JPS62112669A - Polishing type antifouling paint composition - Google Patents

Abstract

PURPOSE:To provide a polishing type antifouling paint compsn. which can retain an antifouling performance over a long period of time and is suitable for use as ship bottom paint, containing a hydrolyzable resin having a tin-contg. antifouling component on its side chain as a vehicle. CONSTITUTION:Tin oxide is reacted with a monobasic org. acid having antifouling properties and a polymerizable unsaturated org. acid and the product is polymerized to produce a resin having a group represented by formula I (wherein X is -CO-, a group of formula II, a group of formula III, methylene, methine, etc.; x is 1-2; R2 is a 1-10C hydrocarbon; R2 is a group of formula IV, -COO-, -S-, etc.; R3 is H, a 1-10C hydrocarbon) at the terminal of at least one side chain. The resulting tin metal-contg. resin compsn. is used as a vehicle to obtain the desired polishing type antifouling paint compsn. When the paint compsn. is applied to a ship bottom to form a coating film, an antifouling agent is gradually released by hydrolysis.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a borising type antifouling paint composition containing a novel metal-containing resin composition as a vehicle.

Conventional technology Today, it is widely practiced to form organic or inorganic antifouling agents into paints with binders such as vinyl resins and alkyd resins and paint them as ship bottom paints. Since the elution rate of the antifouling agent is mainly based on the diffusion phenomenon caused by its concentration gradient, a stable antifouling effect cannot be expected for a long time, and the antifouling agent is After being eluted from the water, the water-insoluble resin components form a skeleton structure, which causes many problems such as increased frictional resistance between the ship and the water, reduced speed, and increased fuel consumption. Therefore, antifouling paints made of antifouling agents and hydrolyzable resin vehicles that create relatively strong coatings and gradually hydrolyze in seawater to dissolve the resin have been attracting attention. It's arrived.

The present inventors previously discovered that a hydrolyzable polyester resin in which a large number of metal-ester bonds are incorporated into the polyester main chain is extremely useful as a vehicle for polishing-type antifouling paints. No. 5
A patent application was filed as No. 8-496900. In the case of darkening resins, the metal-ester portion easily undergoes hydrolysis under alkaline conditions such as seawater, and the resin dissolves into segments with small molecular weight, but the resin itself originally has a relatively low molecular weight. They are small (for example, up to about 2000) and have poor film-forming properties, causing problems such as cracking and peeling of the coating film.

Increasing the molecular weight of the polyester resin certainly improves film-forming properties, but the hydrolyzability becomes extremely poor, and to compensate for this drawback, increasing the metal-ester concentration in the polyester main chain makes it easier to use polar solvents. This creates a new problem of solvent insolubility, which can only be dissolved in seawater, causing the coating film to swell in seawater.
Undesirable.

As a hydrolyzable resin, for example, it has been attempted to have a trialkyl tin ester at the end of the side chain, and to gradually increase the polarity of the resin by hydrolyzing the ester moiety to achieve dissolution and elution. A typical example thereof is an acrylic resin containing triorganotin salts of α, β-, and β-basic acids as constituent units. In this case, in order to create a stable and strong coating film, the resin should preferably be a polymer that does not contain hydrophilic groups as much as possible, and in order for the decomposed resin to be dissolved in water, It must be ensured that the resin has a hydrophilic group concentration above a certain critical value. For this reason, it is common practice to copolymerize triorganotin salts of α, β-, and β-basic acids with acrylic vinyl heptamers, so that the former is present in a high concentration, and the parent group is removed as much as possible from the latter. For example, 55 to 70 wt%
Copolymers of α,β-unsaturated acid-base acid triorganotin salts with acrylic acid esters, acrylamide, styrene, etc. have been put into practical use. Unlike polyester-type resins containing metal ester bonds in the main chain, these resins generate hydrophilic carboxyl groups when the triorganotin moieties in the side chains are released by hydrolysis, and their concentration reaches a certain critical value. It is possible to provide a coating of a preferred form in which the resin is leached only after a certain period of time, but this requires the use of large quantities of expensive organotin compounds.

Also, from a public health standpoint, it is desired to reduce or avoid its use as much as possible.

Therefore, it is a resin with excellent film-forming properties that has a group on the side chain that can generate a hydrophilic group by hydrolysis, and is eluted by moderate hydrolysis in seawater, and is expensive. It is clear that if a new hydrolyzable resin composition that does not rely on triorganotin salts, whose use is considered undesirable from a public health standpoint, could be obtained, it would be extremely useful as an antifouling paint. . The present inventors have proposed, as a means to solve such problems, that the terminal end of at least one side chain or -P; M is a zinc, copper or tellurium atom; X is an integer of 1 to 2; C-R1, -S -R1, or 1○-8-R
, where R is a monovalent organic residue) ■ A metal-containing resin composition comprising a resin having at least one group represented by discovered a coating composition characterized by containing
No., filed on May 17, 1985).

In the invention related to the above application, when a metal-containing resin undergoes hydrolysis in seawater (weakly alkaline), hydrophilic groups of carboxylic acid, sulfonic acid, or phosphoric acid are generated in the side chain portion, and the concentration reaches a certain critical value. Then, the resin itself is eluted into the seawater, and the metal part is also cut off between O and M and between M and R in 10-M-R due to hydrolysis, and the metal parts are made of zinc, copper or tellurium, which have antifouling properties. This was based on the discovery that it is extremely useful as a resin vehicle for antifouling paints because it generates metal ions. However, relying only on such metal ions for antifouling performance is unrealistic due to the relationship between the metal content in the resin and the rate of hydrolysis. Rather, it is necessary to add a regular antifouling agent separately, and to determine the degree of depletion of the resin and the antifouling performance. Balancing performance is considered an easy and practical solution.

Problems to be Solved by the Invention Therefore, the main purpose of the present invention is to create a resin that has a group in its side chain that can generate a hydrophilic group by hydrolysis, and that can undergo moderate hydrolysis and be eluted in seawater. It is a resin with excellent film-forming properties, and when hydrolyzed, a compound with excellent antifouling performance is liberated and exhibits an effective antifouling effect, and the metal species are simply a resin part rich in parent wood groups and antifouling properties. It is an object of the present invention to provide an antifouling paint containing a new type of hydrolyzable resin composition as a resin vehicle, which only serves to bind compounds together.

Means for Solving the Problems The above purpose is to add two 〇
OR.

-p<, methylene group or methine group; X is 1-2
an integer; R1 is a hydrocarbon having 1 to 1 carbon atoms; R2 is -5-c-, -o-c-, S ○ -o-c -, -s +, -0-3-, and in the formula A tin metal-containing resin composition comprising a resin having at least one group represented by an organic compound residue having antifouling properties that is bonded to a tin atom; R1 is hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms. This can be achieved by providing an antifouling paint composition containing as a vehicle.

In the coating composition of the present invention, the tin metal-containing resin composition used as the resin vehicle is characterized by having at least one group represented by the above formula at the end of the side chain. Easily manufactured. That is, a polymerizable unsaturated monomer having a metal ester moiety of an organic acid having antifouling properties at the end is synthesized in advance,
A method of copolymerizing with other polymerizable unsaturated monomers; or a method of copolymerizing a polymerizable unsaturated organic acid monomer with other polymerizable unsaturated monomers to add tin metal oxide to a resin obtained by copolymerizing a polymerizable unsaturated organic acid monomer with other polymerizable unsaturated monomers. Another method is to react a monovalent organic acid having antifouling properties with a chloride or hydroxide, or transesterify the monovalent organic acid with a metal ester of the monovalent organic acid. It is also possible to use a method in which a resin having in the resin side chain through an ester bond is reacted with dialkyl tin oxide, and the dialkyl tin oxide is inserted into the ester moiety.

More specifically, the resin composition of the present invention is produced as follows.

(1) (a) I! Gold metal oxide, hydroxide, sulfide or chloride; (b) a monovalent organic acid having antifouling properties or an alkali metal salt thereof; and (c) a polymerizable unsaturated organic acid or an alkali metal salt thereof. and are heated and stirred below the decomposition temperature of the metal salt, and if desired, the by-product alkali metal chloride,
Water, a tin metal ester of a -valent organic acid, and a tin metal ester of a trifunctional polymerizable unsaturated organic acid are separated and purified from the purified polymerizable unsaturated organic acid and tin metal of a monovalent organic acid having antifouling properties. Obtain ester. In the above reaction, the amounts of (a), (b), and (c) do not necessarily have to be equal equivalents, with 0.8 to 3 equivalents of b) and 0.8 to 3 equivalents of b) per 1 equivalent of (a). The desired product can also be obtained using 8 to 2 equivalents.

The thus obtained tin metal ester of a polymerizable unsaturated organic acid and a monovalent organic acid having antifouling properties or the mixture of the tin metal ester and an acid-valent organic acid tin metal ester can be prepared by homopolymerization or other methods. Copolymerization with a copolymerizable monomer leads to the desired resin having a tin metal ester moiety at the end of the side chain.

or (2) (d) a resin containing an organic acid or its alkali metal salt in its side chain, (e) an oxide, hydroxide, sulfide, or chloride of tin metal, and (f) having antifouling properties. A resin having a tin metal ester moiety in the resin side chain can be obtained by heating and stirring a monovalent organic acid at a temperature below the decomposition temperature of the metal salt, and separating and purifying by-products if desired. The ratio of raw materials used in this reaction is (
e) is 0.8 to 1.5 equivalents (particularly preferably 1.0 to 1
．． 2 equivalents), and (f) is preferably 0.8 to 2 equivalents (particularly preferably 1.0 to 1.5 equivalents). In addition, when selecting a monovalent organic acid with a low boiling point and using a reaction format that involves a dehydration reaction, the monovalent organic acid is distilled out of the system together with water, and tin metal ester bonds are formed between the resins, resulting in an increase in viscosity or Since there is a risk of gelation, it is preferable to use the amount of (f) greater than the above. Alternatively, (3) a tin metal ester (h) of a monovalent organic acid having antifouling properties is reacted with a resin (g) having an organic acid in its side chain at a temperature below its decomposition temperature, and the resin side chain is A tin metal ester moiety is introduced at the end. In this reaction, if the monovalent organic acid has a low boiling point (for example, acetic acid), the acid may come out of the system upon heating and form a tin metal ester bond between the resins, so the reaction must proceed carefully. usually(
h) The amount is 0.3 to 3 per equivalent of organic acid in resin (g).
equivalent, preferably 0.4 to 2.5 equivalent.

(4) Furthermore, a method may also be used in which a resin having an antifouling agent in a side chain as an ester bond is reacted with a dialkyl tin oxide to insert the dialkyl tin oxide into the ester moiety to form a tin ester bond.

Examples of the polymerizable unsaturated organic acids (C) used in the above method include methacrylic acid, acrylic acid, p-styrenesulfonic acid, 2-methyl-2-acrylamidopropanesulfonic acid, methacrylic acid phosphooxypropyl,
3-chloro-2-acidophosphooxypropyl methacrylate, acidophosphooxyethyl methacrylate, itaconic acid, (anhydrous) maleic acid, monoalkyl itaconate (
For example, methyl, ethyl, butyl, 2-ethylhexyl, etc.), monoalkyl maleate (for example, methyl, ethyl,
(butyl, 2-ethylhexyl, etc.); hafestation of an OH group-containing polymerizable unsaturated monomer and an acid anhydride, e.g. (meth)
Examples include hafesters of 2-hydroxyethyl acrylate such as succinic anhydride, maleic anhydride, and phthalic anhydride, and one type or a combination of two or more of these can be used.

As the monovalent organic acid (b) having antifouling properties, any aliphatic, aromatic, alicyclic, or heterocyclic organic acid can be used as long as it has antifouling properties, and representative ones are as follows. It is.

○ (1) Those having -0-C- bonds, such as alicyclic carboxylic acids such as naphthenic acid; salicylic acid,
Cresotic acid, α-naphthoic acid, β-naphthoic acid, p-
Aromatic carboxylic acids such as oxybenzoic acid; halogen-containing aliphatic carboxylic acids such as monochloroacetic acid and monofluoroacetic acid; 2,4.5-trichlorophenoxyacetic acid, 2.4
- Halogen-containing aromatic carboxylic acids such as dichlorophenoxyacetic acid; organic nitrogen-containing carboxylic acids such as quinoline carboxylic acid, nitrobenzoic acid, dinitrobenzoic acid, and nitronaphthalene carboxylic acid; lactone carboxylic acids such as pulpic acid and purpic acid (2 ) Dithiocarbamates such as dimethyl dithiocarbamate (3) Those having a -8-bond 1-naphthol-4-sulfonic acid, paraphenylbenzenesulfonic acid, β-naphthalenesulfonic acid, Sulfur-containing aromatic compounds such as quinoline sulfonic acid, triethylpyrophosphoric acid, dimethylamino phosphate, and other various organic phosphoric acid compounds (5) Things with a -3-bond (6) Thiocarboxylic acids with an -0-C-bond is a typical example of an organic acid that can be used, but the present invention is not limited to such organic acids. For example, a sample may be placed in a recess of a test plate having a recess.

Any organic acid can be used as long as it is a compound that has antifouling properties by a simple test such as covering it with gold netting, immersing it in seawater for a certain period of time, and checking the adhesion of marine organisms on the gold netting. can.

In the present invention, tin metal is usually used in the form of an oxide, hydroxide, or chloride, but halides other than chloride, nitrates, sulfates, carbonates, etc. can also be used if desired. Furthermore, organic tin metal salts such as dibutyltin oxide can also be used.

Other polymerizable unsaturated monomers used in copolymerization are not particularly limited and any copolymerizable monomers known to those skilled in the art may be used, such as (meth)acrylic acid. Methyl, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene, vinyltoluene,
Vinylpyridine, vinylpyrrolidone, vinyl acetate, acrylonitrile, methacrylonitrile, dimethyl itaconate, dibutyl itaconate, di-2-ethylhexyl itaconate, dimethyl maleate, di(2-ethylhexyl) maleate, ethylene, propylene, vinyl chloride If desired, OH-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. can also be used.

Resin (d) having an organic acid in the side chain used in the present invention (
Examples of g) include not only vinyl resins but also resins containing organic acids such as polyester resins, oil-modified alkyd resins, fatty acid-modified alkyd resins, and epoxy resins.

In the resin having an antifouling-valent organic acid tin metal ester at the end of the side chain used in the present invention, it is not necessary that all the organic acids in the resin side chain have such a tin metal ester bond. It may be left as a base to some extent.

The molecular weight of the resin of the present invention obtained by the above method is not particularly limited, but the number average molecular weight is 4000.
~40,000 is preferred.

Particularly preferred is a range of 6,000 to 35,000.

If it is less than 4,000, the film forming properties of the paint will be insufficient and there is a risk of cracking or peeling.If it exceeds 40,000, the storage stability of the paint will deteriorate, making it unsuitable for practical use, and a large amount of diluting solvent will be used during painting. public health,
This is because it is unfavorable from the economic point of view.

The resin composition of the present invention can be used for coating underwater structures, and has the characteristic that the coating or film is gradually hydrolyzed and eluted in an alkaline atmosphere, and is useful, for example, as a coating for fishing nets, an antifouling coating for ships, etc. be.

As already mentioned, unlike polyester resins that have many metal ester moieties in the main chain, the resin of the present invention has metal ester bonds at the end of the side chain, and when hydrolyzed in an alkaline atmosphere, the resin becomes small. Rather than being broken down into segments and eluted all at once.

Hydrophilic groups are generated in the side chain portions, and the concentration reaches a certain critical value before elution begins. Therefore, when used as a vehicle for ship bottom paint, the metal content required for the six resins, which have the characteristic of controlling the antifouling period over a long period of time, to be eluted into seawater is in the range of 0.3 wt% to 20 wt%. It has also been found that 0.5 wt% to 15 wt% is preferred, particularly optimal. This is because if the metal content in the resin is less than 0.3 wt%, even if the metal ester part is hydrolyzed, elution from the resin will be extremely slow;
This is because if it exceeds this, the elution rate will be too fast, which is not preferable.

The acid value and hydroxyl value in the tin metal-containing resin of the present invention do not necessarily have to be 0, and are allowed to a certain extent as long as the resin does not dissolve or elute in water. More specifically, the acid value is up to 40K OH/g, preferably 30K
The permissible range of hydroxyl value is up to 200 KOHmg/g, preferably up to 150 KOHmg/g.

In the antifouling paint of the present invention, the above resin composition is used as a resin vehicle, and this resin undergoes gradual hydrolysis in seawater (weakly alkaline), and the concentration of hydrophilic groups in the resin increases until it reaches a certain critical value. Once reached, the resin is eluted, and the tin metal itself is used only for the purpose of binding the resin with hydrophilic groups and the organic acid with antifouling properties and separating the two through hydrolysis.
Furthermore, during hydrolysis, a monovalent organic acid with antifouling properties is released into seawater, and tin is also released as a less toxic dialkyltin compound. It can be said to be an extremely new and useful resin in that it can be selected from a wide range and does not depend on the monovalent organic acid at the end of the side chain to achieve an effective antifouling effect without adding any other antifouling agent. .

When making a paint, any pigment, solvent, etc. are selected as appropriate, and an antifouling paint is made by a conventional method.

As already mentioned, since the resin composition of the present invention has antifouling properties itself, there is no need to add other antifouling agents, but if desired, other known antifouling agents may be added to the paint.

A disinfectant or the like may be added. Such agents include, for example, bis(tributyltin) oxide, tributyltin chloride, tributyltin fluoride, tributyltin acetate, tributyltin nicotinate, tributyltin persate, bis(tributyltin) alpha.
, α'-dibrom succinate, triphenyltin hydroxide, 1-rephenyltin nicotinito, triphenyltin persate, bis(triphenyltin) α, α'-dibrom succinate, bis(triphenyltin) ) Can also be used in combination with organic tin compounds such as oxides. In addition, commonly used coloring pigments, extender pigments, organic solvents, etc. can be freely selected and used.

The compositions of the invention can be prepared by methods known per se in the paint manufacturing art.

For compounding, known machines such as ball mills, Hebrew mills, roll mills, speed run mills, etc. can be used.

The antifouling paint made using the resin composition of the present invention exhibits a stable antifouling effect over a long period of time, and is completely comparable in performance to conventional antifouling paints based on triorganotin-containing acrylic resins. Since the process does not rely on expensive triorganic tin, the cost can be greatly reduced and public health problems can be avoided.

The present invention will be explained below with reference to Examples. Parts and percentages are by weight unless otherwise specified.

Varnish Production Example 1 75 parts of pheasant roll and 75 parts of n-butanol are added to a four-bottle flask equipped with a stirrer, a reflux condenser, and a dropping funnel, and maintained at 110°C to 115°C. In this solution, 70 parts of ethyl acrylate, 35 parts of 2-ethylhexyl methacrylate,
A mixed solution of 15 parts of acrylic acid and 3 parts of azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours, and the temperature was kept for 2 hours after dropping.6 The solid content of the obtained resin solution was 39.6%, and the viscosity was 2.
．． Varnish A with 3 voids was obtained.

Varnish Production Example 2 Into the same reaction vessel as in Varnish Production Example 1, 75 parts of pheasant roll and 75 parts of n-butanol are added and kept at 110°C to 115°C. In this solution, 2-ethylhexyl methacrylate 5
0 parts, methyl methacrylate 45 parts, methacrylic acid 5 parts,
A mixed solution of 2 parts of benzoyl peroxide was added dropwise over 3 hours, and the mixture was kept warm for 2 hours. The solid content is 39.9% and the viscosity is 0.
It was 9 poise. Varnish B was obtained by adding 46 g of a 5vt/wt% solution of sodium hydroxide in methanol to the mixture.

Example 1 100 parts of toluene, 250 parts of dibutyltin oxide, 86 parts of methacrylic acid, and 167 parts of nitrobenzoic acid were added to the same reaction vessel as in Varnish Production Example 2, and the mixture was heated under an air valve for 12 hours.
The reaction was carried out at 0° C. for 3 hours, and the generated water was removed. Next, insoluble matter was filtered off. The obtained toluene solution has a green color,
A toluene solution of which vinyl groups and tin carboxylates were confirmed by IR was added to the same reaction solution as in Varnish Production Example 1, and 150 parts of xylene were added to the solid content.

Maintain at 100°C to 115°C. In this, methacrylic acid n-
150 parts of butyl, 2 parts of azobisisobutyronitrile
The mixture was dropped over a period of time and kept warm for 2 hours.

Varnish V-1 was obtained with a solid content of 54.8% and a viscosity of 1.8 poise. The tin content of this varnish was determined by fluorescent X-ray method and was found to be 5 wt%.

Furthermore, the presence of nitrobenzoic acid was confirmed by UV absorption. This resin varnish is designated as R-1.

Example 2 100 parts of toluene, 249 parts of dibutyltin oxide, 86 parts of methacrylic acid, and 138 parts of salicylic acid were added to the same reaction vessel as in Varnish Production Example 2, and the mixture was heated at 120°C under an air valve.
The reaction was carried out for 3 hours and the produced water was removed. Next, insoluble matter was filtered off. Vinyl groups and tin carboxylate were confirmed in the solid content of the obtained toluene solution by IR.

100 parts of this toluene solution was added to the same reaction solution as in Varnish Production Example 1, 200 parts of xylene were added, and the temperature was raised to 100°C. 150 parts of methyl methacrylate and 2 parts of azobisisobutyronitrile were added dropwise to this mixture over 3 hours, and the mixture was kept warm for 2 hours. The solid content of this varnish is 49.2% and the viscosity is 2.1.
Boies varnish V-2 was obtained. The tin content of this varnish was determined in the same manner as in Example 1, and the tin content was 4.2 tit%.
Met.

Example 3 100 parts of varnish A, 14 parts of nitrobenzoic acid, and 20.7 parts of dibutyltin oxide were added to a four-bottle flask equipped with a stirrer, a reflux condenser, and a decanter, and the temperature was raised to 120°C and kept for 2 hours. did. During this time, the water produced was removed. The resulting varnish was Varnish V-3 with a solid content of 53.8% and a viscosity of 2.3 poise. This varnish was reprecipitated from white spirit, and the tin content in the resulting resin was determined by fluorescent X-ray method and was found to be 6.5 νt%.

Example 4 150 parts of varnish A, 11.8 parts of monochloroacetic acid, and 31 parts of dibutyltin oxide were added to the same reaction vessel as in Example 3, and the temperature was raised to 120° C. and kept for 2 hours. During this time, the water produced was removed. The resulting varnish had a solid content of 51.8%.
, Varnish V-4 having a viscosity of 2.1 poise was obtained. This varnish was reprecipitated from white spirit, and the tin content in the resulting resin was determined by fluorescent X-ray method and was found to be 6.8 wt%. into a lo flask.

Varnish B 100 parts, diethyldithiocarbamic acid-Na
40 parts and 70 parts of dibutyltin chloride were added.

React at 120 °C for 2 hours, filter, and remove Varnish V-5.
I got it. This varnish had a solid content of 39.6% and a viscosity of 1.4 voids. The tin content of this varnish was determined in the same manner as in Example 2, and the tin content was 2.2 t%.

Example 6 Into the same reaction vessel as in Example 3, 100 parts of varnish A, 5-
14.4 parts of quinolinecarboxylic acid and 20.7 parts of dibutyltin oxide were added, the temperature was raised to 120°C, and the temperature was kept for 2 hours. During this time, the water produced was removed. The obtained varnish V-6 had a solid content of 51.6% and a viscosity of 2.3 voids. This varnish was reprecipitated from white spirit, and tin in the resulting resin was quantified by fluorescent X-ray method, and was found to be 5.1 wt%.
It contained.

Example 7 In the same reaction vessel as in varnish production example 1, Kijirol 150
100°C to 110°C. In this solution, 100 parts of monochloroacetic acid, 2 parts of azobisisobutyronitrile,
A mixed solution of 1 part was added dropwise over 3 hours, and the mixture was kept warm for 2 hours.

The solid content was 36.6% and the viscosity was 0.6 voids.

Add 150 parts of this varnish to 20 parts of dibutyltin oxide, and while removing the refluxing solvent, raise the temperature to 140°C.
Keep at 145°C. As the reaction progressed, the varnish became clear and a pale yellow varnish V-7 with a viscosity of 1.3 poise and a solid content of 51.3% was obtained.

The tin content in this resin solid was 11 wt%.

Examples 8 to 13 The same method as in Example 7 was repeated using the raw materials listed in Table 1 to obtain resin varnishes V-8 to -13, respectively.

Comparative varnish production example Comparative example 1 Varnish A of Varnish Production Example 1 is referred to as Comparative Varnish A.

Comparative Example 2 100 parts of varnish A, 16.7 parts of lauric acid, and 20.7 parts of dibutyltin oxide were added to a four-roof flask equipped with a stirrer, a reflux condenser, and a decanter, and the temperature was raised to 120°C for 2 hours. I kept it warm. During this time, the water produced was removed. The obtained varnish had a solid content of 54.5% and a varnish viscosity of 1.9.
Comparison varnish B of Poise was obtained. This varnish was reprecipitated from white spirit, and the tin content in the resulting resin was determined by fluorescent X-ray method, and was found to be 6.3 wt%.

Comparative Example 3 In a four-bottle flask equipped with a stirrer, a reflux condenser, and a dropping funnel, 100 parts of pheasant roll was added, and the temperature was maintained at 80°C to 85°C. A mixed solution of 50 parts of methyl methacrylate, 40 parts of 2-ethylhexyl methacrylate, and 1.5 parts of azobisisobutyronitrile was dropped into this solution at a uniform rate over 3 hours, and the mixture was kept warm for 2 hours after the dropwise addition. Next, nitrobenzoin filo parts and 8 parts of iron hydroxide were added and stirred at 120'C for 2 hours to obtain Comparative Varnish C with a solid content of 50.2% and a viscosity of 3.9 voids. Ta.

This varnish was reprecipitated in the same manner as in Example 2, and the iron content in the resin was determined, and the iron content was 0.01 wt% or less.

The varnishes used in Clear Paint Consumption Test Examples 1 to 13 and Comparative Examples 1 to 3 were (
(as a clear paint) to a test plate with a dry film thickness of 140μ, and this test plate was attached to the disc rotor plate at a constant speed (peripheral speed of about 30 knots) in seawater (water temperature 20°C ± 2°C). The elution film thickness was measured by rotating day and night for several months. The results are shown in Table 2.

Table 2 Paint film wear test Example 14 40 parts by weight of varnish V-1 obtained in Example 1, 2 parts by weight of cuprous oxide
5 parts by weight, 10 parts by weight of zinc white, 2 parts by weight of colloidal silica, 5 parts by weight of titanium oxide, 5 parts by weight of red iron oxide, 3 parts by weight of n-butanol and 10 parts by weight of Kijirole were dispersed in a ball mill for 5 hours to form a coating composition. I got something.

Examples 15 to 26 and Comparative Examples 4 to 6 Using the resin varnishes obtained in Examples 2 to 13 and Comparative Examples 1 to 3, paints were prepared according to Example 14 according to the paint formulations shown in Tables 3 and 4, respectively. A composition was obtained.

Each paint obtained in Examples 1 to 26 and Comparative Examples 1 to 6 was applied to a sandblasted steel plate coated with anti-rust paint in advance to a dry film thickness of approximately 200 μm. A test plate was prepared by brush painting twice so that the stain resistance was immersed in a test raft in Aioi Bay, Hyogo Prefecture.The results are shown in Table 5.

The clear paints of Examples 1 to 13 had antifouling properties for more than 18 months, and the paints of Examples 14 to 26 had good antifouling properties for 30 months.

As described above, since the hydrolyzable resin composition having an antifouling agent in the side chain obtained by the present invention gradually releases the antifouling agent through hydrolysis, it is necessary to add a known antifouling agent. This is an epoch-making resin composition that can maintain its antifouling performance for a long period of time. In addition, if desired, known antifouling agents, pigments,
Antifouling paints containing additives not only improve their antifouling performance, but because the paint film gradually dissolves into seawater, they eliminate unevenness on the surface of the paint film, reducing fuel consumption during navigation, and provide antifouling for an unprecedentedly long period of time. The stain performance can be maintained.

Claims (1)

[Claims] (1) The end of at least one side chain has a formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (In the formula, X is ▲A mathematical formula, a chemical formula, a table, etc.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼, methylene group or methine group; x is an integer of 1 to 2; R_1 is a hydrocarbon having 1 to 10 carbon atoms; , chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -S-, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ An organic compound residue with antifouling properties that is bonded to the tin atom in the formula through a bond ; R_3 is hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms) A polishing-type antifouling paint composition characterized by containing as a vehicle a tin metal-containing resin composition comprising a resin having at least one group represented by hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms. .