JPH01193201A - Antifouling agent composition for fishing net - Google Patents

Abstract

PURPOSE:To obtain the title composition showing long-term antifouling effects, extremely small tack in spite of high flexibility, free from stiffness, by blending a tributyltin methacrylate copolymer useful as an excellent antifouling agent for fishing net with a purified mineral oil. CONSTITUTION:An antifouling agent for fishing net consisting essentially of a tributyltin methacrylate copolymer (e.g. one obtained by copolymerizing a tri-organotin salt of polymerizable unsaturated monobasic acid or polybasic acid with a polymerizable unsaturated monomer) containing at least one group shown by the formula -COOSnR3 (R is alkyl or phenyl) in the molecule is blended with preferably 1-50wt.% based on the organotin-containing copolymer of one or more purified mineral oil (e.g. insulating oil, refrigerator oil or turbine oil).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antifouling agent composition for fishing nets that does not cause stiffness or stickiness in fishing nets.

[Conventional technology]

Tributyltin methacrylate copolymer is used as an excellent antifouling agent for fishing nets.

[Problem that the invention seeks to solve]

However, fishing nets treated with conventional tributyltin methacrylate copolymers produce a little more than 100 lbs. in cold regions.

For this reason, the net becomes bulky when it is rolled up or piled up, making it difficult to move and transport the fishing net, and in extreme cases, it causes cracks in the membrane, which leads to fouling.

In order to improve this, methods include copolymerizing a polymer with a lower glass transition point with tributyltin methacrylate, and adding plasticizers (chlorinated paraffin, dioctyl phthalate, tricresyl phosphate, etc.) to the tributyltin methacrylate copolymer. Although there are methods, the use of tributyl/l/a methacrylate copolymers obtained by these methods results in extreme tackiness of the coating and the copolymer film is destroyed.

It also speeds up the solubility of the paint film and shortens the antifouling effect.

[Failure to solve the problem]

As a result of intensive research to improve the above drawbacks, the inventors of the present invention found that
In organic tin-based antifouling agents for fishing nets, if an antifouling agent composition for fishing nets obtained by adding refined mineral oil is used,
The inventors have found a solution to the above problems and have arrived at the present invention.

That is, in the present invention, at least one group -C in one molecule
A fishing net antifouling agent containing a triorganotin-containing copolymer having OO5nR3 (in the formula R represents a lower alkyl group or a phenyl group) as a main component, which is characterized in that it is used with the addition of purified mineral oil. It is a stain composition.

As the triorganotin-containing copolymer in the present invention, a copolymer 1 having at least one group -COO5nRs (R has the same meaning as above) in nine molecules is used, for example, No. 44-9579.

Special Publication No. 46-IL192 and Special Publication No. 49-2049
A triorganotin-containing copolymer obtained by copolymerizing a triorganotin salt of a monopolymerizable unsaturated/basic acid or a polybasic acid described in Publication No. 1 with a polymerizable unsaturated monomer.

■British Patent No. 1408827 and Japanese Unexamined Patent Publication No. 55-696
A high acid value vinyl resin obtained by copolymerizing a polymerizable unsaturated basic acid or a polybasic acid and a polymerizable unsaturated monomer described in Publication No. 62 is reacted with a triorganotin compound. tri-organotin-containing copolymer.

Examples include.

Here, the triorganotin group in the triorganotin-containing copolymer is when the organic group is a lower alkyl group having 1 to 8 carbon atoms or a phenyl group.

It is a trialkyltin group or a triphenyltin group.

In addition, examples of the polymerizable unsaturated basic acids used in the above methods Examples of polymerizable unsaturated polymers which can be further used in copolymerization include acids or acid anhydrides, such as methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, ethyl acrylate, and butyl acrylate.

Acrylic compounds such as octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, cyclohexyl acrylate, phenyl acrylate, and hydroxyethyl acrylate.

Vinyl chloride, vinylidene chloride, acrylonitrile.

methacrylonitrile, vinyl acetate, vinyl petite),
Examples include vinyl compounds containing functional groups such as 7" thylhinyl ether, octyl vinyl ether, and dodecyl vinyl ether, and vinyl hydrocarbons such as ethylene, butadiene, and styrene.
Used in one species or in combination of two or more.

The refined mineral oil used in the present invention is 9,000 yen, usually 1 petroleum heavy gas oil,
Alternatively, it is a light lubricating oil or a lubricating oil fraction.

It has a boiling point of 800° C. or higher at normal pressure, and contains paraffin as the main component, but may also contain naphthenes and aromatics.

In addition, the above-mentioned fractions are further purified using solvents, chemical and/or physical treatment means, and the above. There are 1 types
Examples include refined mineral oils listed in Table 1 of JIS.

Table 1 The antifouling agent composition for fishing nets of the present invention has a triorganotin-containing copolymer as its main component, and is obtained by adding one or more refined mineral oils listed in Table 1. The refined mineral oil is usually added in an amount of 1 to 50% by weight based on the triorganotin-containing copolymer. If the addition ratio is less than 1% by weight, the hardness cannot be improved.

Flexibility cannot be compensated by the copolymer composition alone in the copolymer. On the other hand, if the addition ratio exceeds 50% by weight, the coating film strength will decrease, which is not preferable.

The thus obtained antifouling agent composition for fishing nets of the present invention is prepared by adding a coloring dye, if necessary, to toluene.

Hydrocarbons such as xylene, alcohols such as denatured alcohol, butyl alcohol, isopropyl alcohol, and ethyl acetate. Esters such as butyl acetate.

It is dissolved in various solvents such as ketones and placed in a dipping bath.
It is applied to fishing nets by immersing them in this bath, taking them out and drying them.

[For production]

The antifouling agent composition for fishing nets of the present invention has the following features. In other words, by adding refined mineral oil to the organotin-containing copolymer of the present invention, it exhibits a long-term antifouling effect compared to conventional tributyltin methacrylate copolymers, and also has less tackiness despite its greater flexibility. It is possible to obtain a dirt-proof fishing net with extremely few burrs.

Pickled beak-Isu-kai-i, etc. [Example] Next, the present invention will be described with reference to production examples and examples, in which % in each example indicates weight %.

Production Example A In an Xt-four flask equipped with a thermometer, a reflux condenser, and a stirrer, tributyltin methacrylate 260f, methyl methacrylate 1409, and xylene 4002 were charged, and further 5t of benzoyl peroxide was added.
Polymerization was carried out at 90 to 95°C for 8 hours to obtain a copolymer solution (A). This copolymer solution [A] was a pale yellow liquid with a heating residue of 49.8%, a viscosity (25° C.) of 525 cps, and a weight average molecular weight of 41,000.

Production Example B In a 14-eye flask equipped with a thermometer, reflux condenser, stirrer, and dropping spout, add 59.6 f of methacrylic acid, 1169.2-ethylhexyl acrylate (4F), 200 f of xylene, and 200 t of isopropyl alcohol/' was charged, 15 f of azobisisobutyronitrile/l was added, polymerization was carried out at 75 to 8°C for 8 hours, and bis(tributyltin) oxide 222 was added to the resulting copolymer solution. ．． ．． Drop 5f and add 100~1
The mixture was stirred at 10° C. for 1 hour to obtain a copolymer solution (B). This copolymer solution CB) is a slightly yellow liquid with a heating residue of 49.6
%, viscosity (25°C) 450Cp8 and weight average molecular weight 4
5,000.

Production Example C In a reaction vessel similar to Production Example B, maleic anhydride 34f,
20 f of methyl methacrylate 1409.2-ethylhexyl acrylate and 400 t of xylene were added, and further 8 f of benzoyl peroxide was added.
Polymerization was carried out at ℃ for 8 hours, and bis(tributyltin) oxide 2062 was further added dropwise to the obtained copolymer solution.
The mixture was stirred at 00 to 110°C for 1 hour to obtain a copolymer solution [C]. This copolymer solution [C] was a pale yellow liquid with a heating residue of 49.8%, a viscosity (at 25° C.) of 525 C20, and a weight average molecular weight of 45,000.

Equipped with a manufacturing example thermometer, reflux condenser with dehydration device, and stirrer Lfcl
To T-Yotsuro Wonuko, anhydrous maleic fi 31.22, methyl methacrylate 1209.2-ethylhexyl acrylate 20 f and xylene 4001 were charged, and azobisisobutyronitrile was added at 32, and the mixture was heated to 75-80
Polymerization was carried out at ℃ for 8 hours, and 2848 t of triphenyltin hydrooxide was added to the obtained copolymer solution, and 90
The mixture was heated to ˜100° C. and stirred for 2 hours under reduced pressure (800 mmHg) with reflux dehydration.

A copolymer solution [D] was obtained. This copolymer solution [D] is a slightly yellow liquid with a heating residue of 49.7% and a viscosity (25°C) of 41
Ocps and weight average molecular weight of 44,000.

Production Example E Into the same reaction vessel as Production Example B, methacrylic acid 6 & 9F,
Methyl methacrylate 100 f, xylene 20
0 f and iso7'' RobiμAlco-A/200f, add azobisisobutyronitrile 52 to the salad, and add 7
Polymerization was carried out at 5 to 80°C for 8 hours, and 238.49% of bis(tributyltin) oxide was added to the resulting copolymer solution.
was added dropwise and stirred at 100 to 110°C for 1 hour to obtain a copolymer solution [E]. This copolymer solution [E] is a slightly yellow liquid with a heating residue of 49.6% and a viscosity (25°C) of '490.
cps and a weight average molecular weight of 48,000.

Production Example F In a reaction vessel similar to Production Example A, aoo t of triglytin methacrylate and 90 f of methyl methacrylate were added.

n-butyl acrylate lOt and xylene 400f
and further added benzoyl peroxide 5f and polymerized at 90 to 95°C for 8 hours to form a copolymer solution CF.
, l was obtained. This copolymer solution [F] was a pale yellow liquid with a heating fraction of 49.9%, a viscosity (at 25° C.) of 440 Cpm, and a weight average molecular weight of 87,000.

Production Example G In a reaction vessel similar to Production Example A, 280 f of tributyltin methacrylate and 20 t of methyl methacrylate were added.

Charge 682 tons of 2-ethylhexyl acrylate (n-butyl acrylate) and 400 tons of xylene, and add 5 grams of benzoyl peroxide.

Polymerization was carried out at 90 to 95°C for 8 hours to form a copolymer solution [G]
I got it. This copolymer solution (Gel) was a pale yellow liquid with a heating residue of 49.8%, a viscosity (at 25° C.) of 870 cps, and a weight average molecular weight of 86,000.

Examples 1 to 8 and Comparative Examples 1-4 Using the copolymer solutions [A] to (F) obtained in Production Examples A to F, refined mineral oil was added in the proportions shown in Table 2 below to prepare the copolymer solutions of the present invention. Antifouling agent compositions for fishing nets (!ii! Examples 1 to 8) were obtained.

In addition, a plasticizer was added to the copolymer solution [A) or [E] (Comparative Examples 1 to 2) to internally plasticize the copolymer solution CG).
(Comparative Example 3) and conventional copolymer solution [
A] alone (Comparative Example 4) to obtain fishing net antifouling agent compositions of Comparative Examples.

The above is summarized in Table 2.

Table 2 (Note) The following refined mineral oils or plasticizers listed in Table 2 were used.

(Note 1) Neovac MR-100. Manufactured by Matsumura Oil Co., Ltd. (?
l) Cosmo Gya 5E, manufactured by Cosmo Oil Co., Ltd. (Note 3)
Sumoi/VP-150, manufactured by Matsumura Oil Co., Ltd. (Note 4) Chlorine content 40%, Reagent grade (Note 5) Reagent grade 11 Strength and adhesion evaluation test Examples 1 to 8 and Comparative Example 1- 100 parts of xylene was added to 100 parts of each fishing net antifouling agent composition obtained in step 4 to dilute it.

A polyethylene fishing net (400D, 20
(Book, Section 8) 20 x 40 slices were immersed, removed after a few minutes, and air-dried at room temperature for one day. The stickiness of the net is at room temperature (1
It was examined by touch at 5°C.

After drying, the net was left in a room at -5°C for 8 hours.

In the same room, untreated fishing nets of the same shape were used as blanks to check the degree of burrs by touch.

(2) Immersion antifouling test 250 parts of xylene was added to 100 parts of each fishing net antifouling agent composition obtained in Examples 1 to 8 and Comparative Examples 1 to 4 to dilute it.

A polyethylene fishing net (400D, 20
(Book, Section 8) 80 x 40α sections were immersed, removed after a few minutes, and air-dried at room temperature for 1 day. Each net treated with an antifouling agent was attached to an iron frame and immersed in a raft for 6 months in Owase Bay, Mie Prefecture, and the state of adhesion of contaminant organisms was observed every month.

The results of each of the above tests are shown in Table 3.

The symbols in the table represent the following evaluations.

Strong adhesion Antifouling effect ○: Almost none Almost none Slime after 3 months △
: A little reed A little reed Fujibbo in the 3rd month × :
Extremely large Extremely large Fujibbo in the second month
3 Table [Effects of the Invention] As is clear from Table 3, when treated with the antifouling agent composition for fishing nets of the present invention, the fishing nets are free of strong stains and stickiness and exhibit excellent antifouling effects. be able to. Such effects can only be achieved by using a triorganotin-containing copolymer as the main component and adding refined mineral oil.

Claims (2)

[Claims] (1) At least one group -COOSnR_3 in the molecule
(In the formula, R represents a lower alkyl group or a phenyl group) A fishing net antifouling agent mainly composed of a triorganotin-containing copolymer, which is characterized in that it is used with the addition of purified mineral oil. agent composition. (2) The antifouling agent composition for fishing nets according to claim 1, wherein the amount of refined mineral oil added is 1 to 50% by weight based on the triorganotin-containing copolymer.