Fishing gear

Abstract

To provide a fishing gear having excellent adhesion resistance.SOLUTION: The fishing gear includes an organic-inorganic composite hydrogel layer (A) on a surface of a substrate, wherein the organic-inorganic composite hydrogel layer (A) contains a polymer of a water-soluble organic monomer, a water-swellable clay mineral, and water, and the total amount of the polymer of a water-soluble organic monomer and the water-swellable clay mineral in the organic-inorganic composite hydrogel layer (A) is 1 to 90% by mass.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to fishing gear. [Background technology]

[0002] Conventionally, antifouling paints containing organotin compounds have been used to prevent marine organisms from attaching to fishing nets and other fishing gear, but their use has been restricted due to concerns about environmental pollution.

[0003] In response to this regulation, antifouling paint compositions containing cuprous oxide as a repellent have been proposed (see, for example, Patent Document 1). However, these antifouling paint compositions also basically prevent adhesion through their toxic effects, and their adverse effects on the environment have been viewed as a problem. Therefore, there has been a demand for fishing gear that is more environmentally friendly and has excellent anti-fouling properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5691102 Summary of the Invention [Problem to be solved by the invention]

[0005] The problem to be solved by the present invention is to provide fishing gear that has excellent anti-adherence properties. [Means for solving the problem]

[0006] The present inventors have found that the above problems can be solved by using fishing gear having a specific organic-inorganic composite hydrogel layer on the surface of a substrate, and have completed the present invention.

[0007] That is, the present invention provides fishing gear having an organic-inorganic composite hydrogel layer (A) on the surface of a substrate, wherein the organic-inorganic composite hydrogel layer (A) contains a polymer of a water-soluble organic monomer, a water-swellable clay mineral, and water, and the total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the organic-inorganic composite hydrogel layer (A) is 1 to 90 mass%. [Effects of the Invention]

[0008] Because the fishing gear of the present invention has excellent anti-fouling properties, it can be suitably used as fishing nets such as aquaculture nets, fixed nets, baskets, gill nets, drift nets, seine nets, purse seine nets and bottom nets, as well as mooring ropes (hawsers) for ships and fishing ropes. DETAILED DESCRIPTION OF THE INVENTION

[0009] The fishing gear of the present invention is a fishing gear having an organic-inorganic composite hydrogel layer (A) on the surface of a substrate, the organic-inorganic composite hydrogel layer (A) containing a polymer of a water-soluble organic monomer, a water-swellable clay mineral, and water, and the total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the organic-inorganic composite hydrogel layer (A) is 1 to 90 mass %. Hereinafter, the organic-inorganic composite hydrogel and the organic-inorganic composite hydrogel layer (A) may be abbreviated as hydrogel and hydrogel layer (A), respectively.

[0010] The polymer of the water-soluble organic monomer is obtained by polymerizing the water-soluble organic monomer, and examples of the water-soluble organic monomer include a monomer having a (meth)acrylamide group, a monomer having a (meth)acryloyloxy group, and an acrylic monomer having a hydroxyl group.

[0011] Examples of the monomer having a (meth)acrylamide group include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-cyclopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, and (meth)acryloylmorpholine.

[0012] Examples of the monomer having a (meth)acryloyloxy group include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxymethyl (meth)acrylate, and ethoxymethyl (meth)acrylate.

[0013] Examples of the acrylic monomer having a hydroxyl group include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

[0014] Among these, from the viewpoints of solubility and the physical properties of the resulting organic-inorganic composite hydrogel layer, it is preferable to use a monomer having a (meth)acrylamide group, it is more preferable to use acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, or acryloylmorpholine, it is even more preferable to use N,N-dimethylacrylamide or acryloylmorpholine, and from the viewpoint of ease of polymerization, N,N-dimethylacrylamide is particularly preferable.

[0015] The above-mentioned water-soluble organic monomers may be used alone or in combination of two or more kinds.

[0016] The polymer of the water-soluble organic monomer may be copolymerized with other monomers than the water-soluble organic monomer, if necessary.

[0017] The content of the polymer of the water-soluble organic monomer in the hydrogel layer (A) is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. When the content of the polymer of the water-soluble organic monomer is 1% by mass or more, a hydrogel having excellent mechanical properties can be obtained, which is preferable. On the other hand, when the content of the polymer of the water-soluble organic monomer (A) is 50% by mass or less, it is preferable because the preparation of the hydrogel precursor composition before polymerization is easy.

[0018] The water-swellable clay mineral forms a three-dimensional network structure together with the polymer of the water-soluble organic monomer, and becomes a constituent element of the hydrogel layer (A).

[0019] The water-swellable clay mineral is not particularly limited, but examples thereof include water-swellable smectite and water-swellable mica.

[0020] Examples of the water-swellable smectite include water-swellable hectorite, water-swellable montmorillonite, and water-swellable saponite.

[0021] Examples of the water-swellable mica include water-swellable synthetic mica.

[0022] Among these, from the viewpoint of the stability of the hydrogel precursor composition, it is preferable to use water-swellable hectorite or water-swellable montmorillonite, and it is more preferable to use water-swellable hectorite.

[0023] The water-swellable clay mineral may be naturally occurring, synthetic, or surface-modified. Examples of surface-modified water-swellable clay minerals include phosphonic acid-modified hectorite and fluorine-modified hectorite. From the viewpoint of the strength and adhesiveness of the resulting organic-inorganic composite hydrogel, it is preferable to use phosphonic acid-modified hectorite.

[0024] Examples of the phosphonic acid-modified hectorite that can be used include pyrophosphate-modified hectorite, etidronic acid-modified hectorite, alendronic acid-modified hectorite, methylenediphosphonic acid-modified hectorite, phytic acid-modified hectorite, etc. These phosphonic acid-modified hectorites may be used alone or in combination of two or more.

[0025] The above-mentioned water-swellable clay minerals may be used alone or in combination of two or more kinds.

[0026] The content of the water-swellable clay mineral in the hydrogel layer (A) is preferably 1% by mass or more, more preferably 2% by mass or more, since the mechanical properties of the resulting hydrogel are further improved. The content of the water-swellable clay mineral in the hydrogel layer (A) is preferably 20% by mass or less, more preferably 10% by mass or less, since the increase in viscosity of the hydrogel precursor composition can be further suppressed.

[0027] The hydrogel layer (A) may contain an organic solvent, and a hydrogel can be obtained that exhibits little change in mass even under open atmospheric conditions and can stably maintain mechanical properties such as flexibility, substrate adhesion, and breaking strength. Therefore, the organic solvent is preferably selected from those having a volatility of 1 cm in an open system at 60°C and 1 atmosphere. 2 Less than 0.1g per hour (0.1g / cm 2 1000g / cm 3 10 ... 2 ·hr·60℃·1atm), diglycerin (0.001g or less / cm 2 ·hr·60℃·1atm), ethylene glycol (0.01g or less / cm 2 hr 60℃ 1atm), propylene glycol (0.001g or less / cm 2 ·hr·60℃·1atm), polyethylene glycol (0.001g or less / cm 21 cm in an open system at 60°C and 1 atmosphere. 2 A polyhydric alcohol is preferably used in an amount of 0.01 g or less per hour, with glycerin and diglycerin being more preferred. These organic solvents may be used alone or in combination of two or more. It is also desirable that these organic solvents are uniformly contained in the hydrogel.

[0028] The mass ratio of water to the organic solvent (water / organic solvent) in the hydrogel layer (A) is not particularly limited, but is preferably 100 / 0 to 30 / 70, more preferably 100 / 0 to 40 / 60, since this can prevent the hydrogel precursor composition from becoming too viscous before polymerization.

[0029] The total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the hydrogel layer (A) is 1 to 90% by mass, preferably 2 to 90% by mass, more preferably 7 to 90% by mass, because this improves gel strength. On the other hand, if the total amount exceeds 90% by mass, it may be difficult to maintain the low-adhesion properties.

[0030] The total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the hydrogel layer (A) can be adjusted by the components of the hydrogel precursor composition before polymerization, but can also be adjusted by volatilizing or absorbing water, etc. after the formation of the hydrogel layer (A).

[0031] A preferred method for producing the hydrogel layer (A) is to polymerize the water-soluble organic monomer in a hydrogel precursor composition containing a mixture of a water-soluble organic monomer, a water-swellable clay mineral, water, and optionally an organic solvent, a polymerization initiator, and a polymerization accelerator, because this method allows for the easy production of a hydrogel having a three-dimensional network structure. The resulting polymer of the water-soluble organic monomer forms a three-dimensional network structure together with the water-swellable clay mineral, becoming a component of the hydrogel.

[0032] The polymerization initiator preferably has a solubility in water at 20° C. of 50 g / 100 ml or more, since it can sufficiently promote the polymerization of the water-soluble organic monomer even in an air atmosphere.

[0033] Examples of the polymerization initiator include water-soluble peroxides and water-soluble azo compounds having a solubility in water at 20° C. of 50 g / 100 ml or more.

[0034] Examples of the water-soluble peroxide include ammonium persulfate, sodium persulfate, and t-butyl hydroperoxide.

[0035] Examples of the water-soluble azo compounds include 2,2'-azobis(2-methylpropionamidine) dihydrochloride and 4,4'-azobis(4-cyanovaleric acid).

[0036] Among these, from the viewpoint of interaction with the water-swellable clay mineral, it is preferable to use a water-soluble peroxide, and it is more preferable to use ammonium persulfate or sodium persulfate.

[0037] The polymerization initiators may be used alone or in combination of two or more.

[0038] The molar ratio of the polymerization initiator to the water-soluble organic monomer in the hydrogel precursor composition is preferably 0.01 to 0.1, and more preferably 0.01 to 0.05, because this allows the polymerization of the water-soluble organic monomer to proceed sufficiently even in an air atmosphere.

[0039] Examples of the polymerization accelerator include tertiary amine compounds, thiosulfates, and ascorbic acids.

[0040] Examples of the tertiary amine compound include N,N,N',N'-tetramethylethylenediamine and 3-dimethylaminopropionitrile.

[0041] Examples of the thiosulfates include sodium thiosulfate and ammonium thiosulfate.

[0042] Examples of the ascorbic acids include L-ascorbic acid and sodium L-ascorbate.

[0043] Of these, from the viewpoint of affinity and interaction with the water-swellable clay mineral, it is preferable to use a tertiary amine compound, and it is more preferable to use N,N,N',N'-tetramethylethylenediamine.

[0044] The polymerization accelerators may be used alone or in combination of two or more.

[0045] The content of the polymerization accelerator in the hydrogel precursor composition is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass. A content of 0.01% by mass or more is preferred because it can efficiently promote the polymerization of the organic monomers of the resulting hydrogel. On the other hand, a content of 1% by mass or less is preferred because it allows the hydrogel precursor composition to be used without aggregation before polymerization, improving handleability.

[0046] The hydrogel precursor composition may further contain an organic crosslinking agent, a preservative, a thickener, etc., as needed.

[0047] The polymerization temperature of the water-soluble organic monomer is preferably 10 to 80° C., and more preferably 20 to 80° C. A polymerization temperature of 10° C. or higher is preferred because the radical reaction can proceed in a chain reaction. On the other hand, a polymerization temperature of 80° C. or lower is preferred because the polymerization can be carried out without boiling water.

[0048] The polymerization time varies depending on the type of polymerization initiator and polymerization accelerator, but is typically between several tens of seconds and 24 hours. In particular, in the case of radical polymerization using heat or redox, the polymerization time is preferably between 1 and 24 hours, and more preferably between 5 and 24 hours. If the polymerization time is less than 1 hour, when a substrate such as a net or rope is dipped into the hydrogel precursor composition, the composition may not be able to sufficiently penetrate into the gaps between the twists, and the water-swellable clay mineral and the polymer of the water-soluble organic monomer may not be able to form a three-dimensional network. On the other hand, from the viewpoint of quickly completing the formation of the hydrogel layer (A) on the substrate surface, it is preferable to substantially complete the polymerization reaction within 24 hours.

[0049] A preferred method for forming the hydrogel layer (A) on the surface of a fishing gear substrate is to paint the hydrogel precursor composition onto the surface of the fishing gear substrate and generate the organic-inorganic composite hydrogel on the surface of the fishing gear substrate.

[0050] The hydrogel precursor composition can be applied to the surface of a fishing gear substrate by any of a variety of known application methods, but application by dipping, brushing, spatula, spraying, etc. is preferred because it allows easy application. By reducing the pressure during dipping, the hydrogel precursor composition can be further penetrated into the substrate, such as a net or rope.

[0051] The base material of the fishing gear of the present invention is not particularly limited, but examples thereof include ropes and nets.

[0052] The material of the substrate is not particularly limited, but examples thereof include vinylon, polyester, tetron, nylon, and polyethylene.

[0053] In the fishing gear of the present invention, the hydrogel layer (A) is preferably present in an amount of 10 parts by mass or more relative to 100 parts by mass of the substrate, since this improves adhesion to the substrate and the anti-adhesion properties of the fishing gear surface. On the other hand, the amount is preferably 300 parts by mass or less, more preferably 100 parts by mass or less, relative to 100 parts by mass of the substrate, since this makes the fishing gear lighter and easier to handle.

[0054] The fishing gear of the present invention has excellent anti-adhesion properties in water, and therefore can be suitably used for, for example, fishing nets such as aquaculture nets, fixed nets, baskets, gill nets, drift nets, seine nets, purse seine nets and bottom nets, mooring ropes (hawsers) for ships, fishing ropes, etc. [Example]

[0055] The present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to these examples.

[0056] (Preparation Example 1: Preparation of Hydrogel Precursor Composition (P-1)) A flat-bottomed glass container was charged with 40 g of purified water, 63 g of purified glycerin, 4.8 g of phosphonic acid-modified synthetic hectorite ("Laponite RDS" manufactured by BYK Japan Co., Ltd.), 20 g of dimethylacrylamide (hereinafter abbreviated as "DMAA"), and 20 mg of N,N'-methylenebisacrylamide, and the mixture was stirred to prepare a uniform, transparent composition (1). The viscosity of this composition (1), after being kept in a thermostatic bath at 25°C, was measured using a B-type viscometer ("VISCOMETER TV-20" manufactured by Toki Sangyo Co., Ltd.), and found to be 1000 mPa s. Next, 12.6 g of water and 80 μL of tetramethylethylenediamine (hereinafter abbreviated as "TEMED") were placed in another flat-bottom glass container and stirred to prepare a homogeneous TEMED solution. The entire amount of composition (1) was placed in a 200 mL glass beaker, and 0.5 g of sodium persulfate (hereinafter abbreviated as "NPS") was added thereto and stirred until dissolved. The TEMED solution prepared above was then gradually added, and stirring was continued until the mixture was uniformly mixed to prepare a hydrogel precursor composition (P-1).

[0057] (Preparation Example 2: Preparation of Hydrogel Precursor Composition (P-2)) A hydrogel precursor composition (P-2) was prepared in the same manner as in Preparation Example 1, except that the 63 g of purified glycerin used in Preparation Example 1 was entirely replaced with pure water.

[0058] Example 1 A Cremona rope (made of vinylon, diameter approximately 6 mm, length approximately 500 mm, rope mass 9.5 g) used for fishing nets was immersed (dipped) into a container containing 200 g of the hydrogel precursor composition (P-1) obtained above. The Cremona rope was then removed from the container and allowed to stand for 5 hours at 23°C to obtain a Cremona rope (1) having an organic-inorganic composite hydrogel layer (A-1) on its surface. The total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the organic-inorganic composite hydrogel layer was 18% by mass, and the organic-inorganic composite hydrogel layer was 242 parts by mass per 100 parts by mass of the Cremona rope substrate.

[0059] Example 2 A Cremona rope (2) having an organic-inorganic composite hydrogel layer (A-2) on its surface was obtained in the same manner as in Example 1, except that the hydrogel precursor composition (P-1) used in Example 1 was replaced with a hydrogel precursor composition (P-2). The total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the organic-inorganic composite hydrogel layer was 18 mass %, and the organic-inorganic composite hydrogel layer was 72 mass parts per 100 mass parts of the Cremona rope base material.

[0060] Example 3 The Cremona rope (2) obtained in Example 2 was further allowed to stand for 2 hours at 60°C to obtain a Cremona rope (3) having an organic-inorganic composite hydrogel layer (A-3) on its surface. The total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the organic-inorganic composite hydrogel layer was 88 mass%, and the organic-inorganic composite hydrogel layer was 14.5 mass parts per 100 mass parts of the Cremona rope base material.

[0061] (Comparative Example 1) The Cremona rope (2) obtained in Example 2 was further allowed to stand for 4 hours at 60°C to obtain a Cremona rope (R1) having an organic-inorganic composite hydrogel layer (RA-1) on its surface. The total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the organic-inorganic composite hydrogel layer was 93 mass %, and the organic-inorganic composite hydrogel layer accounted for 13.7 parts by mass per 100 parts by mass of the Cremona rope substrate.

[0062] [Evaluation of poor adhesion] The Cremona rope obtained above was coated with various topcoats shown in Table 1 using a brush or spatula, and left to stand for 3 hours at 23°C. After that, the rope was immersed in water for 24 hours, and the lifting and peeling of the topcoat was checked, and the adhesion resistance was evaluated according to the following criteria. ○: Lifting or peeling ×: No lifting or peeling

[0063] The operations in the above examples and comparative examples were carried out in a laboratory at 23°C and 50% RH.

[0064] The evaluation results of Examples 1 to 3 and Comparative Example 1 are shown in Table 1.

[0065] [Table 1]

[0066] The topcoat materials in the table are as follows: Urethane resin: DIC Corporation's "Polylite Primer PD" Adhesive A: "Quick Mender" manufactured by Konishi Co., Ltd. Adhesive B: Aron Alpha F221 manufactured by Toagosei Co., Ltd.

[0067] It was confirmed that the fishing gear of Examples 1 to 3 had excellent anti-adhesion properties.

[0068] On the other hand, in Comparative Example 1, the total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the organic-inorganic composite hydrogel layer (A) was greater than 90 mass %, which is the upper limit of the present invention, and it was confirmed that the adhesion resistance was poor.

Claims

1. A fishing gear having an organic-inorganic composite hydrogel layer (A) on the surface of a substrate, wherein the organic-inorganic composite hydrogel layer (A) contains a polymer of a water-soluble organic monomer, a water-swellable clay mineral, and water, and the total amount of the polymer of the water-soluble organic monomer and the water-swellable clay mineral in the organic-inorganic composite hydrogel layer (A) is 1 to 90 mass %.

2. 2. The fishing gear according to claim 1, wherein the water-soluble organic monomer comprises one or more monomers selected from the group consisting of a monomer having a (meth)acrylamide group, a monomer having a (meth)acryloyloxy group, and a (meth)acrylic monomer having a hydroxyl group.

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