JPH0120665B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antifouling paint containing an imide compound as a main ingredient. Fishing nets such as fixed nets and aquaculture nets, the bottom of ships, equipment placed in seawater such as buoys, heat exchangers for various industries,
In areas that come into contact with water for a long period of time, such as cooling water intake channels, aquatic organisms such as shellfish and algae adhere and proliferate significantly, leading to a decline in the performance of these equipment. The intake channel has to be cleaned within a short period of time, and the economic loss caused by this is enormous. Therefore, it is essential to prevent the attachment and reproduction of harmful aquatic organisms in freshwater or seawater, and the use of antifouling agents may be considered to achieve this objective. Traditionally, as antifouling agents, copper compounds, organic tin compounds such as tributyltin oxide, heavy metal compounds such as mercury oxide, and organic chlorine or organic sulfur compounds have been generally used in combination with spreading agents. It is said that tin compounds have great antifouling effects.
However, these compounds are highly toxic and are not necessarily desirable from the viewpoint of environmental protection and safety and health. As a result of extensive research aimed at improving the drawbacks of such conventional antifouling paints, the present inventors have discovered that antifouling paints using imide compounds as antifouling agents are effective, and have achieved the present invention. . That is, the present invention is based on the general formula () [Wherein, D represents the following general formulas (a), (b) and (c)

【formula】

【formula】

[Formula] (However, in the above formula (a), X and Y are the same or different and each represents a hydrogen atom or a halogen atom, and in formulas (b) and (c), l and m are respectively 0
or 1. ), where R is n consisting of 2 to 150 carbon atoms.
represents a valent aliphatic group, and n represents an integer of 1 to 3. ]
This is an antifouling paint characterized by containing an imide compound represented by: Group R in the imide compound represented by the general formula () used as an active ingredient of the antifouling paint of the present invention
is a straight chain or branched alkyl group, alkenyl group,
It may be an alkylene group, an alkenylene group, a cycloalkyl group, or a cycloalkylene group,
Furthermore, the group R may include several alkyl groups, alkenyl groups, alkylene groups, which are bonded to each other by oxygen atoms,
Also included are groups consisting of an alkenylene group, a cycloalkyl group, or a cycloalkylene group. The imide compound represented by the general formula () can be prepared by preparing a primary amine or a polyamine using the formula () in an organic solvent by a known method. (In the formula, D has the same meaning as in the above formula ().) It can be produced by reacting with a carboxylic acid anhydride represented by the following formula. Very typical examples of imide compounds contained in the antifouling paint of the present invention include N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-
Allylmaleimide, N-n-butylmaleimide,
N-2-methyl-propylmaleimide, N-cyclohexylmaleimide, 2-N-maleimidoheptane, N-2-ethylhexylmaleimide, N-
Octylmaleimide, N-heptylmaleimide,
N-n-octadecylmaleimide, N-t-octadecylmaleimide, N-n-eicosylmaleimide, N-t-eicosylmaleimide, N-pentylmaleimide, N-neopentanolmaleimide, N-(2,2'- hydroxyethoxyethyl)
Maleimide, N-(2-dimethylaminoethyl)
Maleimide, N-(1-methoxymethylpropyl)
maleimide, N,N'-ethylene bismaleimide,
N,N'-1,4-butane bismaleimide, N,
N'-1,6-hexane bismaleimide, N,
N'-neopentane bismaleimide, N, N'-1,
12-dodecane bismaleimide, N,N'-1,16
-hexadecane bismaleimide, N, N'-4,
7-dioxadecane-1,10-bismaleimide,
N,N'-4,9-dioxadodecane-1,12-
Bismaleimide, N,N'-4,7,10-trioxatridecane-1,13-bismaleimide, N,
N'-7-methyl-4,10-dioxatridecane-1,13-bismaleimide, N,N'-3,6,
9,12-tetraoxatetradecane-1,14-bismaleimide, N,N'-3,6,9,12,15-
Pentaoxaheptadecane-1,17-bismaleimide, bis(3-N-maleimidopropyl)polytetrahydrofuran, and further (In the formula, a=2.6, 5.6, or 33.1, and hereinafter abbreviated as BMI D-230, BMI D-400, or BMI D-2000, respectively.) (In the formula, a+c≒3.5, b≒13.5, 20.5 or
It is 45.5. ) (In the formula, x, y, and z are all numbers greater than or equal to 1, and x+
y+z≒5.3, and is abbreviated as TMI T-403. ), Maleimide compounds such as 1,2(1,3 or 1,4)-bis(N-maleimidomethyl)cyclohexane, in which the hydrogen atom bonded to the unsaturated carbon atom in the maleimide group of these maleimide compounds is replaced with a chlorine atom. maleimide compound, N-methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalimide, N-isopropyl-
3,6-endomethylene-1,2,3,6-tetrahydrophthalimide, N-(1-methoxymethylpropyl)-3',6'-endomethylene-1',2',
3′,6′,-tetrahydrophthalimide, N,N′-
(1,6-hexane)bis-3',6'-endomethylene-1',2',3',6'-tetrahydrophthalimide, N,N'-(4,7-dioxadecane)-1,
10-bis[or N,N'-(1,12-dodecane)bis]-3',6'-endomethylene-1',2',3',6'
−
Tetrahydrophthalimide, N,N'-(4,9-
dioxadodecane)-1,12-bis-3′,6′-endomethylene-1′,2′,3′,6′-tetrahydrophthalimide, and furthermore, (In the formula, a = 2.6, 5.6 or 33.1.) Similarly, the maleimide compound of the above maleimide compound has a 3 (or 4)-methyl-1,2,3,6-tetrahydrophthalimide group, 1,2,3,6-tetrahydrophthalimide group, 3,6-endoethylidene-1,2,3,6
-tetrahydrophthalimide group or 3 (or 4)-methyl-3,6-endomethylene-1,
Mention may be made of imide compounds substituted with 2,3,6-tetrahydrophthalimide groups. In addition, when n is plural in the imide compound of general formula (), it is desirable from the viewpoint of production that the groups D are the same type, but they may be different types. Particularly preferred imide compounds include N-(1-methoxymethylpropyl)maleimide, N-n-octadecylmaleimide, N,N'-(4,7-dioxadecane)-1,
10-bismaleimide, N,N'-1,12-dodecanebismaleimide, N,N'-4,9-dioxadodecane-1,12-bismaleimide, N,N'-
3,6,9,12-tetraoxatetradecane-
1,14-bismaleimide, N,N'-7-methyl-4,10-dioxatridecane-1,13-bismaleimide, BMI D-230, BMI D-400, BMI
D-2000, N,N'-4,7-dioxadecane-
1,10-bis-3',4'-dichloromaleimide and TMI T-403. In the present invention, these imide compounds can be used not only alone, but also in combination of two or more, and known antifouling agents, such as copper compounds such as copper naphthenate and cuprous oxide, bis(trifluoride), etc. -organotin compounds such as n-butyltin) oxide, bis(tri-n-butyltin) mesodibrosuccinate, triphenyltin hydroxide, tributyltin chloride, or N-trichloromethylthio-4-cyclohexene-1,2 - Of course, it is also possible to use it in combination with a compound such as dicarboximide. Since organic tin compounds have the above-mentioned drawbacks, it is preferable to avoid their combined use unless absolutely necessary. The amount of the imide compound that is the antifouling agent of the present invention is not particularly limited, but it is usually 0.1 to 0.1 of the total amount of the antifouling paint.
In the range of 50% by weight, preferably from 1 to 40% by weight
Prepare and use the paint so that it falls within the following range. If the antifouling agent is less than 0.1 weight, it will have little antifouling effect;
On the other hand, if it is more than 50% by weight, the amount is excessively large and no superior effect is observed. The imide compound of the present invention is mixed with a film forming agent, that is, a spreading agent, to prepare an antifouling paint, which is applied to fishing nets, ship bottoms, cooling water intake channel walls, etc. to prevent the adhesion and propagation of aquatic organisms. be able to. As a spreading agent, oil varnish, acrylic resin,
Synthetic resins such as vinyl resin or polybutene, petroleum resins such as coumaron indene resin, rosins such as gum rosin or modified rosin, and artificial rubber are used. There are no particular restrictions on the diluent used in the antifouling paint of the present invention, and commonly used diluents such as toluene, o(m or p)-xylene, isopropyl alcohol, ethyl acetate, and methyl isobutyl ketone may be used. The amount of diluent to be used is not particularly regulated, but for example, when used in fishing nets, the amount of solids attached to the fishing net after drying is generally about 50%.
From the weight%, the antifouling paint's 40 to 60
Weight percent is preferred. Next, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited to these Examples. In Examples and Comparative Examples, the formulation composition is shown in parts by weight. Example 1 N-(1-methoxymethylpropyl)maleimide 10, polybutene (molecular weight 650) 20, rosin 40,
An antifouling paint was prepared by blending titanium white 5, talc 25, toluene 60, and methyl isobutyl ketone 40 as ingredients, sufficiently pulverizing and mixing in a pocket mill, and then sizing.
Next, apply the antifouling paint to a polyethylene net (2 mm thick).
φ, mesh size 40mm, size 400mm x 400mm),
This net was immersed in the sea and the amount of marine life attached to it over time was observed. Evaluation was performed in five stages based on the following criteria (hereinafter based on these criteria). 5...No attached organisms were observed. 4...Slight adhesion is observed. 3... Considerable adhesion is observed. 2... Severe adhesion. 1... It adheres to such an extent that the mesh is no longer visible. The results are shown in Table 5. Examples 2 to 6 Antifouling paints consisting of the components shown in Table 1 were prepared in the same manner as in Example 1, using various imide compounds instead of N-(1-methoxymethylpropyl)maleimide, and an immersion test was conducted. The results are shown in Table 5. Examples 7 to 9 Antifouling paints consisting of the ingredients shown in Table 2 were prepared in the same manner as in Example 1 using vinyl resin and boiling oil instead of polybutene, and after being applied to fishing nets, an immersion test was conducted in the sea. Ta. The results are shown in Table 5. Examples 10 to 14 Antifouling paints having the components shown in Table 3 were prepared in the same manner as in Example 1 using various imide compounds and known antifouling agents, and the results of an immersion test are shown in Table 5. Comparative Examples 1 to 3 Bistributyltin oxide, N-(trichloromethylthio)-4-cyclohexene-1,2-
An antifouling paint consisting of the components shown in Table 4 was prepared in the same manner as in Example 1 using dicarboximide or copper naphthenate as an antifouling agent, and an immersion test was conducted. The results are shown in Table 5. Examples 15-33 N-(1-methoxymethylpropyl) of Example 1
Antifouling paints were prepared in the same manner as in Example 1, except that various imide compounds shown in Table 6 were used in place of maleimide, and the results of the immersion test are shown in Table 6. Examples 34-37 N,N'-4,7-dioxadecane- as antifouling agent
An antifouling paint consisting of the ingredients shown in Table 7 was prepared in the same manner as in Example 1 using 1,10-bismaleimide, and an immersion test was conducted. Table 7 shows the results.

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Claims (1)

[Claims] 1 General formula () [Wherein, D represents the following general formulas (a), (b) and (c) [Formula] [Formula] [Formula] (However, in the above formula (a), X and Y are the same or different, and each represents a hydrogen atom or a halogen atom, and in formulas (b) and (c), l and m are each 0 or 1.), and R has 2 to 150 carbon atoms. It represents an n-valent aliphatic group, and n represents an integer of 1 to 3. ] An antifouling paint characterized by containing an imide compound represented by the following.