WO2010009656A1

WO2010009656A1 - False fish bait having biodegradability and producing method thereof

Info

Publication number: WO2010009656A1
Application number: PCT/CN2009/072739
Authority: WO
Inventors: 王德祥
Original assignee: 集伍国际控股集团有限公司; 丁晓冬
Priority date: 2008-07-20
Filing date: 2009-07-13
Publication date: 2010-01-28
Also published as: CN101525480A; CN101525480B

Abstract

A false fish bait having biodegradability and producing method thereof. The bait is mainly composed of polyhydroxyalkanoates (PHAs), which include homopolymer, copolymer, and mixture thereof belonging to the group of PHAs. In addition to the main component, PCL, PBS, APC, or natural elastomers and petroleum-based elastomers can be added into the false fish bait. Assistants, fish attractants and colorants can also be added. The false fish bait having biodegradability can be formed by injection molding or press molding.

Description

Biodegradable artificial fishing bait and manufacturing method thereof

The invention relates to the technical field of artificial biodegradable fake fishing lures, in particular to the use of a degradable material as a main material of a fishing lure, which can be degraded in the environment, without causing harm to the environment, the present invention It also relates to the method of making artificial fake fishing lures using these materials.

Background technique

Due to the depletion of petroleum resources and the pressure on the environment, as well as safety considerations, people are paying more and more attention to the application of degradable materials, especially in certain special fields, due to non-degradable Articles made of materials can cause significant harmful or deleterious effects. This is especially true for the marine environment, where more and more reports indicate that even very small non-degradable items, such as artificial polymer fake fishing lures, can not adversely affect the marine environment due to their inability to degrade in the ocean, and often even Traces are found in the body of certain marine organisms.

Fishing with artificial fake bait is a very popular fishing method in the coastal areas. The traditional method of making fake fishing lures from natural wood is due to environmental protection and the use performance and simulation of finished products. The use of petroleum-based plastics to make artificial fishing lures has become popular. Some common polymer materials have begun to be widely used in this field. Polyvinyl chloride (PVC) is a widely used one, but PVC does not degrade and is derived from Petroleum-based materials, which are unattractive to fish, require the addition of a large number of attractants, and the fish, after ingesting the fake bait, will block its digestive system and cause its death. More deadly, PVC must add a large amount (possibly up to 80%) of plasticizer to achieve a suitable degree of softness and softness (plasticization and flexibility) to achieve simulation effects in swimming in the water, the most common of which is Adding dioctyl phthalate (DIOP), this plasticizer is in liquid form, insoluble in water, and will be present in rivers/oceans for a long time after use. And a large number of experiments have shown that this plasticizer is a serious hazard to organisms. Such plasticizers have been banned from being used in food-related fields at home and abroad, and the use of fake fishing lures and the consequent series of safety problems may lead to serious consequences.

Domestically, other types of polymer materials are used to make fake fishing lures. For example, Chinese patent CN200510109105.1 uses polycarbonate (PC), polyethylene resin (PE), and acrylonitrile-butadiene-styrene resin mixture. PC itself is harder in material, in addition to the similar problems with PVC, and because of its addition of peroxide initiator and azo blowing agent (1~4%), it will also have adverse effects on the environment and the animals and plants in the water. .

In addition, certain fish bait formula compounds are very harmful to fish survival, such as Japanese Patent Application No. 4,360,637 and 4,365,454, using potassium polyphosphate (sodium) as a binder, and sodium chondroitin sulfate as a water retaining agent. , its hazard may even lead to the death of different degrees of fresh fish. Since the bait made of natural organisms (worms or squids, etc.) is difficult to store, it is easy to emit an unpleasant odor. The fake bait is durable and will not lose its integrity due to its long time in the water. It has better strength and can be shaped into any shape that attracts fish. It is easy to hook and is loved by most fishing enthusiasts. In view of the above drawbacks, the prior art must find a suitable new type of degradation material to make a fake fishing lure to solve the problem. Since no suitable matrix materials have been found, there are currently no patents related to the manufacture of fake fishing lures in polymers in China.

US Patent No. 4,385,302 describes a method of making a fishing lure using PVA as a main material. The manufacturing process is very complicated, and the process of making the gel requires 2 to 50 hours of freezing, which is not only time consuming but also uneconomical, and The patented PVA polymerization degree can not exceed 2000, so its strength can not reach the effect of the traditional PVC fishing lure, and its application is also limited.

U.S. Patent No. 6,174,525 discloses a molded fishing lure using a water-soluble long chain polyhydroxy polymer, but similar to the above patents, merely increases the degree of polymerization of PVA, PVA in terms of degradability and processability. The defect still exists.

U.S. Patent No. 4,375,481, the disclosure of which is incorporated herein by reference in its entirety, the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire disclosure However, the co-adhesiveness of such a gel is very poor, and it is difficult to hook the fish, and the adhesive strength, elasticity and softness cannot meet the requirements of the bait.

European Patent EP0515231 discloses a fake fishing lure using a polyurethane (PU) polymer glue or a foaming material, the polymer structure comprising hydrolytically unstable ester bonds and other additives, according to the patent, the degradation properties of the novel material Depending on the hydrolysis-labile ester bond in the PU foam, this ester bond is obtained by polycondensation of an acid and an alcohol by a polyhydric alcohol with a (hydroxyl acid) to produce a hydrolysis-labile ester bond. However, at the time of synthesis It needs to use isocyanate, and the isocyanate gas, steam, dust or aerosol is inhaled into the human body, which will endanger human health and may cause irritation to the skin. The synthesis process is complicated. More importantly, the synthesized multilayer PU structure is not fully biodegradable, and it still has adverse effects on the organism. Hydrolysis also needs to be under certain conditions. Patented US 5,266,323 and US 5,270,044 It is similar.

In summary, the current domestic and foreign bait patents have not proposed a truly biodegradable, good performance, safe and environmentally friendly bait material, so there is no fundamental solution to the degradation of the bait.

Currently, the world's biodegradable materials mainly include PHA, PLA (polylactic acid), PBS (polybutylene succinate), PCL (polycaprolactone), APC (carbon dioxide / epoxy compound copolymer), starch-based Materials, modified PVA, etc. After the biodegradable plastic is degraded, it becomes water and carbon dioxide, so it does not harm the environment. Among them, polyhydroxyalkanoate PHAs are derived from natural renewable raw materials and have various compositions, good performance, wide application, good physical, mechanical and processing properties, good biodegradability and biocompatibility. It can be absorbed by living organisms and has a bright future. In particular, PHAs copolymers (such as PHBV, PHBH, P3HB4HB, etc.) can be used to achieve elastomeric materials from brittle materials to excellent toughness.

Since bait needs to have a good biomimetic effect in water, it is necessary to use a high toughness material similar to elastomer to achieve this. As required, some rigid PHA structures similar to PLA, such as poly-3-hydroxybutyrate P (3HB) composed of 3-hydroxybutyric acid, cannot meet the requirements for use. However, the properties of some copolymers of P(3HB) can be changed from hard and brittle to soft and tough, such as PHBV, which is a semi-crystalline polymer, which increases the mechanical properties by increasing the toughness of PHB. Other copolymers such as P3HB4HB, due to the introduction of the linear aliphatic flexible monomer 4HB, have improved toughness and greatly improved ductility, and are close to the properties of rubber. As the number of flexible units increases, the copolymer transitions from a crystalline hard plastic to a resilient rubbery state, and has good thermal stability, becoming an elastomer. In the PHAs copolymer, the physical and mechanical properties of the polymer are changed by changing the content of the flexible molecules in the polymer to obtain materials having different rigidity, crystallinity, melting point and glass transition temperature suitable for different uses. PHAs are currently the only fully biodegradable materials that can be used as elastomers, and have broad prospects for certain special applications.

Summary of the invention

SUMMARY OF THE INVENTION The object of the present invention is to provide a novel, low-cost bait that has excellent durability, tensile strength, flexibility, elasticity, bond strength, and aesthetic simulation. More importantly, this new type of bait can be degraded without harming the environment and organisms. This bait can be made into any shape that fish likes by injection molding or molding, such as worms, cockroaches, squid, crayfish, squid eggs and the like. This bait has good biocompatibility and is absorbed by the organism without any side effects.

The object of the present invention can be achieved by the following technical solutions:

A biodegradable artificial fishing lure, the main constituent material of the fishing lure being PHAs (polyhydroxyalkanoate), including monomers, copolymers and blends thereof in the PHAs family.

The biodegradable artificial fishing lure whose main constituent material PHAs is a copolymer is P3HB4HB.

The biodegradable artificial fishing lure, wherein the fishing lure further comprises any one of PCL (polycaprolactone), PBS (polybutylene succinate), PPC (polypropylene carbonate), or any More than one material.

The biodegradable artificial fishing lure, wherein the fishing lure further comprises a natural or petroleum-based elastic material.

The biodegradable artificial fishing lure further comprises one or more of an auxiliary agent, a fish attractant, and a toner in order to improve the attraction and use performance of the fishing lure to the fish.

The biodegradable artificial fishing lure, wherein the artificial fishing lure is composed of the following weight percentages:

(A) Polyhydroxyalkanoates (PHAs) 1 to 99

(B) Other high toughness fully degradable materials 1~60

(C) Natural or petroleum based elastomers 0 to 40.

(A) Polyhydroxyalkanoates (PHAs) 1 to 99

(B) Other high toughness fully degradable materials 1~50 (C) petroleum-based elastomers 0~30

(D) Additives 0~20

(E) Fish attractant 0~3

(F) Toner 0~2

(A) Polyhydroxyalkanoates (PHAs) 60 to 99

(B) Other high toughness fully degradable materials 0~30

(C) petroleum-based elastomer 0~10

(D) Additives 0~3

(E) Fish attractant, toner 0~1.5

(F) Toner 0~0.5

A method for manufacturing a biodegradable artificial fishing lure comprising the following steps:

1) mixing and mixing the above materials according to the formula;

2) drying the above uniformly stirred mixture at 40-160 degrees Celsius, and extruding and granulating using a twin-screw extruder to obtain a pellet raw material;

3) The above raw materials are heated to 40-160 degrees Celsius, injected into the molding die by injection molding or molding, and the pressure is maintained for 10 to 200 MPA for a period of time, the mold is opened, and the natural environment is cooled and shaped to obtain a molded artificial fish bait.

The invention has the advantages that the PHAs copolymer is used as the base material of the degradable fishing lure, and the traditional fishing bait can not be degraded, has no biocompatibility problem, and has good biomimetic performance, and the physical and mechanical properties are close to the traditional bait, and has good performance. The simulated simultaneous processing performance is good, and the fishing lure can be formed by conventional injection molding or molding.

Specific embodiment

In this patent, the monomers, copolymers and blends thereof in the PHA family are proposed as the matrix material of the degradable fishing lure. Since the PHAs have many different molecular compositions and copolymerized units, the PHAs copolymer referred to in this patent It should include, but is not limited to, a single polymer and copolymer in PHA, such as P3HB4HB, PHBV, PHBH, etc., and mixtures of these copolymers or homopolymers.

In order to improve certain properties of PHAs, reduce costs and enhance performance, this patent proposes to use PHAs as matrix materials for degradable bait, and can also be blended with other tougher degradable materials, such as polycaprolactone (PCL). , butyl succinate (PBS), aliphatic polycarbonate (APC), etc., to form a new fully biodegradable material to meet different application requirements.

In order to improve biodegradable processing performance, reduce cost, and improve performance in certain aspects, the present invention proposes Natural elastic materials and petroleum-based elastic materials may also be added to the fake fishing lure material, including natural and elastic materials including but not limited to PU, EVA (ethylene-vinyl acetate copolymer), SEBS (styrene-ethylene/butene) A styrene copolymer), etc., form a new degradable material to meet different use requirements.

Therefore, the components involved in this patent mainly include:

Polyhydroxyalkanoate elastomer PHAs;

Other high toughness fully degradable materials, including but not limited to PCL, PBS, APC, etc.;

Natural elastic materials, petroleum-based elastic materials, including but not limited to PU, EVA, SEBS, etc.;

Auxiliary.

The auxiliaries referred to in the present invention should include, but are not limited to, plasticizers, slip agents, nucleating agents, crosslinking agents, surfactants, colorants, lubricants, heat stabilizers, antioxidants, flame retardants, Waxes, tackifying resins, extenders, anti-fastening agents or other inorganic or organic fillers and mixtures thereof. In order to improve safety and environmental performance, biomass sources and auxiliaries that are not harmful to living organisms should be used. The purpose is to ensure the performance and appearance of the bait.

In order to achieve the effect of attracting fish, the fish attractant of the present invention includes a flavoring agent, a sweetener, a koji, a fish oil, and the like, and other natural, artificial materials which are attractive to fish.

In order to achieve the effect of attracting fish, the toner in the present invention may be a natural, artificial pigment material.

The PHAs used in the present invention may be modified by changing the composition of the copolymer in the PHA (e.g., the content of 4HB in P3HB4HB), or the composition of the PHA (such as using a PHA blend to change the content of P3HB4HB and PHBH), or PHAs and The composition of other biodegradable materials to change the properties of the blend, and depending on the processing method, a small amount of additives are added to obtain a high-performance composite.

The biodegradable artificial fishing lure proposed by the invention has the following weight percentages:

(A) Polyhydroxyalkanoates (PHAs) 1 to 99

(B) Other high toughness fully degradable materials 1~50

(C) petroleum-based elastomer 0~30

(D) Additives 0~20

(E) Fish attractant 0~1.5

(F) Toner 0~0.5

The invention also proposes a biodegradable artificial fishing lure method comprising the following steps:

1. Weighing: According to the final use of the product, choose the appropriate PHA / other degradation materials / natural, petroleum-based elastic material ratio, and the specific composition of PHA, the content of comonomer in each copolymer, called Take the corresponding weight of polymer.

2. Blending: Blend PHAs with petroleum-based elastomers according to the above ratio, and choose to add suitable according to the end use. Additives, stir in a high speed mixer.

3. Drying: The above blends, which were uniformly stirred, were placed in an electric blast drying oven for drying.

4. Plasticization: The dried blend was re-plasticized using a twin-screw extruder to complete the blending modification to form a new degradable material.

5. Granulation: After the twin-screw extruded blend was cooled in a water bath, the draw was cut into pellets by a conventional pelletizer.

6. Molding: The granulated degradation masterbatch is formed into a suitable shape by injection molding or molding.

In the above step 2, the blending material is stirred in the mixer for 1 to 30 minutes, preferably 5 to 10 minutes.

In the above step 3, the temperature of the electric blast drying oven is 40 to 100 ° C, and the drying time is 2 to 48 hours, preferably 50 to 50

80 ° C, drying time is 6 to 12 hours;

The blending materials in the above step 4 are plasticized in a twin-screw extruder. According to the composition of the PHAs and the formulation, the temperature range of the feeding section, the compression section and the homogenizing section of the entire twin-screw extruder is in the range of 90 to 180°. Between C, maintain the die temperature at 110~

Between 170 ° C, wherein the feed section, the compression section and the homogenization section of the extruder preferably have a temperature ranging from 110 to 165 ° C and a die temperature of between 120 and 155 ° C.

Example 1

100 kg of P3HB4HB (40 4HB), 0.5 kg of cod liver oil, 0.3 kg of natural flavor, and 0.2 kg of food coloring were weighed, and stirred at room temperature for 5 minutes in a blender to obtain a raw material mixture of fully biodegradable plastic. The stirred mixture was placed in an electric blast drying oven at 60 ° C for 10 hours, and then the above dried mixture was extruded through a 45 twin-screw extruder having a length to diameter ratio of 28:1, and the die temperature was At 115 ° C, direct granulation after extrusion gives a fully biodegradable plastic masterbatch. The masterbatch is obtained by injection molding or molding to obtain a biodegradable artificial fishing lure.

Example 2

Weigh 80kg P3HB4HB (45% 4HB^B20kgPHBV (20 HV) and 0.2kg silkworm cocoon powder, 0.2kg honey, 0.2kg yellow wine, 0.2kg food coloring, stir in the mixer for 8 minutes at room temperature to obtain the raw material mixture of fully biodegradable plastic. The stirred mixture was placed in an electric blast drying oven and dried at 65 ° C for 10 hours, and then the above dried mixture was extruded through a 45 twin-screw extruder having a length to diameter ratio of 28:1, and the die temperature. A fully biodegradable plastic masterbatch is obtained by direct granulation after extrusion at 130 ° C. The masterbatch is obtained by injection molding or molding to obtain a biodegradable artificial fish bait.

Example 3

Weigh 80kg of P3HB4HB (40%4HB), 10kg of PCL and PBS, 0.3kg of shrimp powder, 0.2kg of fishmeal, 0.5kg of fish oil, 0.2kg of natural pigment, and stir at room temperature for 10 minutes in a blender to obtain a mixture of raw materials for fully biodegradable plastics. material. The stirred mixture was placed in an electric blast drying oven at 65 ° C for 10 hours, and then the above dried mixture was extruded through a 45 twin-screw extruder having a length to diameter ratio of 28:1, and the die temperature was 120 ° C, directly granulated after extrusion to obtain a fully biodegradable plastic masterbatch. The masterbatch is obtained by injection molding or molding to obtain a biodegradable artificial fishing lure. Example 4

Weigh 90kg of P3HB4HB (35 % 4HB), PCL5kg, SEBS5KG and 0.2kg disodium glycyrrhizinate, 0.3kg of liqueur, 0.3kg of citric acid, 0.2kg of food coloring in a blender for 15 minutes at room temperature to obtain a raw material mixture of degradable plastics. . The stirred mixture was placed in an electric blast drying oven and dried at 70 ° C for 10 hours, and then the above dried mixture was extruded through a 45 twin-screw extruder having a length to diameter ratio of 28:1, and the die temperature was 120 ° C, directly granulated after extrusion to obtain a fully biodegradable plastic masterbatch. The masterbatch is obtained by injection molding or molding to obtain a biodegradable artificial fishing lure.

Claims

Claim

A biodegradable artificial fishing lure characterized in that the main constituent material of the fishing lure is PHAs, including monomers, copolymers and blends thereof in the PHAs family.

The biodegradable artificial fishing lure according to claim 1, wherein the copolymer of the main constituent material PHAs is P3HB4HB.

The biodegradable artificial fishing lure according to claim 1, wherein the fishing lure further comprises any one or more of PCL, PBS, and PPC.

The biodegradable artificial fishing lure according to claim 1 or 2, characterized in that the fishing lure further comprises a natural or petroleum-based elastic material.

The biodegradable artificial fishing lure according to claim 1 or 2 or 3, characterized in that in order to improve the attraction and performance of the fishing lure to the fish, the fishing lure further comprises an auxiliary agent, a fish attractant, and a toner. One or more of them.

The biodegradable artificial fishing lure according to claim 4, characterized in that in order to improve the attraction and performance of the fishing lure to the fish, the fishing lure further comprises one of an auxiliary agent, a fish attractant, and a toner. More than one.

The biodegradable artificial fishing lure according to claim 5, characterized in that the artificial fishing lure is composed of the following weight percentages:

(A) Polyhydroxyalkanoates (PHAs) 1 to 99

(B) Other high toughness fully degradable materials 1~60

(C) Natural or petroleum based elastomers 0 to 40.

The biodegradable artificial fishing lure according to claim 6, wherein the artificial fishing lure is composed of the following weight percentages:

(A) Polyhydroxyalkanoates (PHAs) 1 to 99

(B) Other high toughness fully degradable materials 1~50

(C) petroleum-based elastomer 0~30

(D) Additives 0~20

(E) Fish attractant 0~3

(F) Toner 0~2.

The biodegradable artificial fishing lure according to claim 6, wherein the artificial fishing lure is pressed

1 The following weight percentages are composed:

(A) Polyhydroxyalkanoates (PHAs) 60 to 99

(B) Other high toughness fully degradable materials 0~30

(C) petroleum-based elastomer 0~10

(D) Additives 0~3

(E) Fish attractant 0~1.5

(F) Toner 0 to 0.5.

A method of manufacturing a biodegradable artificial fishing lure, comprising the steps of:

1) mixing and mixing the above materials according to the formula;

2) drying the above uniformly stirred mixture at 40-160 degrees Celsius, and extruding the granules using a twin-screw extruder to obtain granule raw materials;

3) The above raw materials are heated to 40-160 degrees Celsius, injected into the molding tool by injection molding or molding, and the pressure is maintained for 10 to 200 MPA for a period of time, the mold is opened, and the natural environment is cooled and shaped to obtain a molded artificial fishing lure.