereby promoting oxidative decomposition of the resin. Such an organic oxidation initiator may advantageously have a low molecular weight structure for the purpose of improving the decomposability and may be a C18-based alpha-linolenic acid (ALA), gamma-linolenic acid (GLA) , A weight ratio of 4: 6 to 6: 4, more specifically, a weight ratio of 5: 5) is preferably used. The organic oxidation initiator is preferably used in an amount of 0.5 to 2% by weight based on the total weight of the natural decomposition catalyst. If the organic oxidation initiator is used in an amount of less than 0.5% by weight, the degradation effect becomes insufficient. With the rise, too much oxidation can be caused.

The metal ion salt can be used to initiate a radical reaction by energy generated by repeated oxidation-reduction reactions with peroxides described below. By this reaction, the polymer carbon chain is cleaved and an oxidative decomposition action occurs, so that the polymer can be made low molecular weight. The low molecular weight oxidized low molecular weight material is finally decomposed and absorbed by the microorganisms in the natural environment and converted into water and carbon dioxide, and the decomposition can be completed. The metal ion salts according to the present invention are preferably selected from the group consisting of nickel acetylacetate, nickel oxalate, manganous acetate, manganic acetate, manganous oxalate, It may be at least one selected from the group consisting of Cobaltous acetate, Cobaltic acetate, Cobaltous oxalate, Ferric formate and Ferrous lactate. The metal ion salt is preferably used in an amount of 1 to 5% by weight based on the total weight of the natural decomposition catalyst, and when it is used in an amount of less than 1% by weight, the effect of oxidative decomposition of the resin is insufficient. Resulting in an increase in manufacturing cost.

The peroxide can be used for activating the radical reaction by energy generated by the oxidation-reduction reaction with the metal ion salt, and can be further used for the grafting of the plasticized sesame seed powder and a binder polymer to be described later. The peroxide may be selected from the group consisting of azo-bis-isobutylonitrile, tributyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, di-tributyl peroxide, 2,5 dimethyl-2,5-di (t- butylperoxy) And 1,3-bis (t-butylperoxy-isopropyl) benzene, peroxide is preferably used in an amount of 0.01 to 1% by weight based on the total weight of the natural decomposition catalyst. If it is used in an amount of less than 0.01% by weight, it may be difficult to expect a graft-linking effect with the polymer because the resin macromolecule end groups are less likely to be produced, or the natural decomposition and oxidizing effect of the resin may be decreased, If it is used in excess of 1% by weight, it can be decomposed too early.

The organic acid may be used to induce crosslinking between the plasticized sesame seed powder and a binder polymer to be described later and to accelerate the decomposition of the polymer by reacting with metal ions. The organic acid according to the present invention is preferably selected from the group consisting of propionic acid, Citric acid, malic acid, and maleic acid. The organic acid is preferably used in an amount of 0.5 to 2% by weight based on the total weight of the natural decomposition catalyst, and when it is used in an amount of less than 0.5% by weight, the oxidative decomposition function of the resin is poor. It can invite a rise.

The azo compound is preferably used as a thermal decomposition initiator in the present invention by causing both radicals of the azo group (-N = N-) to be decomposed by heating to form two radicals to initiate a radical initiation reaction. As thermal decomposition initiators, azobenzene, methyl red, 2,2'-azobisisobutyronitrile, Bismarck Brown, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (Aminodipropane) dihydrochloride, 1,1'-azobis (cyclohexane carbonitrile), 1,1'-azobis (N, N-dimethylformamide) and 2,2'-azobis -Methoxy-2,4-dimethylvaleronitrile), and is preferably used in an amount of 1 to 2% by weight based on the total weight of the natural decomposition catalyst.

The binder polymer is selected from the group consisting of polyethylene (PE), linear low-density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), ethylene vinyl acetate (EVA), polyvinyl alcohol (PVA), polypropylene PLA) and polyhydroxybutyrate (PHB), and is preferably used in an amount of 40 to 82% by weight based on the total weight of the natural decomposition catalyst. If it is used in an amount less than 82% by weight, the bonding strength with the compounding raw material may be weakened, and if it is used in excess of 82% by weight, the oxidative biodegradation function of the resin may be deteriorated.

Minerals can be used as the decomposition assist accelerator, and such minerals can contribute to improvement in durability of a fish meal prepared from the naturally degradable polymer composition according to the present invention. As the decomposition assist accelerator according to the present invention, a mixture of calcium carbonate and talc (for example, mixed at a weight ratio of 1: 6 to 6: 1) may be used, and a mixture of calcium carbonate and talc may be imparted with translucency I have. The decomposition assist accelerator is used in an amount of 1 to 30% by weight based on the total weight of the natural decomposition catalyst.

The natural decomposition catalyst according to the present invention may further comprise a redox initiator.

As redox initiators, persulfate-based initiators and hydroperoxide-based initiators may be used. As the persulfate-based initiator, ammonium persulfate (APS), potassium persulfate (PPS) may be used, and ammonium persulfate may be used alone or in combination with a reducing agent such as ammonium bisulfite, sodium metabisulfite As the hydroperoxide-series initiator, cumene hydroperoxide can be preferably used. The redox initiator is preferably used in an amount of 1 to 2% by weight based on the total weight of the natural decomposition catalyst.

The natural decomposition catalyst according to the present invention may further comprise an antioxidant.

The antioxidant may be used to retard deterioration of the product due to premature oxidative decomposition of the resin, oxidative decomposition, yellowing, etc. Depending on the purpose, one selected from the group consisting of primary antioxidants, secondary antioxidants and antioxidants for preventing yellowing Or more can be used. The primary antioxidant can be used to stabilize the resin by capturing the radicals. Particularly, the phenolic primary antioxidant is not only inexpensive, but also has antioxidant functions due to maximization of resonance effect and electron induction effect. . In the present invention, as a primary antioxidant, tetrakis methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane, octadecyl 3- (3'5'-di- 4'-hydroxyphenyl) propionate, 2,2'-ethylidenebis [4,6-di-t-butylphenol], 1,3,5-tris (1H, 3H, 5H) -triene, triethylene glycol bis [3- (3-thiobutyl) -4,5- Methylphenyl) propionate] and N, N'-hexamethylenebis [3- (3,5-di-thi-butyl-4-hydroxyphenyl) propionamide] Or more can be used. As the secondary antioxidant, a phosphite-based secondary antioxidant such as tris (2,4-di-t-butylphenyl) phosphite may be preferably used, and the phosphite-based secondary antioxidant may have a function of releasing peroxide And has an advantage of excellent heat resistance, processability and coloring prevention effect. The antioxidant for preventing yellowing can prevent sulfur change caused by oxidation by oxygen in the air to maintain the inherent physical properties of the resin, and preferably thioester thiodipropionate can be used. The antioxidant is preferably used in an amount of 0.5 to 5 wt% based on the total weight of the natural decomposition catalyst, and when it is used in an amount of less than 0.5 wt%, it is difficult to prevent oxidation, yellowing, The period can be extended too much.

The present invention relates to a closed net pellet; New biodegradable polymers; A natural decomposition catalyst and a barium sulphate can be added to an extruder to produce a primary molded product such as a pellet or a chip for radial processing to obtain a monofilament or directly spin to obtain a monofilament. The obtained monofilaments can be applied to a catch net, a crab catch net and a conger eel trap by being manufactured as a fishing net by a flattening machine, and the obtained filament is not limited to a fishing net but is manufactured by an injection molding method, The present invention can be applied to various forms of phrases.

[Example]

Example  One

Dried fish net with a moisture content of 0.005% was put into a pellet molding machine equipped with a temperature condition of 125 to 140 캜 and then melt-kneaded for 30 minutes to obtain a closed-pellet pellet having a diameter of 10 mm and a length of 20 mm. 55% by weight of the obtained pellets, 60% by weight of fresh polybutylene succinate, 8% by weight of a natural decomposition catalyst and 2% by weight of barium sulfate were placed in a reactor equipped with a temperature condition of 150 to 170 ° C to prepare a melt, To prepare a specimen having an average particle size of 10 mm.

At this time, as the natural decomposition catalyst, 15 wt% 0.25% by weight of polyethylene wax; 1.2% by weight of a mixture of sodium metasilicate and sodium borate decahydrate mixed at a weight ratio of 5: 5; 1% by weight of a mixture of alpha linolenic acid and gamma linolenic acid mixed at a weight ratio of 5: 5; 2.5% by weight of ferric formate and ferric lactate mixed in a weight ratio of 5: 5; 0.05% by weight of 1,3-bis (t-butylperoxy-isopropyl) benzene; 1% by weight of propionic acid; 1.5% by weight of 2,2'-azobisisobutyronitrile; 1.5% by weight cumene hydroperoxide; And 76% by weight of polyethylene;

Example  2

A test piece was prepared in the same manner as in Example 1 except that 57 wt% of the pellets of the closed net, 40 wt% of the new polybutylene succinate, and 1 wt% of the natural decomposition catalyst were used.

Example  3

A specimen was prepared in the same manner as in Example 1 except that 50 wt% of the used pellets, 38 wt% of the new polybutylene succinate, and 10 wt% of the natural decomposition catalyst were used.

Example  4

A monofilament sample was prepared in the same manner as in Example 1 except that a melt of 0.285 mm in diameter was obtained by using a spinner before being crushed.

Example  5

A monofilament sample was prepared in the same manner as in Example 4, except that a new polybutylene succinate / polybutylene adipate terephthalate polymer having a weight ratio of 95/5 was used instead of the new polybutylene succinate. .

Example  6

Except that a new polybutylene succinate / polybutylene adipate terephthalate polymer having a weight ratio of 99/1 was used in place of the new polybutylene succinate, the monofilament sample was prepared in the same manner as in Example 4, .

Example  7

A monofilament sample was prepared in the same manner as in Example 4, except that a new polybutylene succinate / polybutylene adipate terephthalate polymer having a weight ratio of 90/10 was used instead of the new polybutylene succinate. .

[Comparative Example]

Comparative Example  One

A specimen was prepared in the same manner as in Example 2 except that 0.5 wt% of a spontaneous decomposition catalyst and 2.5 wt% of barium sulfate were used.

Evaluation of the biodegradation of the specimens and the monofilament samples according to the above-described Examples and Comparative Examples in the seawater environment and the evaluation of the properties of the strength and elongation were carried out as follows.

[Experimental Example]

(1) Evaluation of biodegradation in sea water environment

Carried out in accordance with ASTM D6691 with a mean particle diameter of 10 ㎜ Examples 1 to 3 and Comparative Example 1, the specimen 1 g, sea water 400 ㎖ and beach sand 100 g are put into each of four 5 L vessel prepared, within the CO ₂ container The emission was measured by measuring with a vessel PASCO IR detector. A bomb calorimeter was used to measure the initial carbon content of the specimen, and the mass of carbon in the released CO ₂ can be calculated by the following equation (1), and the biodegradability (% ) Are shown in Table 1 below. Cellulose powder was used as a control.

( Bomb calorimeter  Volume: 0.34 L)

As a result of the test, it was found that as the addition amount of the natural decomposition additive was increased, the oxidative biodegradation of the polymer was promoted and the CO ₂ emission was increased. The biodegradability of the standard material after 60 days was measured to be 10.01%, and the biodegradability after 60 days from Examples 1 to 3 and Comparative Example 1 was 20% or more of the standard material, cellulose. Based on the tendency of biodegradation after 60 days and 180 days, the time required for complete decomposition was about 2 years and 6 months for Example 1, 5 years for Example 2, 1 year for Example 3, and 5 years for Comparative Example 1 Of the total. Comparative Example 1 is not preferable because it takes a comparatively long time to complete decomposition, and is not preferable because it is applied to a fishing gear. In Examples 1 to 3, biodegradability after 60 days is relatively low, It is confirmed that the biodegradation within 5 years is suitable to apply to fish.

(2) Evaluation of strength and elongation

The strength and elongation of Examples 4 to 7 were measured using a constant-rate tensile tester in accordance with KS K 0412, and the results are shown in Table 2 below.

As a result of the test, it was found that the strength tended to decrease as the polymerization ratio of polybutylene adipate terephthalate increased, and it was confirmed that the polymer exhibited the highest strength in Example 4, which was not polymerized. It was confirmed that the monofilaments prepared from Examples 4 to 7 sufficiently satisfied the certification of the performance of a netting having a breaking strength of 4700 kgf / cm ² or more and an elongation of 25% or more at a diameter of 0.285 ± 0.01. And it was found that it has the best strength and elongation to be applied.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the scope of the present invention should be interpreted based on the scope of the following claims, and all technical ideas within the scope of the present invention should be interpreted as follows. It is to be understood that the invention is not limited thereto.

Claims (5)

a) collecting and preparing a closed network;
b) removing foreign matter from the closed network;
c) removing the odor generated from the abandoned speech by a chemical treatment method;
d) cutting and compressing the closed network;
e) cleaning the closed network;
f) drying the scourge; And
g) pelletizing the dried waste net using a pellet mill; 40 to 70% by weight of waste net pellets prepared from;
20 to 40% by weight of a polybutylene succinate or polybutylene succinate / polybutylene adipate terephthalate polymer as a novel biodegradable polymer;
1 to 15% by weight of a spontaneous decomposition catalyst; And
1 to 5% by weight of barium sulfate;
Wherein the natural decomposition catalyst comprises:
10 to 30% by weight of the haze powder;
0.05 to 0.6 wt% of wax;
1 to 2% by weight of a sodium-based plasticizer;
0.5 to 2% by weight of an organic oxidation initiator;
0.01 to 1% by weight peroxide;
1 to 5% by weight of a metal ion salt;
1 to 2% by weight of a thermal decomposition initiator;
0.5 to 2% by weight of organic acid;
40 to 82% by weight of a binder polymer; And
1 to 30% by weight of a decomposition assist accelerator,
Wherein the sodium plasticizer is at least one selected from the group consisting of sodium metasilicate (Na ₂ SiO ₃ ) and sodium borate decahydrate (Na ₂ B ₄ O ₇ .10H ₂ O)
Wherein the organic oxidation initiator is a C18-based alpha-linolenic acid (ALA), gamma-linolenic acid (GLA) or a mixture thereof,
The metal ion salt may be at least one selected from the group consisting of nickel nickel acetate, nickel oxalate, manganous acetate, manganic acetate, manganous oxalate, cobaltous acetate ), At least one selected from the group consisting of Cobaltic acetate, Cobaltous oxalate, Ferric formate and Ferrous lactate,
The pyrolysis initiator may be azobenzene, methyl red, 2,2'-azobisisobutyronitrile, Bismarck Brown, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (Aminodipropane) dihydrochloride, 1,1'-azobis (cyclohexane carbonitrile), 1,1'-azobis (N, N-dimethylformamide) and 2,2'-azobis -Methoxy-2,4-dimethylvaleronitrile), and at least one selected from the group consisting of
Wherein the organic acid is at least one selected from the group consisting of propionic acid, p-nitrilobenzoic acid, citric acid, malic acid, and maleic acid,
Wherein the decomposition assist accelerator is a mixture of calcium carbonate and talc.
A naturally degradable polymer composition for fishing use using closed fishes.
The method according to claim 1,
Wherein the redox initiator is at least one selected from the group consisting of ammonium persulfate (APS), potassium persulfate (PPS), and cumene hydroperoxide.
A naturally degradable polymer composition for fishing use using closed fishes.
The method according to claim 1,
Wherein the antioxidant further comprises at least one selected from the group consisting of a primary antioxidant, a secondary antioxidant and a yellowing-preventing antioxidant, wherein the primary antioxidant is at least one selected from the group consisting of tetrakis methylene (3,5-di-t-butyl- (3'-5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylidenebis [4,6-di Butylphenol], 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6 dimethylbenzyl) -1,3,5-triazine- , 3H, 5H) -triene, triethylene glycol bis [3- (3-thi-butyl-4-hydroxy-5-methylphenyl) propionate] and N, N'-hexamethylenebis [3- Butyl-4-hydroxyphenyl) propionamide], the secondary antioxidant is tris (2,4-di-t-butylphenyl) phosphite, The antioxidant for prevention is thioester thiodipropionate ), ≪ / RTI >
A naturally degradable polymer composition for fishing use using closed fishes.
The method according to claim 1,
Characterized in that the weight ratio of the polybutylene succinate / polybutylene adipate terephthalate polymer is 99/1, 95/5 or 90/10.
A naturally degradable polymer composition for fishing use using closed fishes.
A fish paste prepared from a natural degradable polymer composition for fishing using a closed net according to any one of claims 1 to 4.