JPS60123569A - Antifouling coating compound - Google Patents

Abstract

PURPOSE:An antifouling coating compound for coating constructions in water, etc. hving improved storage stability, capable of being processing into a high solids state, comprising an organotin high polymer composition as a vehicle obtained by using a radical polymerization initiator having specific properties, having no free acid group. CONSTITUTION:For example, (A) an organotin high polymer composition obtained by blending (i) a tris organotin salt of a carboxilic acid containing one radically polymerizable double bond in the molecule wth (ii) a monomer containing one radically polymerizable double bond and no free acid group in the molecule in a weight ratio of preferably (30:70)-(70:30), polymerizing the blend in the presence of (iii) a radical polymerization initiator (e.g. azo polymerization initiator) having no acid group, not forming a free acid group, is used as a vehicle, and it is optionally blended with (B) an antifouling coating compound component (e.g., copper compound, etc.), to give the desired coating compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an underwater antifouling coating which is highly storage stable and capable of high solids.

Marine organisms such as Fujitbo and Ulva adhere to ships, underwater structures, fishing nets, etc., causing damage such as corrosion of structures, increased seawater frictional resistance of ships, and mass death of fish due to clogging of nets. . In order to prevent the attachment of these harmful aquatic organisms, underwater antifouling paints containing antifouling agents such as cuprous oxide are applied.

Vinyl resin-based antifouling paints and oil-based antifouling paints that have been commonly used in the past have a large amount of copper ion elution at the initial stage, and therefore cannot maintain their antifouling properties over a long period of time.

To compensate for this drawback, antifouling paints using trialkyltin polymer compounds as vehicles have appeared and have attracted attention. This antifouling paint is outstanding in that it suppresses the elution amount of the antifouling agent to the minimum level that maintains the antifouling property, and elutes a constant amount over a long period of time. The feature of this paint is that the trialkyltin polymer compound used as the vehicle is hydrolyzed in a slightly alkaline atmosphere in seawater, releasing the tin compound, and the vehicle becomes water-soluble and the paint film is worn away. Therefore, the unevenness of the paint film becomes smooth,
It reduces the seawater frictional resistance of ships and contributes to fuel cost savings.

Underwater anti-TTI paints using this trialkylssus polymer compound as a vehicle usually contain a sparingly soluble copper compound such as cuprous oxide in order to enhance the antifouling effect. However, antifouling paints containing a trialkyltin polymer compound and cuprous oxide have the drawback of low storage stability, as they may thicken over time during storage or sometimes gel.

Eliminate this.

Attempts to do so include a method in which cuprous oxide and a trialkyltin compound are stored separately and used together at the time of painting (Japanese Patent Application Laid-Open No. 119534/1983), and a method in which copper rhodanide is used instead of cuprous oxide. (Unexamined Japanese Patent Publication No. 54-125233),
Method of mixing various additives (Japanese Patent Application Laid-Open No. 1983/1989+O92E2)
．． 57-141466) have been proposed, but none of them are satisfactory in terms of work inconvenience, economy, and effectiveness.

Furthermore, it has recently been found that antifouling paints containing the trialkyltin polymer compound and copper compound have poor slime resistance. Slime is a general term for diatoms, a viscous film of various underwater bacteria and bacterial metabolites, and when this slime lands on water, spores of sea lettuce, sea cucumbers, or barnacle larvae enter, causing the reproduction of contaminant organisms. Therefore, it is very meaningful for an antifouling paint to have excellent slime resistance.

Therefore, in order to expand the antifouling spectrum of the antifouling paint containing the trialkyltin polymer compound and copper compound to include slime resistance, it is possible to use an organic nitrogen-containing sulfur compound with excellent slime resistance. Dithiocarbamate compounds, which have poor slime resistance, are used in combination with inorganic copper compounds, which have long-term antifouling properties, and are combined with conventionally used peroxide polymerization initiators that generate acid groups. When a polymerized trialkyltin polymer compound is used in an antifouling paint as a vehicle, the paint thickens and becomes kelp in a short period of time during storage, or the antifouling property after storage deteriorates significantly, making it unsuitable for practical use. I understand. For this reason, attempts were made to microcapsule both or one of an inorganic copper compound and a nitrogen-containing sulfur compound, but although storage stability was improved, other aspects such as antifouling properties and workability deteriorated, making it unsatisfactory. No results were obtained.

Combining an inorganic copper compound and a nitrogen-containing sulfur compound, especially thiocarbamates, into an antifouling paint using a trialkyltin polymeric vehicle as a vehicle, without adversely affecting the storage stability or other performance of the paint. If this is possible, it is expected that an antifouling paint with excellent long-term antifouling properties and slime resistance will be obtained, and its performance will be further improved.

An object of the present invention is to provide an underwater antifouling paint that satisfies such requirements.

In addition, the conventional anti-leta paints that use rosin as a base use synthetic resins such as chlorinated rubber and polyvinyl chloride as vehicle components, and these resins and rosin are dissolved to make paintable paints. These antifouling paints required a large amount of solvent, and the volume non-volatility percentage was about 30-40%, and the film thickness of one coat was 50-7.
It was 0μ. There are various methods of applying these thickly in one coat, and using an anti-flow agent is one of them, but the result is not satisfactory. The film thickness is at most 80μ/time.However, in systems where these anti-flow agents are added, the viscosity increases due to the addition of additives, making painting work more difficult.As a result, during painting work, it is difficult to improve workability or Since it is an airless coating, it is necessary to add a solvent.Therefore, a large amount of solvent is scattered into the atmosphere, which is undesirable from the viewpoint of resource saving and environmental protection.

In antifouling paints that use 1-realkyltin polymer compounds as vehicles, which have been attracting attention recently, the trialkyltin polymer compounds are hydrolyzed in a slightly alkaline atmosphere in water, releasing soot compounds, and the vehicle becomes water-soluble. ■Since the coating is self-polishing, the coating film remains smooth and does not reduce the seawater frictional resistance of the ship, so the duration of the coating film is proportional to the thickness of the coating film, so it is possible to It is advisable to apply it thickly. However, simply increasing the number of times a car is coated will not only increase the amount of solvent splashed into the atmosphere, but also increase the cost of painting. In order to coat thickly without such drawbacks, there is a need for a high solids paint that uses less solvent and has a larger film thickness per coat.

An object of the present invention is to provide a high solid antifouling paint that satisfies such demands. "High solids" as used herein means that the volumetric non-volatile content of the paint is 45 to 70%.

The present invention includes, as a vehicle, an organotin polymer composition having no free acid groups, which is obtained using a radical polymerization initiator that does not have acid groups and does not generate free acid groups. The present invention relates to an antifouling paint containing antifouling paint components.

The organotin polymer composition comprises (a) a mono- to organic tin salt of a carboxylic acid containing one radically polymerizable double bond in each molecule; and (b) containing one radically polymerizable double bond in each molecule. A mixture of monomers copolymerizable with the above-mentioned (Al) which has the above-mentioned properties and does not have free acid groups, using a radical polymerization initiator which does not have the above-mentioned acid groups and does not generate one or more free acid groups. and polymerize it by a conventional method (A).

Examples of radical polymerization initiators that do not have acid groups and do not generate free acid groups include azo polymerization initiators,
2,2′-azobisisobutyronitrile, 2,2′-azobis-t2,4-dimethylvaleronitrile), 2
．． 2"-Azobis(4-methquine-2,4-dimethylvaleronitrile), ■-Azobis-1-cyclohexanetriponitrile, dimethyl-2,2"-azobisisobutycy-1-, etc., or are limited to these. Any azo polymerization initiator without free carboxyl groups can be used.

The radical polymerization initiator that does not have an acid group and does not generate free acid groups may be a peroxide polymerization initiator, examples of which include ketone peroxide, sialkyl peroxide, and hydroperoxide. There are oxides, peroxyketal lamp 1, hydrogen peroxide, etc.

Specific examples thereof are shown in Table 1 below.

(Left below) 1 in the molecule forming the organotin salt ta) which is a constituent unit of the organotin polymer composition having no free acid groups.
Examples of carboxylic acids containing 2 radically polymerizable double bonds include acrylic acid, methacrylic acid, itaconic acid, itaconic acid monoalkyl creester, maleic acid, maleic acid monoalkyfurester, fumaric acid, and fumaric acid. Examples include monoalkyl costil. Examples of the triorganotin organic group in the structural unit tal include ethyl, propyl, butyl, cyclohexyl, and phenyl.

In other words, as an example of the structural unit +a) of the organotin polymer composition having no free acid group, triethylsus,
Triorganotin acrylates and methacrylates such as tripropyltin, tributyltin, 1-lycyclohexyltin, triphenyltin, the corresponding bis-1-lyorganotin salts of itaconic acid, maleic acid and fumaric acid. , itaconic acid monoalkyl ester, maleic acid monoalkyl ester, and the corresponding mono-triorganotin salt.

The other component of the organic soot polymer composition having no free acid groups (monomers such as methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl acrylate, ethyl acrylate, butyl acrylate) , octyl acrylate-1
・Acrylic compounds such as dodecyl acrylate, cyclohexyl acrylate, phenyl acrylate, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylaterile, vinyl acetate, vinyl butyrate, butyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, lauryl vinyl ether, etc. Vinyl hydrocarbons such as vinyl compounds having groups, ethylene, butadiene, and styrene can be mentioned. These monomers are 1
Used in one species or in combination of two or more.

The structural unit (al:(bIO) ratio in the organotin polymer composition having no organic acid group is 3o; 70 by weight)
It is desirable that the content is between 70 and 30, and if the amount of trialkylsus salt + a) in iii.
<111 can't wait, and if there is too much, it will take a long time when used as an antifouling paint] A solid coating film will not be obtained.

The structural unit <al, the molecular weight of the copolymer (b) is,
A number average molecular weight of 6,000 to 30,000 is preferred; a lower molecular weight will not provide a tough coating film, and a higher molecular weight will not result in a paint with good storage stability.

The antifouling paint of the present invention can contain at least one antifouling agent.

These antifouling agents include copper-based antifouling agents such as cuprous oxide, copper rhodanide, copper hydroxide (■), and copper naphthenate; (dithiocarbamic acid) 6G (abbreviated as ZINEB), ethylene-bis(dithiocarbamic acid) manganese (abbreviated as MANEB), tetramethylthiuram monosulfide (abbreviated as TS), his-(dimethyldithiocarbamic acid) copper (abbreviated as TTCu), and the like.

When a copper compound and a nitrogen-containing sulfur compound are used together, the ratio can be varied over a wide range depending on the purpose;
It is appropriate to use 5 to 200 parts by weight, preferably 1 to 150 parts by weight, of the nitrogen-containing sulfur compound.

Also, the total amount of antifouling agent is 5% based on the weight of the entire paint.
to 70 iJ%, preferably 6 to 55% by weight
is appropriate.

The antifouling paint of the present invention exhibits sufficient slime resistance and/or antifouling properties by containing at least one of the above-mentioned antifouling agents, so there is no need to further blend other antifouling agents. This does not preclude the mixing of other known antifouling agents and disinfectants, for example, bis(tributyltin) oxide, tributyltin chloride, tributyltin fluoride, tributyltin acetate, tributyltin nicotinate, and tributyltin. Acetate, his(tributyltin) α, α゛-dibrom succinate, l.liphenyltin hytrooxide, triphenyltin nicotine-1., triphenyltin hazatate, bis(triphenyltin) α.

It is also possible to use it in combination with an organic tin compound such as α''-dibromsuccine-1., bis(l-liphenyltin) oxide.

The antifouling paint of the present invention may contain a polishing agent of 11g. Polishing 8PiI modifier is a polishing agent that accelerates the polishing (sanding) speed of the vehicle used in the present invention.
Or, on the contrary, it is an additive that has a slowing effect, and as a regulator that accelerates the cleaning speed, a substantially water-insoluble metal pigment that can react with water to produce a water-soluble metal compound is used. Examples include zinc white, cuprous oxide, and copper rhodanide. Also, what are the adjustment agents that have the effect of slowing down the cleaning speed? Solubility in wastewater is 5 ppm at 25°C
The following organic compounds are used, typical examples include methylphenyl silicone, chlorinated diphenyl, chlorinated halaffin, and the like.

Other commonly used plasticizers, coloring pigments,
You can freely select and use N agents, LA/8 agents, etc.

The antifouling paint of the present invention can be manufactured in an amount of 1 lil by a method known per se in the field of paint manufacturing technology. For compounding, known machines such as ball mills, Hebrew mills, roll mills, speed run mills, etc. can be used.

According to the present invention, there is provided an underwater antifouling paint that has excellent storage stability and antifouling properties, and also has a self-polishing effect on the coating film by hydrolysis of the triple gilt tin polymer compound used as a vehicle. It is possible to effectively prevent the attachment of harmful aquatic organisms to underwater structures, fishing nets, etc., and to reduce fuel consumption during ship operation.

In addition, according to the present invention, it is possible to make the antifouling paint highly solid, which allows for a thicker coating per coat, resulting in cost savings by reducing the number of coats required to reach the desired coating thickness; Contributes to resource conservation and environmental protection by reducing the amount of flying solvent.

The present invention will be explained in detail below with reference to Examples. Note that "1 part" in "Production Examples", "Examples", and "Comparative Examples" is based on weight.

Production Example 1: Add 67 parts of pheasant into a fourth flask equipped with a reflux condenser, dropping funnel, and stirrer, and heat to 80°C to 85°C.
Keep it. In this solution, 55% of 1-butyltin methacrylate was added.
A mixed solution of 5 parts of methyl methacrylate, 45 parts of methyl methacrylate, and 1.2 parts of 2.2'-azobisisobutyronitrile was added dropwise over 4 hours, and the mixture was kept warm for 3 hours.

The solid content of the obtained IL1 fat melt was 60.1%, the viscosity was 5°2 Boise, and the number average molecular weight of the resin was 116,000.
I got f4.

Production Example 2 Using the same reaction apparatus as Production Example 1, 40 parts of pheasant roll was added to a fourth flask and maintained at 80 to 85°C.

During the night, 4 parts of a mixed solution of 53 parts of triphytyltin methacrylate, 37 parts of methyl methacrylate, 6 parts of isobutyl methacrylate, 4 parts of ethyl acrylate, and 1.0 part of 2,2'-azobisisobutyronitrile was added to the volume of this sample. Drop it over a period of time and keep warm for 3 hours after dropping. After that, 27 parts of pheasant roll was added, resulting in a solid content of 59.8%.

Viscosity 6.4 voices, number average molecule of resin ff1j, 8,0
00 glue varnish 13 was obtained.

Production Example 3 Using the same reactor as in Production Example 1, 30 parts of pheasant roll was added to four 1'' flasks and maintained at 80-85°C.

In this solution, 65 parts of 1-butyltin methacrylate, 30 parts of methyl methacrylate, 5 parts of 2-ethylhexyl methacrylate, 1.
0 parts of Mixture/8 liquid was added dropwise over 4 hours and kept warm for 3 hours after the addition. After that, add 30 parts of Kijiroru and add 6 parts of solids.
0.2%, viscosity 7.2 voids.

Number average molecular weight of resin 21. (100 varnish C was obtained.

Production Example 4 Using the same reactor as in Production Example 1, 30 parts of pheasant roll were added to four flasks and maintained at 80-85°C.

During the night, a mixture of 8 parts of methacrylic fil/butyltin, 30 parts of methyl methacrylate, 25 parts of ethyl acrylate, and 1.0 parts of 2.2'-azobisisobutyronitrile was added to the mixture for 4 hours. After dropping, keep warm for 3 hours. Then add 36 parts of pheasant roll, solid content 60.0%
, viscosity 7.3 voids, number average molecular weight of resin 22,000
Varnish D (M).

Production Example 5 Using the same reaction apparatus as Production Example 1, 30 parts of pheasant roll was added to a 4-coffee flask and maintained at 80 to 85°C.

Methacrylic acid in this solution!・A mixed solution of 40 parts of butyltin, 20 parts of methyl methacrylate, 30 parts of ethyl acrylate, 10 parts of acrylonitrile, and 1.0 part of 2,2''-azobisisobutyronitrile was added dropwise over 4 hours. The mixture was kept warm for the next 3 hours. Thereafter, 36 parts of Pheasant Roll was added to obtain one varnish having a solid content of 60.3% and a viscosity of 7.2 VOID resin with a number average molecular weight of 4122.000.

Production Example 6 Using the same reaction apparatus as in Production Example 1, 50 parts of pheasant, 65 parts of tributyltin methacrylate, and 35 parts of methyl methacrylate were added to a four-bottle flask and maintained at 70 to 75°C.

A mixed solution of 1.2 parts of 1,1'-azohiscyclohexane carbonitrile and 16 parts of quidylol was added dropwise to this solution over a period of 4 hours, and the mixture was kept warm for 3 hours after the addition. The resulting resin solution had a solid content of 60.1%, a viscosity of 5.6 voids, and a resin number average molecule i of 17,000. Varnish F was obtained.

Production Example 7 Using the same reaction apparatus as in Production Example 1, 25 parts of pheasant roll was added to a four-bottle flask and maintained at 75-80°C.

In this solution, 60 parts of tributyl methacrylate, 35 parts of methyl methacrylate, 5 parts of n-butyl acrylate, 2
A mixed solution of 0.8 parts of , 2'-azohisisobutyronitrile was added dropwise over 4 hours, and the temperature was kept for 3 hours after the addition. Then add 41 g++ of kiji roll, solid content 60.1%
, viscosity 8.4 Bo・fs, number average molecular weight of resin 29,00
A varnish G of 0 was obtained.

Production Example 8 Using the same reactor as Production Example 1, process 30 parts of pheasant roll in 4 x 10 flasks and maintain the temperature at 125-130°C.

This 18? Triphytyl methacrylate 60 in RL
1 part, 32 parts of methyl methacrylate, 8 parts of 2-ethylhexyl methacrylate, and 2 parts of dicumyl peroxide were added dropwise over 4 hours, and the mixture was kept warm for 5 hours after the addition. Thereafter, 36 parts of pheasant roll were added to obtain varnish I] having a solid content of 59.2%, a viscosity of 3.3 voices, and a resin number average molecular weight of 11.000.

Production Example 9 Using the same reaction apparatus as in Production Example 1, 30 parts of pheasant roll was added to a four-bottle flask and maintained at a temperature of A-125 to 135°C.

Into this solution, 53 parts of tributyltin methacrylate, 37 parts of methyl methacrylate, 5 parts of 2-ethylhexyl methacrylate, 5 parts of ethyl acrylate, and 2 parts of G-butyl peroxide were added dropwise over 4 hours, and 5 hours after dropping. Keep warm. After that, 36 parts of pheasant roll was added, and the solid content was 59.
7%, viscosity 3.8 voices, number average molecule of resin (ft12
,000 of Varnish I was obtained.

Production Example 10 Using the same reaction apparatus as Production Example 1, in a fourth flask, 10 parts of kijirole, 20 parts of methylisobutylkene,
Add 8 parts of maleic anhydride and maintain at 75-80°C.

To this solution, 67 parts of methyl methacrylate, 10 parts of 2-ethylhexyl methacrylate, 15 parts of styrene, and 1.1 parts of 2,2'-azohisisobutyronitrile were added dropwise over 4 hours, and the mixture was kept warm for 3 hours.

Next, add 48 parts of his(tributylsus) oxide and 3
After stirring for 0 minutes, 68 parts of pheasant roll was added, and the solid content was 60.1.
%, il', Ij degree 6.2 voice, resin number average molecular weight 19,000 varnish J with g7 saw.

Production Example 1 Using the same reaction apparatus as Production Example 1, in the fourth flask 10 parts of ximicol, 20 parts of methyl isobutyl ketone,
Add 12 parts of maleic anhydride and maintain at 75-80°C.

A mixed solution of 72 parts of methyl methacrylate, 8 parts of styrene, 8 parts of ethyl acrylate, and 1.2 parts of 2,2''-azobisisobutyronitrile was added dropwise to this solution over 4 hours, and then kept warm for 3 hours. Next, 10 parts of n-buknol was added and stirred for 30 minutes, and after keeping warm, 35 parts of bis(tributyltin) oxide was added and kept at 80°C for 30 minutes, and water produced by esterification was removed by distillation under reduced pressure. Add the same amount of pheasant roll as the amount, solid content 60.4%, viscosity 5.
Varnish K with 8 voices and a resin number average molecular weight of 18,000
t- got it.

Production Example 12 Using the same reactor as in Production Example 1, 30 parts of pheasant roll was added to a four-bottle flask and maintained at 80-85°C.

In this solution, 65 parts of triphenyltin methacrylate, 20 parts of methyl methacrylate, 15 parts of ethyl acrylate, 2
A mixed solution of 1.2 parts of 2°-azobisisobutyronitrile was added dropwise over 4 hours, and after keeping warm for 3 hours, 37 parts of Kijirole was added to give a solid content of 59.7%, a viscosity of 7.0 voids, and a resin content of 59.7%. Varnish 7 having a number average molecular weight of 23.000 was obtained.

Production Example 13 Using the same reaction apparatus as in Production Example 1, 30 parts of pheasant roll and 50 parts of itaconic acid di(tributyltin) salt are added to a four-bottle flask and maintained at 75 to 85°C.

In this solution, 30 parts of methyl methacrylate, 10 parts of ethyl acrylate, 10 parts of 2-ethylhexyl methacrylate,
A mixed solution of 1.2 parts of 2,2'-azobisisobutyronitrile was added dropwise over 4 hours, and the mixture was kept warm for 3 hours. After that, 35 parts of pheasant roll was added, solid content 59.4%, viscosity 6,
Varnish M with 8 voids and a resin number average molecular weight of 23,000
I got it.

Production Example 14 Using the same reaction apparatus as in Production Example 1, 30 parts of kijirole and itaconic acid (monobutyl ester) were placed in four Lof flasks.
Add 55 parts of monobutyl suth salt and maintain at 75-80°C.

In this solution, 35 parts of methyl methacrylate and 2 parts of acrylic acid were added.
- A mixed solution of 10 parts of ethylhexyl and 1.2 parts of 2.2'-azobisisobutyronitrile was added dropwise over 4 hours, and the mixture was kept warm for 3 hours. After that, 35 parts of Kijiroru was added, and the solid content was 59.3%, the viscosity was 7.0 voids, and the number average molecule of the resin! 23,000 fl of varnish N.

Comparative Production Example 1 Using the same reaction apparatus as in Production Example 1, 67 parts of pheasant roll was added to a fourth flask and maintained at 90-95°C.

A mixed solution of 55 parts of tributyltin methacrylate, 45 parts of methyl methacrylate, and 1.2 parts of hendiyl peroxide was dropped into this solution over 4 hours, and kept warm for 3 hours after the dropwise addition.
A comparison varnish with a solid content of 60.0%, a viscosity of 14.6 voids, and a number average molecular weight of resin N 17 , 000 is (η).

Comparative Production Example 2 Using the same reaction apparatus as in Production Example 1, 25 parts of pheasant roll was added to a four-bottle flask and maintained at 85 to 90°C.

A mixed solution of 65 parts of tributyltin methacrylate, 30 parts of methyl methacrylate, 5 parts of n-butyl acrylate, and 1 to 2 parts of benzoyl peroxide is dropped into this solution over 4 hours, and the mixture is kept warm for 3 hours after the dropwise addition.

After that, 125 parts of pheasant roll was added, solid content 40.2%,
Viscosity 8.5 voids, number average molecule of resin 1i29,000
A comparative varnish P was obtained.

Comparative Production Example 3 Using the same reaction apparatus as in Production Example], 30 parts of pheasant roll was added to a fourth flask and maintained at 80 to 85°C.

A mixed solution of 60 parts of 1-butyltin methacrylate, 35 parts of methyl methacrylate, 5 parts of 2-ethylhexyl acrylate, and 1.2 parts of L-butyl-peroxy-2-ethylhexanoate was added dropwise to this solution over 4 hours. After dropping, keep warm for 3 hours. Then add 36 parts of pheasant roll,
Solid content 60.1%.

Viscosity 17.2 poise, ) 11 fat number average molecular weight 23.0
00 comparison varnish Q (M.

Using varnishes A to N obtained in Production Examples 1 to 14, Table 2
An antifouling paint according to the present invention having the formulation shown in Figure 1 was produced for 8 cycles using a conventional method.

As a comparative example, antifouling paints having the formulations shown in Table 3 were cleaved using comparative varnishes O to Q obtained in Comparative Production Examples 1 to 3.

(Left below) Storage stability test of paint made by LIJR3
The color tone and paint condition (change in viscosity) after being stored in a sealed glass container at 50°C for one month were investigated.

The results are shown in Table 4.

(Margins below) As shown in Table 4, the color tone and paint condition of the paints of Examples and Comparative Examples are both good immediately after manufacture, but at 50°
After storage for CXI months, all of the Example paints were in good condition, but the Comparative Example paints changed in quality and gelled.

Further, the Example paint could be sufficiently coated with an airless atomizer without solvent dilution, but the Comparative Example paint was not atomized with an airless atomizer under the same conditions and required dilution with xylene. In addition, the dry film thickness of the coating film obtained by applying the paints of the Examples and Comparative Examples to the fullest flow limit was 150 to 200 μ/coating in the Examples, and 80 to 100 μ/1 coat in the Comparative Examples. .

Use J-Joshi Varnish C to improve the effects of various polishing conditioners.
I got it.

Method: Each paint was applied to a disc to a dry film thickness of 100μ, attached to a disc rotor plate, and rotated day and night in seawater (water temperature 25-28°C) at a constant speed (peripheral speed 35 knots) for 60 days. The degree of wear and tear was measured by actually measuring the cross-sectional film thickness using a microscope, and each paint was compared by setting the wear and tear level of only the resin to which no polishing modifier was added as 1. Part: Weight % Paint Nisstandart Varnish C No. 1, Varnish C 80 parts Zinc white 20 parts Standard I No. 1 1.4 No. 2 0.7 Patent applicant Nippon Paint Co., Ltd. Agent Patent attorney Takao Akaoka

Claims (1)

[Scope of Claims] (1) Contains as a vehicle an organotin polymer composition that has no acid groups and that is obtained using a radical polymerization initiator that does not generate free acid groups. , an antifouling paint containing conventional antifouling paint components as required. (2) The organotin polymer composition has 1 fa in 1 molecule.
(b) a triorganotin salt of a carboxylic acid containing one radically polymerizable double bond in the molecule; 2. The antifouling paint according to item 1, which is obtained by polymerizing a mixture of polymerizable monomers using a radical polymerization initiator that does not have the acid group and does not generate one or more free acid groups. (3) ratio a of the structural units in the organotin polymer composition;
The antifouling paint according to item 2, wherein b is 30:10 to 70:30 by weight. (4) Does not have the above acid group and M! 3. The antifouling paint according to any one of items 1 to 3, wherein the radical polymerization initiator that does not generate 1lIl of acid groups is an azo polymerization initiator. (5) The azo initiator is 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1-azobis-1-cyclohegyzanyluponitrile, dimethyl- The antifouling paint according to item 4, comprising one or more selected from 2,2゛-azobisisobutyrate. (6) The antifouling paint according to any one of items 1 to 3, wherein the radical polymerization initiator that does not have an acid group and does not generate free acid groups is a peroxide polymerization initiator. (7) The antifouling according to item 6, wherein the peroxide polymerization initiator is one or more selected from ketone peroxides, dialkyl peroxides, hydroperoxides, peroxyketals, and hydrogen peroxide. paint. (8) One radically polymerizable double bond in the molecule,
Carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, itaconic acid monoalkyl ester, maleic acid,
The antifouling paint according to any one of items 2 to 7 selected from monoargyl nisyl maleate, fumaric acid, and monoalkyl fumarate ester. (9) The organic group of the triorganosus is ethyl, propyl,
The antifouling paint according to item 8, comprising one or more selected from butyl, cyclohexyl, and phenyl. α0) The anti-teta paint according to item 9, wherein the 1-triorganotin salt of a carboxylic acid containing one radically polymerizable double bond in the molecule is tributyltin (meth)acrylate. 01) The prevention according to item 9, wherein the 1-triorganotin salt of a carboxylic acid containing one radically polymerizable double bond in the molecule is a bis(tributyltin salt) of itaconic acid, maleic acid, or fumaric acid. Dirty paint. (Incorporated) The 1-triorganotin salt of carboxylic acid containing one radically polymerizable double bond in the molecule is a mono(tributyltin) salt of itaconic acid monoalkyl ester, maleic acid monoalkyl ester, and fumaric acid monoalkyl ester. The antifouling paint of item 9 which is salt). (2) The antifouling paint according to item 9, wherein the triorganotin salt of a carboxylic acid containing one radically polymerizable double bond in the molecule is a triphenyltin (meth)acrylate salt. (2) The antifouling paint according to any one of items 1 to 13, which contains an inorganic and/or organic copper compound as an antifouling agent. ■) The copper compound may be cuprous oxide, copper rhodanide, copper hydroxide (
Antifouling paint of item 14, formerly copper naphthenate. (Support) 1. 1 containing a nitrogen-containing sulfur compound as an antifouling agent.
Anti-/η paint according to any of Items 1 to 15. σI) The nitrogen-containing sulfur compound is ethylene-his(dithiocarbamate)zinc, ethylene-his(dithiocarbamate)manganese, tetramethylthiuram monosulfupide, bis-(dithiocarbamate)copper. Dirty paint. (][l) The anti-stain paint according to any one of items 1 to 17, which contains an organic tin compound as an antifouling agent. (+9) The antifouling paint according to item 18, wherein the organic tin compound is tributyltin fluoride, tributyltin fluoride, triphenyltin hydroxide, l.liphenyltin chloride, or l.liphenyltin fluoride.佽) The antifouling paint according to any one of Items 1 to 19, which contains one or more selected from organic pigments, non-TA pigments, and plasticizers as a polishing regulator.