JPH06271413A - Nylon resin molded article effective for preventing adhesion of aquatic organism - Google Patents

Abstract

PURPOSE:To obtain a nylon resin molded article effective for preventing the adhesion of aquatic organism and capable of keeping the effect in high level over a long period even by molding at high temperature. CONSTITUTION:The objective molded nylon resin article effective for preventing the adhesion of aquatic organism is produced by molding a composition obtained by kneading (A) a molten nylon resin with (B) one or more compounds selected from 2-mercaptobenzimidazole, its zinc salt, an aliphatic carboxylic acid copper salt and dithiocarbamic acid zinc salt, (C) cuprous oxide and (D) a polyamide resin derived from polymerized fatty acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nylon resin molded article having a property of preventing adhesion of organisms adhering to water. More specifically, marine attached organisms such as barnacles, mussels, sea bream, diatoms, and cyanobacteria will attach to fishing nets, their associated ropes, ship bottoms, seawater intake channels, seawater intake channel walls, and undersea structures over a long period of time. TECHNICAL FIELD The present invention relates to a nylon resin molded article for preventing aquatic organisms from adhering.

[0002]

2. Description of the Related Art Conventionally, underwater adhering organisms have adhered to fishing nets, incidental ropes for fishing nets, ship bottoms, undersea structures, etc., which causes a large amount of hay death of seafood due to clogging of fishing nets, sedimentation due to weight increase, and work. In order to prevent adverse effects such as a decrease in efficiency, a ship's operation trouble, and a decrease in seawater inflow, a copper compound (for example, JP-A-56-142203) and an organic chlorine compound (for example, JP-A-56-61304).
No.), organic nitrogen compounds (for example, JP-A-63-156).
No. 703), organic nitrogen-sulfur compounds (see, for example, JP-A No.
Many surface treatment methods using antifouling agents such as JP-A 6-147701) have been proposed. However, the surface treatment method has a remarkable effect of preventing the attachment of aquatic organisms for a short period of time, but has a drawback that the effect cannot be maintained for a long period of time.

In order to maintain the effect of preventing aquatic organisms from adhering to these surface treatment methods over a long period of time, for example, 2
There has also been proposed a method for producing a fishing net or the like as a molded product by kneading a synthetic resin such as polyolefin or polyvinyl chloride with-(4-thiazolyl) benzimidazole and a copper compound (Japanese Patent Application Laid-Open No. 49-80146). Gazette).

In recent years, nylon resins have been often used in aquaculture fishing nets because of their durability, amine decomposition resistance and high strength.
However, when spinning a fiber from a nylon resin, a high temperature condition of 200 to 300 ° C is applied. Therefore, the conventionally known antifouling agent decomposes or volatilizes, which causes a problem such as yarn breakage. May not be possible, or only a small amount can be uniformly contained, so that a sufficient effect of preventing adhesion of aquatic organisms may not be exhibited. For these reasons, it does not decompose or volatilize even when kneaded with nylon resin,
Further, an antifouling agent that can be contained in a large amount and uniformly is desired.

[0005]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide an underwater organism adhesion preventing nylon resin molded product capable of maintaining a high effect of preventing underwater organism adhesion for a long time even when kneading and molding under high temperature conditions. To do.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on an antifouling agent that can be kneaded into a nylon resin and does not decompose or volatilize even under high temperature conditions.
It was found that mercaptobenzimidazole, its zinc salt, copper salt of aliphatic carboxylic acid, zinc salt of dithiocarbamic acid, and cuprous oxide have high heat resistance and good dispersibility in nylon resin. Particularly, one or more compounds selected from the group consisting of 2-mercaptobenzimidazole, a zinc salt thereof, a copper salt of an aliphatic carboxylic acid, and a zinc salt of dithiocarbamic acid are used in combination with cuprous oxide, and these are added to a molten nylon resin. It has been found that a nylon resin molded product obtained by kneading and molding is highly effective in preventing the attachment of aquatic organisms for a long time. And in some cases, further, by kneading and eluting the dissolution rate adjusting agent, it is also found that the aquatic organism adhesion preventing effect lasts for a longer period,
The present invention has been completed. That is, the present invention relates to (1) nylon resin (A), and one or more selected from the group consisting of 2-mercaptobenzimidazole and zinc salt thereof, copper salt of aliphatic carboxylic acid, and zinc salt of dithiocarbamic acid. (B) and cuprous oxide (C) are kneaded and molded, and molded into an aquatic organism adhesion-preventing nylon resin molded product, (2) and a polymerized fatty acid-based polyamide resin (a) is prepared. The aforesaid aquatic organism adhesion-preventing nylon resin molded article is kneaded and molded as the agent (D).

The nylon resin (A) used in the present invention may be a commonly used one, and examples thereof include nylon 6, nylon 66, nylon 7, nylon 9, nylon 11, nylon 12 and the like, and mixtures thereof. Of these, nylon 6 and nylon 66 are preferable, and nylon 6 is particularly preferable.

Of the group (B) of compounds in the present invention, the copper salt of an aliphatic carboxylic acid usually has 6 to 6 carbon atoms.
Examples thereof include copper salts of 36 aliphatic carboxylic acids, preferably copper salts of aliphatic carboxylic acids having 8 to 18 carbon atoms. These aliphatic carboxylic acids may be optionally used in combination.

Among the compounds (B), the particle size of the compound (B) when it is not melted at the melting temperature of the nylon resin (A) is usually 20 μm or less, preferably 5 μm or less. Two
If it exceeds 0 μm, the dispersion in the nylon resin (A) cannot be sufficiently performed, and the resin strength is remarkably lowered, which is not preferable. However, the particle size of the compound (B) when it is melted at the melting temperature of the nylon resin is not limited at all.

The amount of the compound (B) kneaded into the nylon resin (A) is usually 5 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the nylon resin (A). If it is less than 5 parts by weight, a sufficient effect of preventing adhesion of aquatic organisms cannot be obtained, and if it exceeds 30 parts by weight, the strength of the nylon resin is lowered, which is a practical problem when applied to fishing nets and the like.

As the cuprous oxide (C) in the present invention,
Usually, a particle size of 20 μm or less can be used, but a particle size of 5 μm or less is preferable. When it exceeds 20 μ, the resin strength and the like are markedly reduced as in the case of the compound (B).

The amount of cuprous oxide (C) kneaded in the nylon resin (A) is usually 5 to 30 parts by weight with respect to 100 parts by weight of the nylon resin (A). If it is less than 5 parts by weight, a sufficient effect of preventing adhesion of aquatic organisms cannot be obtained, and if it exceeds 60 parts by weight, the strength of the nylon resin is lowered, which is a practical problem when applied to fishing nets and the like.

In order to gradually dissolve the antifouling agent of the compound (B) and cuprous oxide (C) into water over a long period of time, if a further adjusting agent (D) is used, the effect of preventing aquatic organisms from adhering is maintained. Can be extended. Depending on the application, for example, when used for fishing nets, it is desirable to use (D) together in an appropriate amount. Examples of the adjusting agent (D) include polymerized fatty acid-based polyamide resin (a), acid-modified polyolefin (eg, maleic acid-modified polystyrene, maleic acid-modified polypropylene), ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer. , Ethylene ethyl acrylate copolymer, ethylene glycidyl methacrylate copolymer, and polyether ester amide resin. The polymerized fatty acid-based polyamide (a) is preferred.

The polymerized fatty acid-based polyamide resin (a) of the present invention used as a regulator (D) may be a conventional one, and specifically, polymerized fatty acid (a), monocarboxylic acid (a) and polyamine. The resin obtained by reacting (c) is mentioned.

Examples of the polymerized fatty acid (a) in the polymerized fatty acid-based polyamide resin (a) include ordinary fatty acids such as unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, dry oil fatty acids, and semi-dry oil fatty acids. Examples thereof include those obtained by polymerizing lower alcohol esters of these fatty acids in the presence or absence of a catalyst, and various types are commercially available. For example, those having 0 to 5% by weight of monocarboxylic acid having 18 carbon atoms, 60 to 98% by weight of dimer acid having 36 carbon atoms, and 2 to 40% by weight of trimer acid having 34 carbon atoms (Versadim 216; manufactured by Henkel Hakusui Co., Ltd.) are representative. And preferred.

The monocarboxylic acid (a) in the polymerized fatty acid-based polyamide resin (a) has 2 to 28 carbon atoms.
Linear or branched saturated fatty acids (acetic acid, propionic acid,
Caprylic acid, lauric acid, palmitic acid, stearic acid, 2-ethylhexanoic acid, isostearic acid, etc.), unsaturated fatty acids with 2 to 18 carbon atoms (acrylic acid, oleic acid, linoleic acid, linolenic acid, etc.), natural fats and oils Obtained mixed fatty acid (tall oil fatty acid, rice bran oil fatty acid, soybean oil fatty acid, beef tallow fatty acid, etc.), aliphatic oxymonocarboxylic acid (ricinolenic acid, castor oil fatty acid, etc.), aromatic oxymonocarboxylic acid [salicylic acid, P- Oxybenzoic acid, diphenolic acid, such as 1,4-bis (hydroxyphenyl) acetic acid], and mixed fatty acids of two or more of these. If necessary, use a dicarboxylic acid other than polymerized fatty acid, for example, an aliphatic dicarboxylic acid (adipic acid, azelaic acid, sebacic acid, etc.), an aromatic dicarboxylic acid (isophthalic acid, terephthalic acid, etc.), and a mixture of two or more thereof. You can

The amount of the polymerized fatty acid used in the acid component (polymerized fatty acid and monocarboxylic acid) is usually 50 to 9 of the total acid component.
It is 8 equivalent%, preferably 60 to 96 equivalent%, and the amount of monocarboxylic acid used is usually 2 to 50 equivalent%, preferably 4 to 40 equivalent% of the total acid components. The amount of polymerized fatty acid used is less than 50 equivalent% or the amount of monocarboxylic acid used is 50
If the equivalent% is exceeded, the molecular weight of the polyamide resin will decrease,
The persistence of the effect of preventing the attachment of aquatic organisms is reduced. Further, when the amount of polymerized fatty acid used exceeds 98 equivalent%, or the amount of monocarboxylic acid used is less than 2 equivalent%, the molecular weight becomes high, and it cannot be sufficiently eluted from the nylon resin molded product, and as a regulator, It has no effect.

The polyamine (c) in the polymerized fatty acid-based polyamide resin (a) includes aliphatic polyamines (ethylenediamine, diethylenetriamine, propylenediamine, etc.), alicyclic polyamines (isophoronediamine, etc.), polyamines having an aromatic ring ( Xylylenediamine, diaminodiphenylmethane, etc.) and mixtures of two or more thereof. Of these, preferred polyamines are ethylenediamine and diethylenetriamine.

The polymerized fatty acid-based polyamide resin (a)
Has a weight average molecular weight of usually 3,000 to 100,000, preferably 5,000 to 50,000. The method for producing the polyamide resin (a) may be an ordinary method, and the reaction ratio of the acid component and the amine component is 0.8 to 1.
2, preferably 0.9 to 1.1. When the equivalent ratio of the acid component or the amine component is less than 0.8, the molecular weight becomes too low and the durability of the effect of preventing aquatic organisms from adhering decreases, which is not preferable. The reaction temperature is generally 140 to 260 ° C, preferably 180 to 230 ° C. Depending on the case,
The reaction may be carried out under reduced pressure to facilitate the removal of volatile components. If the reaction temperature is lower than 140 ° C, the reaction is difficult to proceed, and if it exceeds 260 ° C, side reactions such as decomposition reaction are promoted.

The amount of the regulator (D) used is determined by the conditions such as the place and period of application of the molded nylon resin product of the present invention. The antifouling agent (B) and the cuprous oxide ( 20 to 5 relative to 100 parts by weight of C).
The amount is 00 parts by weight, preferably 50 to 300 parts by weight. 5
If it exceeds 100 parts by weight, the concentrations of the compound (B) and cuprous oxide (C) will be low, and a sufficient effect of preventing the attachment of aquatic organisms cannot be obtained. The total weight of the compound (B), cuprous oxide (C) and modifier (D) is usually 150 parts by weight or less, preferably 80 parts by weight or less, relative to 100 parts by weight of the nylon resin (A). is there. If it exceeds 150 parts by weight, the resin strength and the like will be significantly reduced.

The kneading of the compound (B) and the cuprous oxide (C) into the nylon resin (A) in the present invention can be carried out by various known mixers, for example, an extruder, a Brabender, a kneader. , Burberry mixer and the like. The temperature at the time of kneading varies depending on the melting temperature of the nylon resin (A), and for example, 6 nylon has a temperature of 200 to 300 ° C, preferably 230 to 260 ° C.

[0022]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The parts in the examples are based on weight.

Example 1 10 parts of 2-mercaptobenzimidazole, 20 parts of cuprous oxide [R-30 (manufactured by Nisshin Chemco)] and 6 for fiber
100 parts of nylon pellets are melt-mixed at 240 ° C. by an extruder type spinning machine and discharged from a spinneret having a hole diameter of 0.6 mm and 96 holes, and then the discharged yarn is heated to 300 mm under the spinneret and heated at the same temperature of 250 ° C. Hold the condition, then 25
It was cooled and solidified by blowing a cooling air of ℃ over 500 mm at 7.0 m ² / min. Then, after stretching and relaxation heat treatment by a conventional method, two obtained stretched yarns were combined. Next, using a knotless knitting machine, the twisted fishing net (10
0 pieces, 5 sections, 40 cm × 60 cm) were prepared.

Example 2 A test fishing net was obtained in the same manner as in Example 1 except that 10 parts of 2-mercaptobenzimidazole in Example 1 was changed to 10 parts of 2-mercaptobenzimidazole zinc salt.

Example 3 In the same manner as in Example 1 except that 10 parts of 2-mercaptobenzimidazole of Example 1 was changed to 10 parts of copper octylate [Nikka Octix copper 18% (manufactured by Nippon Kagaku Sangyo Co., Ltd.)]. A fishing net for testing was obtained.

Example 4 A fishing net for test was obtained in the same manner as in Example 1 except that 10 parts of 2-mercaptobenzimidazole of Example 1 was changed to 10 parts of zinc dimethyldithiocarbamate.

Example 5 Polymerized fatty acid [Versadim 216 (manufactured by Henkel Hakusui)] 270.7 g (0.94 equivalent), rice bran oil oil fatty acid 16.8 g (0.06 equivalent) and ethylenediamine 3
Charge 0.0 g (1.00 equiv.) To a reaction vessel and add 200
The reaction was carried out at 0 ° C. for 5 hours to obtain a polyamide resin (weight average molecular weight by GPC: 23000). In the same manner as in Example 1 except that 10 parts of 2-mercaptobenzimidazole of Example 1, 20 parts of cuprous oxide and 100 parts of 6 nylon for fibers were further added with 10 parts of the polymerized fatty acid-based polyamide resin obtained above. I got a test fishing net.

Example 6 Polymerized fatty acid (Versadim 216) 244.8 g (0.
85 equivalents), rice bran oil fatty acid 7.4 g (0.026 equivalents), acetic acid 7.4 g (0.124 equivalents) ethylenediamine 27.1 g (0.9925 equivalents) and diethylenetriamine (0.0475 equivalents) were used. In the same manner as in Example 5, a polymerized fatty acid-based polyamide resin (weight average molecular weight by GPC: 8000) and a test fishing net to which the polyamide resin was added were obtained.

Comparative Example 1 6 parts were prepared by mixing 15 parts of 3'-isopropyl-benzanilide, 15 parts of a chlorinated rubber resin [Aloprene R-10 (manufactured by ICI)] and 70 parts of xylene in an aquatic organism-preventing agent liquid.
A nylon fishing net (100 pieces, 5 sections, 40 cm x 60 cm) was dipped and air-dried for 2 days to prepare a test fishing net.

Comparative Example 2 10 parts of 2-mercaptobenzimidazole of Example 1,
In the same manner as in Example 1 except that 20 parts of cuprous oxide and 100 parts of nylon pellets for fibers were changed to 8 parts of 2- (4-thiazolyl) benzimidazole, 17 parts of cuprous oxide and 105 parts of 6 nylon pellets for fibers. A fishing net for testing was obtained.

Comparative Example 3 A 6-nylon fishing net without any anti-adhesion treatment was used as a test fishing net.

Sea Immersion Test The test fishing nets prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were attached to a stainless steel frame, hung in the sea, kept at a water depth of 1.5 m, and pulled up at regular intervals to create organisms. Was observed. The anti-adhesion effect is the area of the test net (40 cm x 60 c
It was evaluated by the ratio of the area occupied by the attached organisms to m). The results are shown in Table 1.

[0033]

[Table 1]

[0034]

INDUSTRIAL APPLICABILITY The aquatic organism adhesion preventing nylon resin molded product of the present invention can maintain a high aquatic organism adhesion preventing effect for a long time even if it is kneaded and molded under high temperature conditions.
Therefore, aquatic organisms such as barnacles, mussels, sea bream, diatoms and cyanobacteria adhere to fishing nets formed from the nylon resin of the present invention, incidental ropes, ship bottoms, seawater intake channels, seawater intake channel walls, underwater structures, etc. Can be prevented for a long time.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08K 5/09 KKV 7242-4J 5/3447 5/39 KLA 7242-4J C08L 77/00 KKZ 9286- 4J // (A01N 59/20 43:52) (A01N 59/20 37:02) (A01N 59/20 37:06) (A01N 59/20 47:14)

Claims (4)

[Claims] 1. Nylon resin (A) containing at least one compound (B) selected from the group consisting of 2-mercaptobenzimidazole, zinc salt thereof, copper salt of aliphatic carboxylic acid and zinc salt of dithiocarbamic acid. And a cuprous oxide (C) are kneaded and molded to form an aquatic organism adhesion-preventing nylon resin molded product. 2. The aquatic organism attachment-preventing nylon resin molded product according to claim 1, wherein the amount of the compound (B) is 5 to 30 parts by weight based on 100 parts by weight of the nylon resin (A). 3. The aquatic organism adhesion-preventing nylon resin molded article according to claim 1, wherein the amount of cuprous oxide (C) is 5 to 30 parts by weight with respect to 100 parts by weight of the nylon resin (A). 4. The aquatic organism-attachment-preventing nylon resin molded article according to claim 1, further comprising a polymerized fatty acid-based polyamide resin (a) added and kneaded.