JPS60116615A - Antistaining agent - Google Patents

Abstract

PURPOSE:An antistaining agent, containing a novel triorganotin-containing copolymer containing N-coordinated-triorganotin-containing repeating units and comonomer repeating units as an active constituent, and capable of preventing the adhesion of staining organisms for a long term, and having high storage stability. CONSTITUTION:An antistaining agent containing a triorganotin-containing copolymer containing at least one N-coordinated-triorganotin-containing repeating unit expressed by formulas I -III (R is 1-8C alkyl, cycloalkyl, etc.; X is -NCS, -NCO, etc.; R<1> and R<2> are H, methyl, etc.; p is an integer 1-4; Y is 1-12C alkylene, phnylene, etc; A and B are H, 1-18C alkyl, cycloalkyl, etc.) and comonomer repeating units derived from at least one comonomer selected from acrylic compounds, vinyl based compound, etc. having functional groups as an antistaining component. The film surface is always renewed in dipping in seawater and the antistaining property can be maintained for a long period.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antifouling agent containing as an active ingredient a triorganotin-containing copolymer having an N-coordinated triorganotin-containing repeating unit in the polymer main chain.

Seaweed and seaweed on the bottom of ships; fishing nets such as aquaculture nets and fixed nets, and general underwater structures.

Contaminant organisms such as brown algae and other seaweed, Fujibbo, Serpura, oysters, sea squirts, and bryozoans adhere to the surface, causing various types of damage.

In other words, when these polluting organisms adhere to the bottom of a ship, they increase the frictional resistance between the ship's hull and the seawater, reducing ship speed and increasing fuel consumption. In addition, when contaminated organisms adhere to fishing nets, they clog the nets, obstructing the flow of seawater, causing poor growth of farmed fish, and reducing the amount of fish caught.In some cases, fishing nets with increased resistance due to attached organisms may be washed away by ocean currents. This will result in a situation where the

In order to suppress such damage, various antifouling agents and paints are applied to the sea or to the surface of substrates exposed to water.Today, in particular, antifouling paints are applied to the bottoms of large tankers.
Preventing the attachment of contaminant organisms over a long period of time is considered important from the viewpoint of economic efficiency and resource conservation.

In order to prevent the adhesion of contaminant organisms, tri-organotin compounds9, such as tributyltin compounds (oxide, chloride, fluoride) and triphenyltin compounds (hydroxide, chloride, etc.) have conventionally been used.

Because it is an antifouling agent made by dispersing or dissolving a strong single substance,
In addition to causing problems such as flaking during paint production and application, in terms of antifouling performance, it elutes into seawater at an early stage, and it is difficult to control the elution, so long-term antifouling cannot be obtained.

Therefore, at present, this has been improved to include -COO3nR in the molecule.
A triorganotin-containing polymer type antifouling agent having 3 (R is an alkyl group or a phenyl group) has been used, but it has the following drawbacks. Namely.

First, these polymer-type antifouling agents thicken and gel during storage. For example, triphenyltin-containing polymers are particularly prone to this phenomenon, and if it is severe, it will gel during the polymerization process during production, making it difficult to obtain a stable polymer. In addition, for long-term antifouling purposes, tributyltin-containing polymers and copper compounds, such as cuprous oxide, are used in combination with ship bottom paints, but in this case, the thickening and gelation of the paint during storage is further promoted, making it unusable. A situation arises.

In order to prevent thickening and gelation during storage, methods have been adopted such as adding a stabilizer and separating the polymer component and copper compound component and mixing them immediately before forming the paint, but these methods are essential It's not a solution. Yet another drawback is the difficulty in producing triphenyltin-containing polymers that are particularly effective against algae.

This is the result of the inventors' research from a new perspective.

If a completely new triorganotin-containing copolymer containing an N-coordinated triorganotin compound in the molecule is used as an antifouling component, an antifouling agent that does not have the above drawbacks and exhibits various excellent effects can be obtained. The present invention was based on the discovery that this can be obtained.

That is, the present invention has two components in the main chain of the two polymers.

CIb) (Ic)11 [In the formula, R is the same or different alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 8 carbon atoms, and X is a group -NC8, a group -NCO, a group -N3 or group -CN
R1 and R2 are hydrogen atoms and methyl groups.

independently selected from the ethyl group and the halogen atom.

Is p an integer between 1 and 4? , Y is a group-5 having 1 to 12 carbon atoms
-Z- (wherein Z is an alkylene group or group having 2 to 12 carbon atoms -(
CH2) @4f'f (m: an integer from 1 to 8).

A and B may or may not be bonded to each other.

(i) When A and B are not bonded to each other; A and B are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a hydroxy group having 2 to 12 carbon atoms. Alkyl group or alkoxyalkyl group and i-, c-R3 (in the formula, R3 represents an alkyl group or aryl group having 1 to 18 carbon atoms)
+ (ii) If A and B are bonded to each other; A and B are complex 5~ formed together with the nitrogen atom of formula (Ia) or (Ib). At least one N-coordinated triorganotin-containing repeating unit (b ) At least one member selected from the group consisting of an acrylic compound, a vinyl compound having a functional group, a vinyl hydrocarbon compound, a triorganotin salt of a dipolymerizable unsaturated carboxylic acid, and a polymerizable unsaturated dicarboxylic acid or its anhydride. This is an antifouling agent characterized by containing, as an antifouling component, a triorganotin-containing copolymer containing a comonomer repeating unit derived from a comonomer.

In the above formula (Ia) or (Ib), A and B each represent 2, for example, the following group; (where R' is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group) + R' has 2 or more carbon atoms
Examples of the following groups include three alkylene groups, cyclohexylene groups, or phenylene groups, where q represents an integer of 1 to 5.

The main chain of the bipolymer used in the present invention contains the general formula (Ia
), (Ib) or (Ic) A triorganotin-containing copolymer containing an N-coordinated triorganotin-containing repeating unit (hereinafter referred to as the triorganotin complex-containing copolymer of the present invention) is usually the following: It can be obtained in this way. That is, the quadratic equation (Ua)
1b) or [mouth C] (Ila) (Ilb) (Ilc
) having the same meaning) with the general formula R35n.
It is obtained by directly reacting a triorganotin compound represented by X (wherein R and X have the same meanings as above).

Examples of the unsaturated compound having nitrogen atoms in two molecules represented by the above formula (Ila) used to obtain the triorganotin-containing copolymer of the present invention include N-vinylamine, N-
Examples include vinylamide and N-vinylimide. N-
Vinyl Amint City.

Example L N-vinylethylamine, N-vinyl n-butylamine, N-vinyl n-dodecylamine.

N-vinylcyclohexylamine, N-vinyldimethylamine, N-vinyldiethylamine, N-vinylmethylphenylamine, N-vinylphenylamine, N-
Vinylphenyl β-naphthylamine, N-vinyl p-tolyl α-naphthylamine.

N-vinylpyrrole, N-vinylindole, N-vinyl α-'methylindole, N-vinylcarbazole,
N-vinyl-1,2,3,4-tetrahydrocarbazole, N-vinylphenothiazine, N-vinylnaphthophenothiazine, N-vinylmorpholine, N-vinylpiperidine, N-vinylphenoxazine, N-vinylpyrrolidine, etc. As N-vinylamide, 1, for example, N
-vinylacetamide, N-vinyl N-methylacetamide, N-vinylacetanilide, N-vinyl N-methylbenzamide, N-vinylpyrrolidone, N-vinyl 3
-Methylpyrrolidone, N-vinyl5-methylpyrrolidone, N-vinyl5-phenylpyrrolid/.

Examples of N-vinylimide include N-vinyl 3-benzylpyrrolidone, eg N-vinylsuccinimide,
Examples include N-vinylgeltarimide, N-vinyldiglycolimide, N-vinylphthalimide, and N-vinyltetrahydrophthalimide.

Examples of the unsaturated compound having a nitrogen atom in one molecule represented by the above formula (Ilb) include aminoolefin, aminostyrene, olefinamide, aminoacrylate, aminomethacrylate, aminovinyl ether, aminovinyl sulfide, and the like. Two examples of aminoolefins include allylamine, allylmethylamine,
Allyldimethylamine, allylethylamine, allyldiethylamine, methallylamine, methallylmethylamine.

methallyl ethylamine, methallyl methylethylamine,
Methallyl phenylethylamine, l-ethylamino-3
-butene, 1-dimethylamine-4-pentene, 1-diethylamino-4-pentene.

12-dodecenylamine, allyldibenzylamine.

Allylethylphenylamine, N-allylmorpholine,
N-methallylmorpholine, N-allylpyrrole, N-allylindole, N-methallylpiperidine, N-methallylpyrrolidine, N-methallylpyrrolidone, N-allylcarbazole, N-allylaniline, N-allyl N-methyl Aniline etc., but as aminostyrene 9 e.g. 0
-aminostyrene, m-aminostyrene/, p-aminostyrene, p-dimethylaminostyrene, p-diethylaminostyrene, 0-vinylbenzylamine.

p-N, N-dimethylaminomethylstyrene, N-(
0-vinylbenzyl)pyrrolidine, N-(p-vinylbenzyl)morpholine IN-(0-vinylbenzyl)piperidine, N-(o-vinylbenzyl)pyrrole, N-(
p-vinylbenzyl)indole + N (o-vinylbenzyl)carbazole, etc., and olefin amides such as acrylamide, methacrylamide, N-
Methylacrylamide, N,N-dimethylacrylamide.

N-ethylacrylamide, N,N-diethylacrylamide, N,N-dimethylmethacrylamide.

N,N-diethyl methacrylamide, N-ethyl N-phenylacrylamide, N-methylolacrylamide, N-octylacrylamide, N-methoxymethylacrylamide, N-2,2-dimethylpropoxymethylacrylamide, N,N-jethanolacrylamide , N,N-jethanol methacrylamide, diaseptone acrylamide.

N-methylacrylanilide, acryloylmorpholine, methacryloylpiperidine, acryloylpyrrolidine, methacryloylmorpholine, acryloyl indole, acryloylcarbazole.

Mecryloyltetrahydrocarbazole, etc.

Examples of aminoacrylates or aminomethacrylates include N-methylaminoethyl acrylate, N-ethylaminoethyl acrylate, N.

N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N-methylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, N-ethylaminoethyl methacrylate,
N,N-diethylaminoethyl methacrylate, N
, N-dimethylaminopropyl methacrylate + N-t
-butylaminoethyl acrylate, N,N-diethyl azunohexyl methacrylate, N-methoxymethylaminoethyl acrylate-1"+ N-ethoxyethylaminoethyl methacrylate, N-methyl N-phenylaminoethyl methacrylate, p-N , N-jethylaminobenzyl methacrylate) + o N, N-dimethylaminophenethyl methacrylate, β-morpholinoethyl methacrylate, ni-morpholinopropyl acrylate,
β-pyrrolidylethyl methacrylate, β-carbasolyl ethyl acrylate, etc., and aminovinyl ethers include 2, such as N,N-dimethylamine ethyl vinyl ether, N,N-diethylaminoethyl vinyl ether, 3-aminopropyl vinyl ether, 5-amino Pentyl vinyl ether, 8-aminooctyl vinyl ether, 10-aminodecyl vinyl ether, 2-aminobutyl vinyl ether, N-[-butylaminoethyl vinyl ether, N-methylaminoethyl vinyl ether,
N-2-ethyl hequinyl aminoethyl vinyl ether,
(N-β-hydroxyethyl N-methyl)aminoethyl vinyl ether, N,N-dihydroxyethylaminoethyl vinyl ether + N,N-diphenylaminoethyl vinyl ether, β-dyrolysylethyl vinyl ether, β-morpholinoethyl vinyl ether, β-vinyl ether Veridinoethyl vinyl ether, 2+'''-morpholinopropyl vinyl ether, β-carbazolyl vinyl y-/l/
H = /l/ether, etc., and examples of aminovinyl sulfide include aminoethyl vinyl sulfide, N,N-dimethylaminoethyl vinyl sulfide, etc.
', 5-aminopentyl vinyl sulfide, N-ethyl N-phenylaminopropyl vinyl sulfide, N
, N-diethylaminoethylvinyl sulfide, and the like.

Examples of unsaturated compounds having a nitrogen atom in one molecule represented by the above formula (Inc) include 2-vinylhyphen, 3-vinylhyricine, 4-vinylpyridine,
2-vinyl-4-methylpyridine.

4-Vyral-2-methylpyridine, 2-vinylpiperidine, 4-vinylpiperidine, 4-vinyl-2-methylpiperidine/, 2-vinylpyrrolidine.

Examples include 3-vinylpyrrolidine, 3-vinylpyrrole, 2-vinylquinoline, and the like.

Other polymerizable unsaturated compounds (comonomers) that can be copolymerized with the nitrogen-containing unsaturated compound represented by the formula (Ila), (Ilb) or (Ilc:) include acrylic compounds, vinyl having a functional group, system compound.

Examples of acrylic compounds include vinyl hydrocarbon compounds, triorganotin salts of dipolymerizable unsaturated carboxylic acids, dipolymerizable unsaturated dicarboxylic acids or their anhydrides, and the like. Atom, substituted or unsubstituted carbon number 1-2
0 hydrocarbon group or aryl group, R5 is a hydrogen atom,
Examples include compounds represented by a halogen atom or an alkyl group having 1 to 6 carbon atoms. These compounds include 2
Acrylic or methacrylic acids such as acrylic acid, methacrylic acid, α-ethyl acrylic acid, CM-chloroacrylic acid, etc.; methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, dodecyl acrylate.

Octadecyl, cyclopentyl, cyclohexyl.

Acrylic esters such as phenyl, benzyl, and tetrahydrofurfuryl esters; methacrylic esters such as methyl, ethyl, butyl, hexyl, octyl, and dodecyl esters of methacrylic acid; esters of α-chloroacrylic acid.

Examples include α-substituted acrylic esters such as butyl ester of α-ethyl acrylic acid, and examples of preferably used compounds include methyl acrylate, ethyl acrylate, 11-butyl acrylate, 2-ethylhexyl acrylate, Examples include n-octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, and n-dodecyl methacrylate. These compounds can be used alone or in combination of two or more.

As a vinyl compound having a functional group, the linear formula % formula % [In the formula, Q is a halogen atom 1-CNI-OR*1-5R
*, -COR'' or -〇COR*' (in the formula, R* represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), Q/ is a hydrogen atom, a hydrogen atom, or a carbon number 1 ~6 alkyl groups].These compounds include compounds represented by 2, such as vinyl chloride, vinylidene chloride, etc.; acrylonitriles such as acrylonitrile, methacrylatetril, etc.; Vinyl ether, ethyl vinyl ether, β
-chloroethyl vinyl ether, butyl vinyl ether, octyl vinyl ether, tesyl vinyl ether, lauryl vinyl ether, phenyl vinyl ether, 0-
Methylphenyl vinyl ether.

vinyl ethers such as silvinyl ether, β-naphthyl vinyl ether, etc.; vinyl thioethers such as methyl vinyl sulfide, divinyl sulfide, butyl vinyl sulfide, etc.;) vinyl ketones such as rubinyl ketone, phenyl vinyl ketone, etc. Vinyl pigate .

Vinyl acetate, vinyl propionate, vinyl butyrate.

Examples include vinyl ethers such as vinyl laurate, vinyl benzoate, and vinyl salicylate. Preferably used compounds include, for example, m-vinyl ether, acrylonitrile, butyl vinyl ether, tezoru vinyl ether, lauryl vinyl ether, and vinyl acetate. I can do it. These compounds may be used alone or in combination of two or more.

Examples of vinyl hydrocarbon compounds include compounds represented by the linear formula (% formula % (in the formula, P and P' are hydrogen atoms or hydrocarbon groups having 1 to 18 carbon atoms).

These compounds include olefins such as ethylene, propylene, 1-butene, cyclohexene, α-pinene, etc.; dienes such as 1,3-butadiene; styrene, α-methylstyrene, 0-methylstyrene, etc. Examples include styrenes such as , m-methylstyrene, p-methylstyrene, etc., and examples of preferred compounds include styrene.

In addition, as triorganotin salt of polymerizable unsaturated carboxylic acid, 9
The following formula % formula % (wherein R6 is a hydrogen atom or a group -COOR9, R7 is a hydrogen atom, a lower alkyl group or a group -CH2COOR).

R8, R9, R10 are the same or different triorganotin groups)
Examples include compounds represented by: These compounds include, for example, tripropyltin methacrylate, tributyltin methacrylate, noamyltin methacrylate,
Triphenyltinmethac9ate.

Tripropyltin acrylate, tributyl rylate, triamyltin acrylate, triphenyltin acrylate, bis(tripropyltin) itaconate, bis(tributyltin) itaconate.

Examples include bis(tricyclohexyltin) itaconate, bis(triphenyltin) itaconate, bis(tributyltin) maleate, bis( ) IJ phenyltin) maleate, and a preferably used compound is, for example, tributyltin methacrylate.

Triphenyltin methacrylate, tributyltin acrylate, triphenyltin acrylate, bis(tributyltin) itaconate, bis(triphenyltin) itaconate, bis(tributyltin) maleate, bis(triphenyltin) maletra. can. These compounds may be used alone or in combination of two or more.

Examples of the polymerizable unsaturated dicarboxylic acid or its anhydride include maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride, with itaconic acid and maleic anhydride being preferred.

The triorganotin compound represented by R3SnX (R and
These are so-called triorganotin punylide halides, such as trimethyltin inthiocyanate, trimethyltin incyanate, trimethyltin azide, tripropyltin isothiocyanate, tripropyl root, tributyltin isothiocyanate 1-, 17-methyltin isothiocyanate. /nanate, triphenyltin azide, tributyltin cyanide, trinoamyltin isothiocyanate,
triamyltin incyanate, trinophenyltin isothiocyanate), phenyltin isocyanate, triphenyltin azide, triphenyltin cyanide, tricyclohexyltin isothiocyanate, tricyclohexyltin noanide.

Dibutylphenyltin isothiocyanate, diphenylethyltin incyanate, etc., tributyltin isothiocyanate, dibutyltin incyanate, etc.
Trimethyltin azide
1 phenyltin cyanide, triphenyltin isothiocyanate),)IJ phenyltin isocyanate,)'J
Phenyltin azide, triphenyltin cyanide; preferably 0 Nitrogen-containing unsaturated compounds represented by the above formula Cna]E11b') or CIIC) and other polymerizable unsaturated compounds (arsenic compounds (
Comonomer) can be copolymerized with a suitable polymerization catalyst, polymerization,
This can be carried out by emulsion polymerization or suspension polymerization, but solution polymerization is preferred in view of carrying out the subsequent reaction of introducing the triorganotin pseudonolide.

Since the copolymer thus obtained contains nitrogen atoms in its side chains, the nitrogen atoms are reacted with triorganotin pseudohalide. This reaction involves forming a coordinate bond between the nitrogen atom in the nitrogen-containing copolymer and the tin atom of the triorganotin pseudoride (1) using the nitrogen atom as a ligand.
).

Generally, the compound thus produced is an addition compound (a
dduct compound)+double salt or complex salt compound The solution polymerization and introduction reaction of the triorganotin pseudolide described above are usually carried out using an organic solvent, such as benzene.

Aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexano/etc., and tetrahydrofuran.

Ethers such as dibutyl ether and diglyme.

It can be carried out under isopropanol, butanol, or ethyl cellosolve.

1) Organotin pseudo to be reacted with the nitrogen-containing copolymer;
・The amount of 11% of the nitrogen-containing copolymer is equivalent to or less than the nitrogen atom contained in the copolymer, and is arbitrarily selected depending on the type or antifouling purpose. The formation of the above-mentioned self-positioned compound by the reaction between the nitrogen atoms in the coalescence and the organotin pseudonolide has been confirmed by various instrumental analyzes + infrared absorption spectroscopy (for example, SnC and Sn-CI). Due to the shift of the absorption band of
Self-positioning can be confirmed by the analytical method of line diffraction.

The thus obtained solution of the organotin-containing copolymer of the present invention in an organic solvent is a colorless, pale yellow or yellowish brown viscous liquid. Further, the triorganotin-containing copolymer of the present invention has a molecular weight of 5,000 to 500,000 molecules.
The body solution can be obtained as an organic solvent solution containing usually 10 to 8% by weight, preferably 40 to 60% by weight of the organotin-containing copolymer. The copolymer solution was applied to wooden boards, metal plates, synthetic fiber ropes, nets, etc., and when dried, a triorganotin-containing copolymer coating with good elasticity and adhesion was formed.

The triorganotin-containing copolymer of the present invention can also be produced by the following method. That is, the above formula (Ila),'
The formula % obtained by reacting a triorganotin pseudonolide with each unsaturated compound having a nitrogen atom in the molecule represented by [(Ilb)] or [C] has the same meaning as the formula % [[) [). The triorganotin-containing copolymer of the present invention can be obtained by copolymerizing the unsaturated compound represented by the above formula with another polymerizable unsaturated compound (comonomer).

The formula (lira), (l[Ib) or (li[c
) The starting materials for producing the unsaturated compound represented by formula (Ila), (Ilb) or (llc) are the nitrogen-containing unsaturated compound represented by the formula (Ila), (Ilb) or (llc) and the above-mentioned tri-organotin-dohalide, and also other As for the polymerizable unsaturated compounds (comonomers), those exemplified in the above-mentioned production method can also be used. The polymerization method is carried out in a similar manner. The triorganotin-containing copolymer of the present invention obtained by this method has the above formula (I
Since it is difficult to incorporate a high degree of N-coordinated triorganotin-containing structural unit represented by a), (Ib) or (IC) into the linear polymer chain, if it is necessary, the above-mentioned It is preferably obtained by a method in which a triorganotin pnoid halide is allowed to act on a nitrogen-containing copolymer.

Formula (Ia) in the triorganotin-containing copolymer of the present invention.

The proportion of the N-coordinated triorganotin-containing structural unit represented by ('Ib) or (Ic) is not particularly limited.

It is determined by the ability to form an antifouling coating film and the antifouling performance, but the copolymer contains 10 to 10 N-coordinated triorganotin-containing structural units.
80% by weight and repeating units of comonomers of other polymerizable unsaturated compounds can be contained in proportions of 90 to 20% by weight.

The antifouling agent of the present invention is produced using the triorganotin-containing copolymer of the present invention in various forms depending on the purpose of antifouling.

Namely, 2 solvents used in the solution polymerization of the triorganotin-containing copolymer of the present invention 2, such as hydrocarbons, ketones,
Dissolved in organic solvents or mixed solvents such as esters, alcohols, and ethers.

Alternatively, the triorganotin-containing copolymer solution obtained by each of the above-mentioned production methods can be used as an antifouling agent as it is or after being diluted. Also dyes and pigments.

Support, if necessary, copper compounds such as cuprous oxide and copper rhodan,
It is used in fishing net antifouling agents and ship bottom antifouling paints when mixed with organotin compounds, paint conditioners, toxic elution control agents, and diluents. Although the proportion of the triorganotin-containing copolymer of the present invention in the antifouling agent thus obtained is not limited, it is possible to
-70% by weight. In the present invention, since the triorganotin-containing copolymer itself has both an antifouling component and a coating film forming agent (face), other color vehicles such as oil-based face and vinyl resin face can be used in principle.

Although acrylic resin panels are not required, they may be used depending on the antifouling purpose. As described above, the antifouling agent of the present invention can be embodied in various forms, but the solid content of the antifouling agent contains 0.5% by weight of triorganotin compound (Ra SnX) units.
It is preferable that the content is above.

The antifouling agent of the present invention has the following features.

That is, firstly, the antifouling agent of the present invention has long-term storage stability, and is substantially free from changes over time such as thickening and gelation. In this case, the presence of a copper compound (for example, cuprous oxide) in the antifouling agent makes no difference. Such an effect is caused by -C in the conventional molecule.
This is not observed in the triorganotin-containing polymer type antifouling agent having OOS n R3.

Second, in the present invention, the tri-organotin compound is introduced into the polymer through coordination bonds, so the physiological effect on the human body is extremely reduced compared to the conventional tri-organotin compound-based antifouling agent. 2 There is no need to worry about harm to workers. Third
When the antifouling agent of the present invention is applied to a substrate to be antifouled, it forms a tough coating film with strong adhesive properties, and the protective coating has excellent antifouling performance and physical and chemical resistance. A membrane is obtained. Fourthly, since the antifouling agent of the present invention is a copolymer containing hydrophilic nitrogen-containing compound residues, it has the performance as a soluble matrix, and when immersed in seawater, the coating surface remains constant. It is renewed and can maintain long-term stain resistance.

Therefore, by varying the ratio of N-coordinated triorganotin-containing structural units and comonomer units in the polymer of the present invention depending on the antifouling purpose, a wide range of antifouling products from the insoluble matrix type to the soluble matrix type can be obtained. Adjustment is possible. Furthermore, the present invention has the great advantage of being able to produce an antifouling agent containing a triphenyltin-containing copolymer that is effective against algae.

The antifouling agent of the present invention is particularly advantageously used to protect objects that come into contact with seawater, such as the bottoms of steel ships, wooden ships made of reinforced glass, fishing nets, underwater structures, and seawater inlet pipes, but it can also be used to protect objects that come into contact with seawater, such as the bottoms of steel ships, wooden ships, and ships made of reinforced glass. It also applies to the protection of objects that are susceptible to damage from contaminant organisms due to long-term use of water.

Next, the present invention will be explained with reference to Examples and Test Examples. In Examples and Test Examples, ``part'' and ``part'' refer to parts by weight and parts by weight, respectively.

Example 1 500 ml equipped with thermometer, reflux condenser and stirrer
- Charge 32 g of N-vinyl N-methylacetamide, 55 g of methyl methacrylate, 10 g of octyl acrylic acid, and 200 g of quince in a Mitsuro flask, add 05 g of azobisisobutyronitrile, replace the inside of the container with nitrogen gas, and stir. Then the internal temperature was raised to 80°C. Next, while stirring at the same temperature, 0.2 g of azobisisobutyronitrile was added three times every 3 hours to conduct a polymerization reaction for a total of 12 hours to obtain a nitrogen-containing copolymer solution. Add triphenyltin inthiocyanate 103 f to this solution,
The addition reaction was carried out with stirring at 0°C for 2 hours, and the molecular weight was 9.
A copolymer solution (copolymer solution (A-1)) containing 6.000 N coordination triphenyltin was obtained. This copolymer solution was used as an antifouling agent.

Examples 2-2 The polymerization components shown in Table 1 below were placed in two reaction vessels under the same polymerization and addition reaction conditions as in Example 1.

A solvent and a catalyst are charged, a bipolymerization reaction is carried out to produce a nitrogen-containing copolymer solution, and tri-organotin pseudohashide is added to carry out an addition reaction to form an N-coordination-triorganotin-containing copolymer solution (copolymer solution). (A-2) ~ [l:A'-2
0) ) was obtained. These copolymer solutions (A-2) ~ [
1: A-20) was used as an antifouling agent.

The above is shown in Table 1.

Example 21 In a reaction vessel similar to Example 1, 40 g of N-vinylphenylethylamine and 95 g of butyltin inthiocyanate were added.
and 200 f of xylene were charged and stirred at 50°C for 2 hours to form an N-vinylphenylethylamine/tributyltin inthiocyanate adduct. Next, 50g of methyl methacrylate and 15g of octyl acrylate.
and 0.5 g of benzoyl peroxide were added, and the temperature was raised to 95°C without stirring. At the same temperature, 0.21 g of benzoyl peroxide was added 3 times every 3 hours to carry out the polymerization reaction for a total of 12 hours. 21]
) was obtained. This copolymer solution was used as an antifouling agent.

Examples 22 to 25 Following the same addition reaction conditions and polymerization conditions as in Example 21,
After the nitrogen-containing unsaturated compound, triorganotin compound and solvent shown in Table 2 are charged and an addition reaction is carried out, a comonomer component and a polymerization initiator are added and a polymerization reaction is carried out. Containing copolymer solution (copolymer solution (A-2)
, 2) to (A-25)) were obtained. These copolymer solutions (A-22) to (A-25) were directly used as antifouling agents.

The above is shown in Table 2.

Reference example: 120 g of triphenyltin methacrylate, 64 g of octyl acrylate, 16 g of methyl methacrylate in a reaction vessel.
After preparing f and xylene 200f and dissolving them well,
Add 08 g of azobisisobutyronitrile and polymerize at 75°C for 3 hours with stirring to obtain a molecular weight of 77.00.
0 triphenyltin-containing copolymer solution (copolymer solution [
Reference example]) was obtained.

Examples 26 to 50 Using each of the N-coordination-triorganotin-containing copolymer solutions obtained in Examples 1 to 25, the ingredients listed in Table 3 below were added to the solutions for the ship bottom of the present invention. Obtained antifouling paint.

The above is summarized in Table 3.

(Note) The numbers in Table 3 indicate parts by weight, and the symbols mean the following.

(Bu3S summer) 20: Bis(triphytyltin) oxide PbaSnOH': ) Liphenyltin/hydrooxide■ Antifouling test (clear coating) Antifouling agent of the present invention obtained in Examples 1 to 25 (copolymer The solutions (A-1] to (A-25)) were applied to both sides of a 17X9X0.3C+1 hard vinyl chloride resin plate with a dry film thickness of about 15%.
It was applied so that the thickness was 0μ. Each coated plate was immersed in an underwater raft for 6 months in Owase Bay, Mie Prefecture.

The state of contamination was observed.

The results are shown in Table 4.

The symbols in the table indicate the following (the same applies to subsequent tables).

○ Mark: Marine fauna and flora (-1 No place △ Mark: 〃 5% or less attached × Mark: 5 to 20 inches attached XX mark: 20 to 50% attached × Table 4 Table 4 (continued) 1] Antifouling test (ship bottom paint) The antifouling paint for ship bottoms of the present invention obtained in Examples 26 to 50 was tested at 17 x 9 x, Q, 3 on. It was coated on both sides of a hard vinyl chloride resin plate to a dry film thickness of about 200/i.

The results are shown in Table 5.

Table 5 Table 5 (continued) 1 ■ Antifouling test (fishing net) Antifouling agents of the present invention obtained in Examples 1 to 25 (copolymer solutions (A-1) to (A-25)) 100 Part Ki/Ren 2
It was diluted by adding 0.00 parts. 30X40cm for each diluted solution
Polyethylene fishing nets (24 pieces, 8 sections) were soaked.

After a few minutes, it was taken out, air-dried, and then mounted on an iron frame.

The amount of coating was approximately 20% of the weight of the fishing net. These were immersed in an underwater raft for three months in Owase Bay, Mie Prefecture, and their contamination status was observed every month.

The results are shown in Table 6.

Table 6 Table 6 (continued) ■Storage stability test (antifouling agent) Antifouling agent (copolymer solution (A-
Put each of 1) to (A-25)) into a 100 d glass bottle and store it in an oven at 50°C for 3 months.

After a certain period of time, it was taken out and changes over time were observed. The same procedure was carried out for the copolymer solution [Reference Example].

The results are shown in Table 7.

The symbols in the table indicate the following (the same applies to subsequent tables).

1 field Sho 6o-nebx5 (1B) A: No change in viscosity compared to the antifouling agent or antifouling paint immediately after production B: Slightly increased viscosity compared to the viscosity of the antifouling agent or antifouling paint immediately after production C: Production Viscosity significantly increased compared to the viscosity of the antifouling agent or antifouling paint immediately after D: The antifouling agent or antifouling paint gelled Table 7 Table 7 (Continued) ■ Storage stability test (antifouling paint) Examples 25- The antifouling paints obtained in step 50 were placed in 100 m/glass bottles, stored in an oven at 50°C for 3 weeks, and taken out after a certain period of time to observe changes over time.

The results are shown in Table 8.

Table 8 Table 8 (continued) (Note) *Formulation of antifouling paint in reference example Copolymer solution [Reference example, II 40 parts Cuprous oxide 40 parts Van gala 5 parts Tarri 5 parts Keychain 15 parts Patent applicant Nitto Kasei Co., Ltd. Agent Patent Attorney Tetsuya Matsu

Claims (1)

[Claims] 1. In the polymer main chain. (a) The following general formulas (Ia), (Ib) and (Ic) (I
c) [In the formula, R is the same or different alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 8 carbon atoms, and X is a group -NC5, a group -NGO, a group -N3 or a group -CN
+R'' and R2 are independently selected from a hydrogen atom, a methyl group/ethyl group, and a halogen atom. p is an integer of 1 to 4, Y is an a group having 1 to 12 carbon atoms -5
-Z - (wherein Z is an alkyrev group or group having 2 to 12 carbon atoms -(
CH2)nni()-(m: an integer of 1-8)). A and B may or may not be bonded to each other. (i) When A and B are not bonded to each other, A and B are hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, cycloalkyl groups, aryl groups, aralkyl groups, and hydroxy groups having 2 to 12 carbon atoms. Alkyl group or alkoxyalkyl group and group -C-R3C in the formula, R3 represents an alkyl group or aryl group having 1 to 18 carbon atoms)
selected from the group consisting of r (u) When A and B are bonded to each other, i A and B are a 5- to 6-membered hetero ring formed together with the nitrogen atom of formula (Ia) or (Ib), or The group -0 represents a 5- to 6-membered heterocycle bonded to the carbon atom to which R1 is bonded by a ring member other than the nitrogen atom, or a fused ring thereof.
N-coordination of species - triorganotin-containing repeating unit and (b) acrylic compound, vinyl compound having a functional group, vinyl hydrocarbon compound, triorganotin salt of dipolymerizable unsaturated carboxylic acid and polymerizable unsaturated An antifouling agent comprising, as an antifouling component, a triorganotin-containing copolymer containing a comonomer repeating unit derived from at least one comonomer selected from the group consisting of dicarboxylic acids or anhydrides thereof. The antifouling agent according to claim 1, which is a mino group or an alkylphenylamine group. The antifouling agent according to claim 1, which is COCH3 or a group -N (C6H5) COCH3. The antifouling agent according to claim 1. 1. The antifouling agent according to claim 1. The antifouling agent according to claim 1, which is a group -()-NR2. 0- CH2GHz -N (CH3)2 or group -C-
The antifouling agent according to claim 1, which is 0-1 CH2CH2-N(CzHs)2. The antifouling agent according to claim 1, which is 0-CH2CH2-N O. CH2CH2-N(CH3)2 or group -0-CH2CH
2-N(C2H5)2, Claim 13, Claim 13, wherein in formulas (Ia), (Ib) and (Ic), Ra5nX is tributyltin isothiocyanate or triphenyltin inthiocyanate. The antifouling agent according to scope 1. 14. Claim 1, wherein the triorganotin-containing copolymer contains 10 to 80% by weight of N-coordinated triorganotin-containing repeating units and 90 to 20% by weight of comonomer repeating units. Antifouling agent listed. 15, the triorganotin-containing copolymer has a molecular weight of 5.000 to 500
The antifouling agent according to claim 1, having a molecular weight of ,000.