JP3396349B2 - Biofouling prevention coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater object surface.
The present invention relates to a coating composition for preventing the adhesion of organisms. [0002] 2. Description of the Related Art Ship bottoms, buoys, and fishing nets submerged in seawater
(Cultured nets, fixed nets, etc.), anti-pollution film for water, for cooling
Barnacles,
Various obstacles due to adhesion of selbra, mussels, algae, etc.
Happens. To prevent pollution by those organisms,
Paint that prevents organisms from attaching to the surface of underwater objects
It is well known to be clothed. [0003] As an antifouling paint for preventing the attachment of organisms
In the early stages, it forms the basic skeleton that forms the coating film.
Resin does not dissolve in seawater and is a component of resin.
As the solution dissolves, the antifouling agent is extracted from the coating and
Dissolves in water to prevent marine organisms from attaching
Paints of the type have been used. This type of paint has a basic skeleton
In general, the initial antifouling effect
The result is good, but there is a drawback that the antifouling effect will be insufficient in the long term.
I got it. As an improved type, a basic bone for forming a coating film is provided.
The so-called water content, in which the rated resin is hydrolyzed by seawater
Resolvable self-polishing paints have been used. this
Mold paint is always active because it elutes the coating surface.
The surface of the coating film is maintained, and the durability of the antifouling effect is
There is an advantage that it can be easily obtained. [0005] Such a hydrolytic self-polishing type paint
So far, organotin polymers have been widely used
However, in recent years, it has been released as an antifouling agent after hydrolysis.
Marine pollution by tin compounds has become a major social problem
You. Therefore, a hydrolysis-type antifouling paint that does not contain organotin is used.
It is strongly anticipated. [0006] As a self-polishing hydrolyzable paint,
JP-A-60-500452 discloses various hydrolyzable groups.
A number of examples are disclosed, among which organosilicon (Al
(Having a coxysilyl group or an organosilyl group)
(T) Polymers utilizing the hydrolyzability of acrylate
It is shown. Also, Japanese Patent Application Laid-Open No. 4-103671 discloses
Is a hemiacetal ester group or hemiketa
-Fouling coating using vinyl copolymer having ester group
Feed compositions are also disclosed. [0007] [Problems to be solved by the invention]
Japanese Patent Publication No. 500452 discloses that Tris (4-me
Example of the production of (tyl-2-pentoxy) silyl acrylate
However, the description of
No description of coalescing composition, testing as antifouling paint
No results are shown. In addition, regarding organosilyl groups,
And claims of SiR_Three Is implemented
There is no description in the examples, which composition is
There is no description of the suitability. [0008] The present inventors have proposed an organosilyl group as a side chain.
Acrylate resin, methacrylate tree
Fat, maleic acid ester resin and fumaric acid ester tree
As a result of studying fats, the organosilyl group was added to the side chain.
Just having it is the most important hydrolytic antifouling paint
Rotary test required (test piece on outer surface of cylindrical drum)
Fix and rotate the drum in seawater at a peripheral speed of 16 knots
No solubility in coating film thickness consumption rate test)
It does not exhibit good antifouling properties in
Good adhesion to substrates and primers due to cracking
The coating does not fall off when immersed in seawater,
Is not suitable for
Once. Further, Japanese Patent Application Laid-Open No. 4-103671 discloses
For the antifouling paint composition shown in
An accelerator with a side chain containing a ter group or hemicetal ester group
Lylic acid ester resin, methacrylic acid ester resin, male
About acid ester resin and fumarate ester resin
As a result of examination, it was found that
Introduce the necessary and sufficient amount of the above groups to give resolvability
Vinyl polymers are highly hydrophilic when placed side by side in seawater.
Film swells and wrinkles in
It turned out that the performance could not be exhibited. The present invention has been developed under such circumstances,
As a decomposable self-polishing coating composition,
Dissolves into the sea at a suitable speed and evenly without delamination
Excellent hydrolytic properties and excellent antifouling properties for a long time
DemonstrateFor biofouling preventionProviding a coating composition
It is an object. [0011] Means for Solving the Problems The present inventors have set forth the above-mentioned object.
As a result of extensive research to achieve the goal, organosilyl
Group-containing monomer and hemiacetal ester group-containing monomer
Rotary test by using a copolymer of
Good antifouling property with stable coating consumption rate
For a long period of time and to avoid cracks
Good adhesion to undercoat paint
Satisfies all the properties required for demolding antifouling paint
They have found and completed the present invention. That is, the present invention provides the following general formula:
(1); (However, in the formula, R¹~ R^ThreeAre all alkyl groups,
Groups selected from among the reel groups,
Or a different group. X is acryloyl
Oxy group, methacryloyloxy group, maleinoyl oxy
It is a silyl group or a humaroyloxy group. )
Monomer A and the following general formula (2): (However, in the formula, R^FourIs an alkyl group, R^FiveIs an alkyl group
Or a cycloalkyl group. Y is acryloyl oki
Si group, methacryloyloxy group, maleinoyloxy group
Or a fumaroyloxy group. ) Monomer
B and, if necessary, copolymerizable with these monomers A and B.
Of a monomer mixture containing a vinyl monomer C
And an antifouling agent as essential components.
ToBiofouling prevention coating composition (hereinafter simply referred to as coating composition
That)It is related to. [0013] DESCRIPTION OF THE PREFERRED EMBODIMENTS In the coating composition of the present invention,
One or two types of the monomer A represented by the general formula (1)
And at least one kind of the monomer B represented by the general formula (2).
Species or two or more species and, if necessary, these monomers A and B
One or more of the other copolymerizable vinyl monomers C
The copolymer of the monomer mixture containing
It was used as one. The monomer A is represented by the general formula (1)
Thus, as an unsaturated group (X) in the molecule, acryloyl
Oxy group, methacryloyloxy group, maleinoyl oxy
Si group [mainly monoalkyl (C1-6) ester male
Inoyloxy group) or fumaroyloxy group (mainly
Noalkyl (C1-6) ester fumaroyloxy
Group) and a triorganosilyl group
Things. In the triorganosilyl group, three groups
Alkyl group or aryl group (R¹ ~ R^Three ) Are the same as each other
It may be one group or different groups. Specifically
Is methyl, ethyl, n-propyl, n-butyl, etc.
A linear alkyl group having 20 or less carbon atoms;
Carbon number such as butyl, isobutyl, s-butyl, t-butyl
A branched alkyl group having 20 or less; cyclohexyl group, etc.
Cyclic alkyl group; phenyl group, tolyl group, xylyl
Aryl, naphthyl, etc.
These substituted aryl groups are exemplified. Replacement ants
As the halogen group, halogen, an alcohol having up to about 18 carbon atoms
Substitute with a kill group, acyl group, nitro group or amino group
The aryl group was used. Such a monomer A has a
As those having a (meth) acryloyloxy group,
Trimethylsilyl (meth) acrylate, triethylsilyl
(Meth) acrylate, tri-n-propylsilyl
(Meth) acrylate, tri-n-butylsilyl (meth)
(T) acrylate, tri-n-amylsilyl (meth) a
Acrylate, tri-n-hexylsilyl (meth) acryl
Rate, tri-n-octylsilyl (meth) acrylate
G, tri-n-dodecylsilyl (meth) acrylate,
Triphenylsilyl (meth) acrylate, tri-p-
Methylphenylsilyl (meth) acrylate, triben
Zirsilyl (meth) acrylate, triisopropylsi
Ryl (meth) acrylate, triisobutylsilyl (meth)
T) acrylate, tri-s-butylsilyl (meth) acrylate
Acrylate, tri-2-methylisopropylsilyl (meth
T) acrylate, tri-t-butylsilyl (meth) acrylate
Creat and the like. Further, (meth) acryloyl oxy
As another example having a silyl group, ethyldimethylsilyl (meth
(T) acrylate, n-butyldimethylsilyl (meth)
Acrylate, diisopropyl-n-butylsilyl (meth
(T) acrylate, n-octyldi-n-butylsilyl
(Meth) acrylate, diisopropylstearylsilyl
(Meth) acrylate, dicyclohexylphenyl
Ril (meth) acrylate, t-butyldiphenylsilyl
(Meth) acrylate, lauryldiphenylsilyl
(Meth) acrylate and the like. Further, a maleinoyloxy group or a
Or those having a fumaroyloxy group,
Propylsilyl methyl maleate, triisopropylsilyl
Luamyl maleate, tri-n-butylsilyl-n-butyl
Lumarate, t-butyldiphenylsilylmethyl maleate
G, t-butyldiphenylsilyl-n-butylmale
, Triisopropylsilylmethyl fumarate, torii
Sopropylsilyl amyl fumarate, tri-n-butyl
Silyl-n-butyl fumarate, t-butyl diphenyl
Silylmethyl fumarate, t-butyldiphenylsilyl
-N-butyl fumarate and the like. The monomer B is represented by the general formula (2)
As described above, as the unsaturated group (Y) in the molecule,
An acryloyloxy group similar to the unsaturated group (X) of A,
Tacryloyloxy group, maleinoyloxy group (mainly
Noalkyl (C1-6) ester maleinoyl oki
Group) or fumaroyyloxy group (mainly monoalkyl
(1-6 carbon atoms) ester fumaroyloxy group]
And a hemiacetal group. In the hemiacetal group, R^Four Is meth
, Ethyl, n-propyl, isopropyl, n-butyl
, Isobutyl, t-butyl and the like having 12 or less carbon atoms
A linear or branched alkyl group;^Five Hame
Chill, ethyl, n-propyl, isopropyl, n-butyl
, Isobutyl, t-butyl and the like having 12 or less carbon atoms
A linear or branched alkyl group,
A cycloalkyl group such as sil or substituted cyclohexyl.
You. As such monomer B, acrylic
Acid, methacrylic acid, maleic acid (or maleic acid mono-
Ester), fumaric acid (or fumaric acid monoester)
A carboxyl group-containing vinyl monomer comprising
Nil ether, propyl vinyl ether, butyl vinyl
Ether, hexyl vinyl ether, 2-ethylhexyl
Alkyl vinyl ethers such as ruvinyl ether,
Cycloalkyl vinyls such as cyclohexyl vinyl ether
Addition reaction with nil ethers, etc. by a conventional method
And is obtained by: Other copolymers copolymerizable with these monomers A and B
Examples of the phenyl-based monomer C include acrylates and methacrylates.
Lylic acid ester, styrene, vinyl acetate, propionic acid
Vinyl esters such as vinyl, vinyl butyrate and vinyl benzoate
Ters, vinyltoluene, α-methylstyrene, croto
Acid esters, itaconic acid esters, fumaric acid ester
Tell and the like. In the monomer mixture, monomers A, B and
Of other vinyl monomers C copolymerizable with these
Can be appropriately set according to the purpose of use of the coating composition
However, generally, the monomer A is 1 to 80% by weight, and the monomer B is
1 to 80% by weight of another vinyl monomer copolymerizable therewith
It is preferable that the amount of the monomer C be 0 to 98% by weight. Used as an essential component in the present invention
The copolymer is obtained by subjecting such a monomer mixture to vinyl polymerization.
In the presence of initiator, solution polymerization, bulk polymerization, emulsification according to standard methods
Polymerization by various methods such as polymerization and suspension polymerization
And can be obtained. This copolymer is used for paints.
When used, generally diluted with an organic solvent,
It is convenient to use a polymer solution of viscosity,
It is advisable to use solution polymerization or bulk polymerization.
No. As the vinyl polymerization initiator, azobisiso
Butyronitrile, triphenylmethylazobenzene, etc.
Azo compound, benzoyl peroxide, di-t-butyl
Ruperoxide, t-butylperoxybenzoate,
t-butyl peroxyisopropyl carbonate
A peroxide is used. Organic solvents include xylene and toluene.
Which aromatic hydrocarbon solvents, hexane, heptane, etc.
Aliphatic hydrocarbon solvents, ethyl acetate, butyl acetate, etc.
Ester solvents, isopropyl alcohol, butyl alcohol
Alcohol solvents such as coal, dioxane, diethyl
Ether solvents such as ether, methyl ethyl ketone,
Ketone solvents such as methyl isobutyl ketone
And one or more of these are used. The molecules of the copolymer obtained by such a method
The amount is from 1,000 to 150,000 by weight average.
Desirably within the range. If the molecular weight is too low,
Film formation is difficult, and if too high, paint solids content
Is low, so only one thin coating can be obtained with one coating.
There is a problem that a larger number of paintings is required. Ma
The viscosity of the polymer solution comprising the copolymer was 25 ° C.
It is convenient to be less than 150 poise
The solid content of the polymer solution is 5 to 90% by weight, preferably
Is preferably in the range of 15 to 85% by weight. In the coating composition of the present invention, the essential components
Other known antifouling agents include those known in the art.
Is widely encompassed. Broadly speaking, it contains inorganic compounds and metals.
Organic compounds and metal-free organic compounds. As the inorganic compound, cuprous oxide, copper powder, copper
Copper compounds such as copper ocyanate, copper carbonate, copper chloride, and copper sulfate
Material, zinc sulfate, zinc oxide, nickel sulfate, copper-nickel
Alloys and the like. Organic copper-containing compounds include organic copper-based compounds.
Compounds, organic nickel compounds and organic zinc compounds
And others, such as maneb, mansebu, propineb
Can be used by anyone. Oxin is an organic copper compound.
Copper, copper nonylphenol sulfonate, copper bis (d
Tylenediamine) -bis (dodecylbenzenesulfone)
G), copper acetate, copper naphthenate, bis (pentachlorophenol)
Copper (noryl acid) is an example of an organic nickel compound.
Nickel acetate, nickel dimethyldithiocarbamate
However, as organic zinc compounds, zinc acetate, carbamide
Zincate, zinc dimethyldithiocarbamate, zinc
Lithion, zinc ethylenebisdithiocarbamate, etc.
, Respectively. Examples of the organic compound containing no metal include N-
Trihalomethylthiophthalimide, dithiocarbamine
Acid, N-arylmaleimide, 3-substituted amino-1,3
-Thiazolidine-2,4-dione, dithiocyano compound
Substances, triazine compounds and other substances
You. N-trihalomethylthiophthalimide
N-trichloromethylthiophthalimide, N-phenyl
Such as fluorodichloromethylthiophthalimide,
As carbamic acid, bis (dimethylthiocarbamoy
G) disulphide, N-methyldithiocarbamic acid an
Monium, ethylene bis (dithiocarbamic acid) ammonium
And milneb. N-arylmaleimides include N-
(2,4,6-trichlorophenyl) maleimide, N-
4-tolylmaleimide, N-3-chlorophenylmale
Imide, N- (4-n-butylphenyl) maleimide, N
-(Anilinophenyl) maleimide, N- (2,3-
Silyl) maleimide and the like. 3-Substituted amino-1,3-thiazolidine-
As 2,4-dione, 3-benzylideneamino-
1,3-thiazolidine-2,4-dione, 3- (4-meth
Tylbenzylideneamino) -1,3-thiazolidine-
2,4-dione, 3- (2-hydroxybenzylidenea
Mino) -1,3-thiazolidine-2,4-dione, 3-
(4-dimethylaminobenzylideneamino) -1,3-
Thiazoline-2,4-dione, 3- (2,4-dichloro
Benzylideneamino) -1,3-thiazolidine-2,4
-Dione and the like. As the dithiocyano compound, dithiocyano
Anomethane, dithiocyanoethane, 2,5-dithiocyan
Notthiophene and the like are triazine-based compounds,
-Methylthio-4-tert-butylamino-6-cyclopro
Pillamino-s-triazine and the like, respectively.
You. Other organic compounds containing no metal
Is 2,4,5,6-tetrachloroisophthalonitrile
, N, N-dimethyldichlorophenylurea, 4,5-
Dichloro-2-N-octyl-3- (2H) isothiazo
Ron, N, N-dimethyl-N'-phenyl- (N-fur
Orodichloromethylthio) sulfamide, tetramethyl
Thiuram disulfide, 3-iodo-2-propynylbu
Tyl carbamate, 2- (methoxycarbonylamino)
Benzimidazole, 2,3,5,6-tetrachloro-
4- (methylsulfonyl) pyridine, diiodomethylpa
Latrile sulfone, bisdimethyldithiocarbamoyldi
N-ethylene bisdithiocarbamate, phenyl (bis
Pyridine) bismuth dichloride, 2- (4-thiazoli)
Le) Benzimidazole, triphenylboronpyridine
And the like. In the present invention, various kinds of antifouling as described above are used.
Select and use one or more of these agents
However, the amount of the antifouling agent is usually 0.1 to 80
% By weight, preferably 1 to 60% by weight.
Is good. If the amount of the antifouling agent is too small, the antifouling effect cannot be expected.
Cracks, peeling and other defects in the formed coating film
It is difficult to obtain effective antifouling properties. The coating composition of the present invention thus constituted
The face includes petals, titanium dioxide, talc, zinc oxide, etc.
Colorants such as pigments and dyes, water binders, and paints.
Anti-sagging agent, anti-segregation agent, anti-settling agent, antifoaming agent, etc.
Can be blended. Dip in seawater using the coating composition of the present invention
To form an antifouling coating on the surface of the object to be
After being applied to the surface of the object by appropriate means,
The solvent may be removed by evaporation under heating.
Easily forms a dry coating film with excellent antifouling performance on the surface of the object
Can be achieved. [0040] Next, the present invention will be described with reference to a reference example (Hemiacetal).
Example of synthesis of monomer B which is an ester group-containing monomer)
Specific examples will be given according to the production examples, examples and comparative examples of the coalescence.
Will be explained. Parts in each example are parts by weight and the viscosity is 25 ° C.
Viscosity and molecular weight measured by GPC
It is a converted weight average molecular weight. Reference Examples 1 to 3 In a flask with a stirrer, according to the composition shown in Table 1,
First, EVE (ethyl vinyl ether) as raw material 1,
PrVE (pyrropyl vinyl ether) or CHVE
(Cyclohexyl vinyl ether)
The temperature was raised to 60 ° C. while introducing nitrogen gas. Next,
To this, AA (acrylic acid) was dropped as raw material 2 in one hour.
After completion of the dropwise addition, the temperature was maintained at that temperature for 24 hours to complete the reaction.
Done. As a result, three types of hemiacases having the abbreviations shown in Table 1
Synthesis of a monomer containing a tar ester group, ie, monomer B
Was. [0042] Reference Examples 4 to 6 PrVE (pyrropyl vinyl ether) as raw material 1
MAA (methacrylic acid), MMIA
(Methyl maleate) or MFmA (methyl fumarate)
), Respectively, and according to the composition shown in Table 2,
In the same manner as in Reference Examples 1 to 3, three types of abbreviations shown in Table 2 were used.
Miacetal ester group-containing monomer, that is, monomer B
Synthesized. [0044]Production Examples 1 to 10 In a flask equipped with a stirrer, according to the composition shown in Tables 3 to 6.
First, charge the solvent, stir and introduce nitrogen gas.
Meanwhile, the temperature was raised to 80 ° C. Next, the monomer (single amount
A mixture of the components (A) to (C) and the polymerization catalyst is added dropwise over 3 hours.
The temperature was maintained at that temperature for 5 hours after the completion of the lower to complete the polymerization.
Finally, the mixture is diluted with a diluting solvent to give a silyl ester in the molecule.
1 containing a stele group and a hemiacetal ester group
Zero polymer solutions IX were prepared. Comparative Production Examples 1 and 2 In a flask equipped with a stirrer, according to the composition shown in Table 6,
Without charging the solvent, stirring and introducing nitrogen gas,
The temperature was raised to 80 ° C. Next, a monomer [monomer A
(Or monomer B), monomer C] and a polymerization catalyst
Is dropped in 3 hours, and is maintained at that temperature for 5 hours after the completion of dropping.
To complete the polymerization. Finally, add dilution solvent to dilute
And only a silyl ester group or hemiaceta
Polymer solutions XI to XII having only ester groups
Was manufactured. In Tables 3 to 6, monomer B was prepared in Reference Example 1.
6 were used. Monomer A and monomer C
And AIB used as a polymerization catalyst
"N" is as follows. TBSA: tributylsilyl acrylate TMSA: trimethylsilyl acrylate TESA: triethylsilyl acrylate TPSA: triisopropylsilyl acryle
G TESMA: triethylsilyl methacrylate TBSMMA: tributylsilyl methyl maleate TBSMFA: tributylsilylmethyl fumarate MMA: Methyl methacrylate VAc: vinyl acetate AIBN: 2,2'-azobisisobutyronite
Lil [0048][0049][0050][0051]Examples 1 to 10 Polymer solutions shown in Table 7 below produced in Production Examples 1 to 10
I to X: 32.8 parts, cuprous oxide 57.41 as an antifouling agent
Parts, 1.19 parts of titanium dioxide as a pigment, and an anti-sagging agent
And Despalon 6900-20X [Kusumoto Chemical Co., Ltd.]
3 parts, and 5.6 parts of xylene as a solvent.
, And 10 kinds of paint compositions by paint shaker
Prepared. [0053] Examples 11 to 31 Using the polymer solutions IX produced in Production Examples 1 to 10,
The composition shown in the following Tables 8 to 13 (the numerical values in the table are weight
%), 21 kinds of paints by paint shaker
A composition was prepared. In addition, in the ingredients,
Kusanmoto Kasei Co., Ltd.
It is made. [0055] [Table 1] [0056] [Table 2][0057] [Table 3][0058] [Table 4][0059] [Table 5][0060] [Table 6]Comparative Examples 1 and 2 Comparative Production Examples Instead of Polymer Solutions I to X: 32.8 Parts
Polymer solution XI prepared in 1, 2 (Comparative Example 1), polymer solution
Except that 32.8 parts of Liquid XII (Comparative Example 2) was used, respectively.
Is the same as in Examples 1 to 10,
Prepared. Examples 1 to 31 and Comparative Examples 1 and 2
For each paint composition,
Test, antifouling performance test, adhesion test and crack resistance test
Went. These results are shown in Tables 14 to 17 below.
It was as it was. <Coating film wear test> Each coating composition was applied to the back side.
Rust-proof painted steel plate (100mm x 100mm x 1mm)
Spray on the front surface so that the dry film thickness is 200 μm.
Paint, dry in a room at a temperature of 20 ° C for one week, and test
Pieces were made. On the outer surface of a cylindrical drum with a diameter of 50 cm,
After fixing the test piece described above, the sea surface of Yura Bay, Sumoto City, Hyogo Prefecture
Soak it under 1m and the drum speed will be 16 knots
Rotate with a motor to reduce the consumed coating thickness by 1 every 3 months.
It was measured for 8 months. In addition, the average thickness consumption rate of the coating film (μm /
Month). The average thickness of the coating was 3 μm.
/ Month or more correlates with good antifouling performance. <Test for antifouling performance>
Pre-applied tar vinyl rust preventive paint to blasted steel sheet
Both sides of the painted plate (100mm × 200mm × 1mm)
Spray-coated so that the dry film thickness is 240 μm on one side.
Painted twice with a constant temperature of 20 ° C and humidity of 75%
The specimen was dried for one week in a constant humidity chamber to prepare a test piece. This trial
Aioi, Hyogo Prefecture
Immerse in seawater for 24 months in Ichi Aioi Bay.
Of the area occupied by attached organisms (adhered area)
Specified. <Adhesion test>
A dry film thickness of 125 μm per coating
Spray paint twice, then tarbini
So that the dry film thickness becomes 70 μm.
Painted. On this, each coating composition was dried to a film thickness of 10
Spray paint twice so that it becomes 0 μm,
Dry in a constant temperature and humidity room at a temperature of 20 ° C and a humidity of 75% for one week.
Then, a test piece was prepared. Immerse this test piece in artificial seawater
3 months, 6 months, 9 months, 12 months and
Raised 18 months later, a 2mm-spaced goban test [J
IS K5400 (1990) 8.5.2.
According to the law]. Evaluation of adhesion
○ (pass) when the number of adhered particles is 25/25
X (fail) when the number of adhering is 24 or less / 25
did. <Crack resistance test> Adhesion test
When the test specimen is lifted from artificial seawater,
Visual observation was made to check for the occurrence of cracks. Crack
○ (pass) if there is no, and × (fail) if there is
Was. [0067] [Table 7] [0068] [Table 8][0069] [Table 9][0070] [Table 10]It is clear from the results of Tables 14 to 17 above that
As described above, the coating compositions of the present invention of Examples 1 to 31
Good wear, 24 months of creature adhesion in antifouling performance
No adhesion and no coating film defects
I got it. On the other hand, the coating composition of Comparative Example 1
It has a steal group but no hemiacetal ester group.
Although it is a polymer that uses
Performance is an unsatisfactory result, adhesion and crack resistance
But there were drawbacks. Further, the coating composition of Comparative Example 2 was:
Has hemiacetal ester group but silyl ester group
Although it uses a polymer that does not have
And antifouling performance are both unsatisfactory results.
Defects are seen even in crack resistance, especially over time
Defects such as blisters, cracks and peeling were observed. [0072] According to the present invention, the coating composition of the present invention
Good stability during dispersion and storage
Is the bottom of the ship, fish nets and cooling water that need to prevent biofouling in the sea.
Underwater structures such as pipes, and sludge diffusion in offshore civil engineering works
It can be used for prevention, etc.
No delamination, dissolves in the sea at an appropriate speed and uniformly
Exhibiting hydrolytic properties, causing biofouling on the surface of each of the above objects
Excellent antifouling performance over a long period against contamination
can do.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masahiro Ishidoya 5-9-5-502 Nanko, Chigasaki-shi, Kanagawa (72) Inventor Yoshihiro Honda 1-13-59, Koyodai, Kawanishi-shi, Hyogo (56) References JP JP-A-4-103671 (JP, A) JP-A-4-264168 (JP, A) JP-A-2-675 (JP, A) JP-A-3-35065 (JP, A) JP-A-63-215780 (JP) JP-A-5-186739 (JP, A) JP-A-5-78551 (JP, A) Japanese Translation of PCT Application No. Sho 60-500452 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C09D 1/00-10/00 C09D 101/00-201/10 C08C 19/00-19/44 C08F 6/00-246/00

Claims (1)

(57) [Claims] [Claim 1] The following general formula (1): (Wherein, R ^{1 to} R ³ are all groups selected from an alkyl group and an aryl group and may be the same or different from each other. X is An acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group or a fumaroyloxy group), and the following general formula (2): (Wherein, R ⁴ is an alkyl group, R ⁵ is an alkyl group or a cycloalkyl group, and Y is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, or a fumaroyloxy group). A copolymer of a monomer mixture containing a monomer B and, if necessary, another vinyl monomer C copolymerizable with these monomers A and B, and an antifouling agent. A coating composition for preventing biofouling .