JP2003176444A - Coating material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a coating material composition free from the formation of a residue layer on the coating film surface even after the immersion over a long period, resistant to the generation of defects such as crack and peel of the coating film, dissipating the coating film at a constant rate higher than a specific level to reduce the residue layer, exhibiting the performance to prevent the adhesion of marine life over a long period and having good recoatability and marine life adhesion preventing performance corresponding to the rigging period. <P>SOLUTION: This coating material composition contains (A) one or more kinds of rosin compounds selected from a rosin, a rosin derivative and a rosin metal salt, (B) a polymer containing an organic silyl ester group and composed of a copolymer of a monomer M having a triorganosilyl group wherein at least one of the three alkyl or aryl groups (R<SP>1</SP>to R<SP>3</SP>) is a ≥3C group and polymerizable monomers other than the monomer M and containing acrylic acid or methacrylic acid as an essential component and (C) an antifouling agent as essential components. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to an underwater object surface.
A coating composition for preventing organisms from attaching
Things. [0002] 2. Description of the Related Art Ship bottoms, buoys, and fish immersed in seawater
Nets (stationary nets, aquaculture nets, etc.)
The surface of underwater objects such as various plumbing pipes
Various types of mussel, mussels, serpula, algae, etc.
Trouble occurs. To prevent pollution by those organisms.
Paint to prevent organisms from adhering to the surface of underwater objects
It is well known that is applied. Currently, marine life
The resin used for the paint that prevents the adhesion of
It is roughly divided into polymer type and rosin type. The most typical hydrolyzable polymer system
Examples include organic tin polymers. Organic tin polymer
Paint consists of organic tin groups bonded to the polymer.
Hydrolysis in seawater consumes the paint film,
Maintain activity. It also prevents hydrolyzed organotin compounds.
Long-term adhesion of marine organisms to function as a pollutant
Can be prevented. However, organotin compounds are
Has high accumulation capacity, and its use is regulated due to concerns about environmental pollution.
ing. Hydrolyzable polymer replacing this organotin polymer
— Japanese Patent Publication No. 5-32433,
-215780, JP-A-7-102193
Of polymers containing organic silyl groups as disclosed in
Many have been proposed. [0004] In addition, rosin-based paints have a rosin alkali.
Sea water that is slightly soluble in solution and weakly alkaline
(PH ≒ 7.8-8.2) to dissolve (pH = 8.1
8.6 × 10 in seawater^-FiveMol / litre), effective antifouling agent
It can be gradually released into seawater. Rosin is this seawater
Widely used as anti-fouling paint for marine organisms
It has been used in many publications.
You. For example, “Handbook for Color Material Engineering” (page 821)
~: Edited by the Coloring Materials Association), "Painting and Paints on Ships" (p. 70)
-: Manabu Nakao, Ship Technology Association). However, rosin alone is physically brittle.
Weak (very low film formation performance due to low molecular weight
To compensate for this, blur other synthetic resins, etc.
Need to be installed. To compensate for this vulnerability, rosin
A polymer having good compatibility with the polymer must be used. phase
If the solubility is poor, rosin and polymer are separated and
Physical weakness appears in the aggregated portion of gin. Blend rosin with other polymers
Is proposed in Japanese Patent Application Laid-Open No. 50-135125.
Good compatibility with the polymer to be blended
Control the wear of the coating (self-polishing)
Japanese Patent Application Laid-Open No. 60-28456 describes
It is reported in the gazette. [0007] SUMMARY OF THE INVENTION However, rosin
Even when blending a polymer that is compatible with
Has good film properties, but after long-term immersion,
Decrease, generation of physical property defects of coating film, prevention of marine organism adhesion
It has been found that a problem of lowering the temperature occurs. Also,
After a certain period (about 1 to 3 years), especially for ships
In order to re-coat new paint on the old paint film,
Recoverability is required, but this recoatability is defective.
Turned out to be. [0008] These defects or defects are rosin and
Polymers with good compatibility-their solubility in seawater is
Low or little solubility compared to
The antifouling agent dissolves first with the rosin on the coating surface
A so-called surface residue layer is formed as the (extracted) film.
It is caused by that. [0009] Blend polymers are the physical fragility of rosin
Rosin to improve film formation performance.
Demand for loose or higher molecular weight polymer than rosin
Is done. Because of this difference in molecular weight, rosin and blended polymers
-There is a difference in solubility between This residual layer increases due to immersion.
As it grows, the wear of the coating decreases and the inside of the residual layer
Coating force causes physical defects in coating film
Reduced marine organism adhesion prevention effect, rechargeability
A drop occurs. As described above, rosin is slightly soluble in seawater.
A very suitable performance as a marine organism adhesion prevention paint
Despite the fact that it has
The feed composition has never been present. Also, a hydrolyzable type replacing the organotin polymer
As a polymer, Japanese Patent Publication No. 5-32433 and
No. 215780 discloses a method for hydrolyzing an organic silyl group.
Polymers that have decomposable groups are
Paints fall off when immersed in water.
Defects such as lack of aptitude. Therefore, the present inventors have disclosed in Japanese Patent Application Laid-Open No. 7-102.
No. 193, with an organic silyl group,
With xy or aryloxy polyethylene glycol groups
The above defects can be eliminated according to the specific polymer
I found something. However, in subsequent studies,
According to the polymer, performance after long-term immersion in seawater,
In particular, there is a problem with recoating, and it is required during outfitting
The marine life adhesion prevention performance for the outfitting period
Turned out to be. [0013] The above outfitting period is the time when a ship is built.
After constructing the ship's outer shell inside the ship,
Is the period during which the ship interior is built.
It is usually about three months. During this period, the hull was
The ocean around the shipyard (unlike the open ocean,
Unusual, higher
Marine life corresponding to the outfitting period, which is an excellent marine organism adhesion prevention performance
Adhesion prevention performance is required. After completion of the outfitting, the ship will go into service
Enter the dock again, and after finishing, enter service. During the outfitting period
If biofouling occurs, fuel efficiency will decrease from the start of service.
Can not fly in such a situation
No. Also, even if you enter the dock again, before entering service
To remove attached organisms from
During the outfitting period, it completely serves as a marine organism adhesion prevention paint
Not work, i.e. do not apply marine
It is the same as that. [0015] The present inventors have found that marine organisms adhere to the outfit period.
As a method of evaluating the prevention performance, the start time of the immersion test is biofouling
To be the most intense summer season
Not elute immediately after immersion, but after a certain period
Therefore, immediately after the start of immersion,
The more likely that organisms will attach to them).
This is the sea area that is normally used to evaluate the marine organism adhesion prevention performance.
Mie, which has more severe biofouling than Aioi Bay, Hyogo Prefecture
In Owase Bay, prefecture, for three months from July to September, 1996,
Usually immersed perpendicular to the sea surface,
The test method of immersing horizontally to increase the sound
Devised. According to this test method, the above-mentioned JP-A-7-102 was used.
As a result of evaluating the polymer disclosed in JP 193,
It turns out that there is a problem in the marine organism adhesion prevention performance
It was done. [0016] Therefore, the present invention provides a method for applying a coating even after prolonged immersion.
Since there is no residual layer on the film surface,
No defects such as cracks, peeling, etc.
The speed is higher than a certain speed and the marine organism adhesion prevention performance is long.
Over time, recoverability and outfitting period
Developing paint compositions with good marine organism adhesion prevention performance
The purpose is. [0017] Means for Solving the Problems The present inventors have the following points.
The development of the intended coating composition was carried out. This
The development of paint compositions for
It can be done by doing things. For this, rosin
The solubility of polymers with good compatibility with seawater
Must be increased after water immersion. Launch of such a function
Currently available only for polymers that undergo chemical changes before and after immersion in seawater
Noh. Before immersion in seawater due to polymer with chemical change
Has good compatibility with rosin-based resin,
Change to hydrophilic only with good dissolution rate
Becomes possible. The present inventors have proposed a blend polymer as:
Focusing on polymers in which carboxylic acids are protected with organic silyl groups
Was. This polymer has low polarity of organic silyl group.
Has good compatibility with low-polarity rosin and
Chemical changes after immersion in seawater due to the hydrolytic properties of
The solubility in seawater changes significantly from insoluble to soluble
Become Organotin polymers with similar hydrolyzability are:
Since the polarity is higher than that of the above silyl polymers,
Poor compatibility with styrene, and functions like silyl polymer
It cannot be expressed. Low polarity and seawater
Water degradability is very important for blending with rosin
It is. [0019] These points have been studied intensely.
Rosin and rosin compounds such as rosin and its derivatives
Organic silyl ester group having silyl group as hydrolysis point
By using the contained polymer and the antifouling agent,
It turns out that I can solve the problems I had.
In other words, no residual layer is formed on the coating film surface even after long-term immersion.
Causes defects such as cracks and peeling in the physical properties of the coating film.
At a certain speed with no change in the wear of the coating over time.
The marine organism adhesion prevention performance can be exhibited over a long period of time,
Recoverability and anti-seafouling property for outfitting period
A rosin-based coating composition with good performance was successfully developed. That is, the present invention relates to A) rosin, rosin
Derivatives or rosin-based compounds consisting of rosin metal salts 1
Species or two or more, and B) the following general formula:(Where R¹~ R^ThreeIs an alkyl group or an ant.
Groups that are the same or different from each other.
You can use¹~ R^ThreeAt least one of
It is a group having 3 or more carbon atoms. X is acryloyloxy
Group, methacryloyloxy group, maleinoyloxy group,
Fumaroyloxy, itaconoyloxy or cytosine
Laconoyloxy group. 1) of the monomer M represented by
Acrylic acid or methacrylic acid must be
One of the polymerizable monomers other than the above-described monomer M or
Organic silyl ester group containing two or more polymers
The polymer and C) antifouling agent must be contained as essential components.
And a coating composition characterized by the following. [0021] DESCRIPTION OF THE PREFERRED EMBODIMENTS In the coating composition of the present invention,
The rosin compound of component A used as a component
Rosin derivatives or rosin metal salts. for example
For example, rosin is tol rosin, gum rosin, wood
Rosin and the like, as rosin derivatives, hydrogenated rosin,
Maleated rosin obtained by reacting gin and maleic anhydride,
Formylated rosin, polymerized rosin, etc.
Gin rosinate, calcium rosinate, mosquito
Copper rosinate, magnesium rosinite, other gold
A reaction product of the genus compound and rosin is exemplified. In the present invention, such a rosin compound is
One or two or more are selected and used.
Is an organic silyl ester of this rosin compound and B component
The solid content ratio with the group-containing polymer is usually 1/99 to
99/1, preferably 5/95 to 95/5.
Is good. If the A component is too small, the marine organism adhesion prevention effect,
In particular, it can be expected to have the effect of preventing marine organisms from sticking during the outfitting period.
If it is excessive, the ability to form a coating film will decrease and the coating film will crack,
Defects such as peeling are easy to occur, and effective prevention of marine organisms
It is difficult to obtain stopping performance. In the coating composition of the present invention, the essential components
Component-Containing Organic Silyl Ester Group-Containing Polymer
Is one type of the monomer M represented by the general formula (1) or
Requires two or more and acrylic or methacrylic acid
One or more polymerizable monomers other than the above monomer M
The polymer with the above. The monomer M is represented by the general formula (1)
As an unsaturated group (X) in the molecule, acryloyl
Xy group, methacryloyloxy group, maleinoyloxy
Group [mainly monoalkyl (C1-6) ester male
Noyloxy group), fumaroyloxy group (mainly monoal
Kill (C1-6) ester fumaroyloxy group],
Itaconoyloxy group [mainly monoalkyl (having 1 to 1 carbon atoms)
6) ester itaconoyloxy group] or citracco
Noyloxy group [mainly monoalkyl (C1-6)
(Stericitraconoyloxy group)
It has a liorganosilyl group. In the triorganosilyl group, three groups
Alkyl group or aryl group (R¹~ R^Three) Is the same group
Or a different group.
At least one group is a group having 3 or more carbon atoms. concrete
Contains carbon atoms such as methyl, ethyl, propyl, and butyl
Is a linear or branched alkyl group having 20 or less;
Cyclic alkyl groups such as hexyl and substituted cyclohexyl;
There are an aryl group and a substituted aryl group. Replacement aryl
As the group, halogen, alkyl having up to about 18 carbon atoms
Group, acyl group, nitro group or amino group
And aryl groups. Among such monomers M, (
(T) As those having an acryloyloxy group,
-N-propylsilyl (meth) acrylate, tri-i
-Propylsilyl (meth) acrylate, tri-n-butyl
Tylsilyl (meth) acrylate, tri-i-butyl
Ryl (meth) acrylate, tri-s-butylsilyl
(Meth) acrylate, tri-n-amylsilyl (meth
(T) acrylate, tri-n-hexylsilyl (meth)
Acrylate, tri-n-octylsilyl (meth) ac
Relate, tri-n-dodecylsilyl (meth) acryle
-To, triphenylsilyl (meth) acrylate, tori
-P-methylphenylsilyl (meth) acrylate,
Ribenzylsilyl (meth) acrylate and the like. Further, (meth) acryloyl oxy
As another example having a silyl group, n-butyldimethylsilyl
(Meth) acrylate, di-i-propyl-n-butyl
Silyl (meth) acrylate, n-octyldi-n-butyl
Cylsilyl (meth) acrylate, di-i-propyls
Tearylsilyl (meth) acrylate, dicyclohexyl
Ruphenylsilyl (meth) acrylate, t-butyldi
Phenylsilyl (meth) acrylate, lauryl dihue
Nylsilyl (meth) acrylate, t-butyl-m-di
Trophenylmethylsilyl (meth) acrylate
No. Further, a maleinoyloxy group is added to the molecule.
Having tri-n-propylsilyl-n-
Propyl maleate, tri-n-butylsilyl-n-butyl
Lumarate, tri-n-amylsilyl-n-amylmale
-Tri-n-hexyloctylsilyl maleate, g
L-n-octylsilyl decyl maleate, tri-n-
Dodecylsilylmethyl maleate, triphenylsilylmethyl
Chil maleate, tri-p-tolylsilylethyl maleate
, Triisopropylsilyl isoamyl maleate, tri
Isobutylsilyl phenyl maleate, t-butyl dimethyl
Lucylyl methyl maleate, t-butyldiphenylsilyl
Methyl maleate, n-octyldi-n-butylsilylmethyl
Chil malate and the like. Further, it has a fumaroyloxy group in the molecule.
There may be mentioned tri-n-propylsilyl-n-pro
Pilfmalate, tri-n-butylsilyl-n-butyl
Fumarate, tri-n-amylsilyl-n-amyl fuma
Rate, tri-n-hexylsilyl-n-hexyl fuma
Rate, tri-n-octyl silyl decyl fumale
, Tri-n-dodecylsilylmethyl fumarate, tri
Phenylsilyl methyl fumarate, tri-p-methyl phthalate
Enylsilyl methyl fumarate, triisopropylsilyl
Methyl fumarate, triisobutylsilylmethyl fumarate
Rate, tri-2-chloroisopropylsilylmethylf
Maleate, tri-t-butylsilylmethyl fumarate,
n-butyldimethylsilylmethyl fumarate, n-oct
Tildi-n-butylsilylmethyl fumarate and the like.
Can be Further, itakonoyloxy group is present in the molecule.
May be tri-n-propylsilyl-n-propyl.
Ropirita connect, tri-n-butylsilyl-n-butyl
Tilitanate, tri-n-amylsilyl-n-ami
Luitaconate, tri-n-hexylsilyl-n-hex
Silita connect, tri-n-octyl silyl decyl
Itaconate, tri-n-dodecylsilylmethyl itaco
Nate, triphenylsilylmethylitanate, tri
-P-fluorophenylsilylmethyl itaconate,
Liisopropylsilylmethyl itaconate, triisobu
Tylsilyl methyl itaconate, tri-2-cyanoiso
Propylsilylmethyl itaconate, tri-t-butyl
Silyl methyl itaconate, n-butyldimethylsilyl
Methyl itaconate, n-octyldi-n-butylsilyl
And methyl itaconate. Further, a citraconoyloxy group is contained in the molecule.
Having tri-n-propylsilyl-n
-Propyl citrate, tri-n-butylsilyl-
n-butylcitraconate, tri-n-amylsilyl-
n-amylcitracone, tri-n-hexylsilyl
-N-hexylcitracone, tri-n-octylsi
Lildodecyl citrate, tri-n-dodecylsilicone
Methyl citrate, triphenylsilylmethyl
Traconate, tri-p-hydroxyphenylsilylmethyl
Tylcitracone, triisopropylsilylmethylsi
Traconate, triisobutylsilylmethylcitracone
-To, tri-2-bromoisopropylsilylmethylcyto
Laconate, tri-t-butylsilylmethylcitracone
-To, n-butyldimethylsilylmethylcitracone-
G, n-octyldi-n-butylsilylmethyl citraco
Nate and the like. The polymerizable monomers other than the monomer M are acrylic
With the above-mentioned monomer M which essentially requires an acid or methacrylic acid.
Other monomers that can be polymerized, such as acrylic acid
And methyl acrylate, ethyl acrylate, acrylic acid
n-butyl, t-butyl acrylate, s-butyl acrylate
Chill, 2-ethylhexyl acrylate, acrylic acid
Lohexyl, 2-hydroxyethyl acrylate, acrylic
2-hydroxypropyl luate, glycidyl acrylate,
2-methoxyethyl acrylate, 2-ethoxy acrylate
Acrylic esters such as ethyl, methacrylic acid, etc.
And methyl methacrylate, n-butyl methacrylate,
T-butyl methacrylate, s-butyl methacrylate, meta
2-ethylhexyl acrylate, cyclohexyl methacrylate
Sil, 2-hydroxyethyl methacrylate, methacryl
2-hydroxypropyl acid, glycidyl methacrylate,
2-methoxyethyl methacrylate, 2-d-methacrylic acid
Methacrylic acid esters such as toxic ethyl
Can be As another example of the polymerizable monomer, vinyl acetate is used.
, Vinyl propionate, vinyl butyrate, vinyl benzoate
, Beova 9 and Beova 10 [Showa Ciel Science Co., Ltd.
Esters, etc.), maleic acid
Chill, diethyl maleate, di-n-propyl maleate
Di-i-propyl maleate, di-2-maleate
Maleic esters such as methoxyethyl, fumaric acid
Dimethyl, diethyl fumarate, di-n-propyl fumarate
Di-i-propyl fumarate, di-2-meth-fumarate
Fumaric esters such as xylethyl, crotonic acid
Ters, itaconic esters, citraconic esters
, Styrene, vinyltoluene, α-methylstyrene,
Acrylonitrile and the like are also included. Component B Component Organic Silyl Ester Group-Containing Polymer
In the above, the monomer M represented by the general formula (1) and
The ratio of the outer polymerizable monomer used depends on the purpose of the coating composition.
Can be set as appropriate, but generally, the monomer M is
% Or more, and the other polymerizable monomer is 99% by weight or less.
It is better to be. Component B Organic Silyl Ester Group-Containing Polymer
Is used to prepare such a monomer mixture in the presence of a polymerization catalyst.
Solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc.
It can be obtained by polymerizing by any of various methods.
You. The organic silyl ester group-containing polymer of the component B is applied.
When used as a raw material, it is diluted with an organic solvent and
It is preferable to use a coalescence solution.
It is desirable to employ the bulk or bulk polymerization method. As the above polymerization catalyst, azobisisobut
Such as thyronitrile and trifnielmethylazobenzene
Azo compound, benzoyl peroxide, di-t-butyl
Peroxide, t-butylperoxybenzoate, t
-Overflow of butyl peroxyisopropyl carbonate, etc.
Oxides. In addition, the above-mentioned organic solvent includes
Aromatic solvents such as toluene, toluene, hexane,
Aliphatic hydrocarbon solvents such as heptane, ethyl acetate, vinegar
Ester solvents such as butyl acid, isopropyl alcohol
Alcohol solvents such as alcohol and butyl alcohol,
Ether solvents such as sun and diethyl ether, methyl
Ketones such as ethyl ketone and methyl isobutyl ketone
Solvents, and one or more of these.
The above is used. The organic silicic acid of component B thus obtained is
The ester group-containing polymer has a molecular weight of 1,0 by weight average.
It is desirable to be in the range of 00 to 150,000. molecule
If the amount is too low, it is difficult to form a normal coating film. Also enhance
If it is cut off, the viscosity of the coating composition will increase,
Must be diluted and only one thin film is obtained with one coating
Is not necessary, so more painting is required
Comes out. The viscosity of the polymer solution of the component B is as follows:
Conveniently, it is less than 150 poise at 25 ° C.
For example, the solid content of the polymer solution is 5 to 90% by weight,
Preferably, it should be in the range of 15 to 85% by weight.
Good. In the coating composition of the present invention, the essential components
C component used as another one is an antifouling agent,
Are widely known. Broadly classified, inorganic
Organic compounds containing compounds and metals and metals free of metals
There are organic compounds. Of these, as inorganic compounds,
For example, cuprous oxide, copper powder, cuprous thiocyanate, copper carbonate,
Copper compounds such as copper chloride and copper sulfate, zinc sulfate, zinc oxide,
Nickel sulfate, copper-nickel alloy, and the like. As the organic compound containing a metal, for example,
For example, organic copper compounds, organic nickel compounds and organic
There are zinc-based compounds and others, Maneb, Mansebu,
Propineb can also be used. As an organic copper compound
Are copper oxine, copper nonylphenolsulfonate, cutlet
Perbis (ethylenediamine) -bis (dodecylbenze
Sulfonate), copper acetate, copper naphthenate, bis (pen
Copper, copper pyrithione, etc.
Nickel-based compounds include nickel acetate,
Nickel thiocarbamate and the like
Are zinc acetate, zinc carbamate, dimethyldithio
Zinc carbamate, zinc pyrithione, ethylene bisdi
Examples thereof include zinc thiocarbamate. Examples of the organic compound containing no metal include:
For example, N-trihalomethylthiophthalimide, dithioca
Rubamic acid, N-arylmaleimide, 3-substituted amino
-1,3-thiazolidine-2,4-dione, dithiocyanate
Compounds, triazine compounds and others
is there. N-trihalomethylthiophthalimide
N-trichloromethylthiophthalimide, N-phenyl
Such as difluorochloromethylthiophthalimide,
As carbamic acid, bis (dimethylthiocarbamoy
G) disulphide, N-methyldithiocarbamate
Monium, ethylene bis (dithiocarbamic acid) ammonium
And milneb. As N-arylmaleimide, N-arylmaleimide
(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. Examples of the dithiocyano compound include dithiocyano compounds.
Anomethane, dithiocyanoethane, 2,5-dithiocyan
Notthiophene is a triazine-based compound,
-Methylthio-4-t-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-dimethyl-N'-dichlorophenylurea,
4,5-dichloro-2-n-octyl-isoazoline-
3-one, N, N-dimethyl-N'-phenyl- (N-
Fluorodichloromethylthio) sulfamide, tetrame
Tilthiuram disulphide, 3-iodo-2-propini
Rubutyl carbamate, 2- (methoxycarbonylamido
No.) Benzimidazole, 2,3,5,6-tetrachloro
B-4- (Methylsulfonyl) pyridine, diiodomethyi
Lupatoritol sulfone, phenyl (bispyridine) bis
Masdichloride, 2- (4-thiazolyl) benziimi
Dazol, triphenylboronpyridine, etc.
You. In the present invention, such various kinds of antifouling
From the agents, one or two or more are selected and used,
As the amount used, the proportion of the antifouling agent in the paint solids is usually
0.1 to 80% by weight, preferably 1 to 60% by weight
It is better to do so. Antifouling effect expected when antifouling agent is too low
If it is not possible, cracks and peels off the coating film if it is excessive
Defects are likely to occur, making it difficult to obtain effective antifouling properties.
No. The coating composition of the present invention thus constituted
Include pigments and dyes such as red stalks, zinc oxide, and talc.
Coloring agents, water binders, anti-sagging agents commonly used in paints,
Chlorinated paraffin, dioctyl phthalate, trickle
Plasticizers such as rufuosphate, benzophenone compounds
Substances, ultraviolet absorbers such as benzotriazole compounds,
Anti-segregation agent, anti-settling agent, defoamer, silanol,
Various additives such as siloxane and alkoxysilane
It can be appropriately blended. Dipping in seawater using the coating composition of the present invention
To form an antifouling coating on the surface of the object
After applying it to the surface of the
The solvent can be removed by evaporation under this method.
A dry coating film can be easily formed on the body surface. [0050] EXAMPLES Next, the present invention will be described with reference to Production Examples and Experiments (Examples and Examples).
And a reference example) and a comparative example.
The parts in the examples are parts by weight, and the molecular weight is GPC (gel
Polystyrene by permeation chromatography
It is a weight average molecular weight in terms of len. Also used in the production example
Monomer M₁~ M₉Is a simple unit represented by the general formula (1).
And is represented by R in the general formula (1)¹~ R^ThreeAnd X
Is as shown in Table 1. [0051] [Table 1] Production Examples 1-4 In a flask equipped with a stirrer, add the solvent a according to the formulation in Table 2.
Charge, raise the temperature to the specified reaction temperature, and stir
Of the mixture of the polymer M, other monomers and the polymerization catalyst a.
The solution was dropped into the tray in 3 hours.
Hold for minutes. Then, a mixture of the solvent b and the polymerization catalyst b
Is added dropwise over 20 minutes, and stirring is continued for another 2 hours at the same temperature.
To complete the polymerization reaction. Finally, add a diluent solvent to dilute
Each polymer solution S₁~ S_FourGot. Production Examples 5 to 8 In a container having heat and pressure resistance, according to the composition shown in Table 3, monomer M was added.
Charge other monomers and polymerization catalyst, and seal completely
Raise the temperature to the specified reaction temperature while shaking, and at 8:00
The shaking was continued to complete the reaction. Next, the diluting solvent
In addition, shake for 1 hour to dissolve each polymer solution S_Five~ S₈
Got. Production Examples 9 to 16 Dissolve in a flask equipped with a stirrer according to the formulations in Tables 4 and 5.
Agent, monomer M, other monomers and polymerization catalyst
And raise the temperature to a predetermined reaction temperature while stirring.
Stirring was continued for 6 hours to complete the reaction. Next,
Each polymer solution S₉~ S₁₆Got. In Tables 2 to 5, "Veoba 9" and "Veo 9"
BA10 ”(trade name of Showa Ciel Science Co., Ltd.)
These are also vinyl ester monomers, and "perbutyl"
I "(trade name, manufactured by NOF Corporation) is an organic peroxide
is there. [0056] [Table 2] [0057] [Table 3][0058] [Table 4][0059] [Table 5]Experiments 1 to 20 Polymer solution S₁~ S₁₆Are used, the arrangements shown in Tables 6 to 10 are used.
Each component is mixed according to the total composition (the values in the table are% by weight).
And mixed and dispersed with a homomixer of 2,000 rpm,
Zero coating compositions were prepared. Comparative Examples 1 to 6 Polymer solution S₇, Polyisobutylene, Larroflex
MP-15 "(trade name, manufactured by BASF, vinyl chloride resin
Fat), "Priolite S-5B" (Goodyear)
Brand name, styrene butadiene rubber), "Toyopara
Tsukus A-70 ”[trade name, salt, manufactured by Toyo Soda Kogyo Co., Ltd.]
Paraffin resin], "Polysol EVA-AD-
3 "[trade name, manufactured by Showa High Polymer Co., Ltd.
Nyl copolymer (50% by weight solution)]
Depending on the composition shown (the values in the table are% by weight), each component is
Mix, mix and disperse with a 2,000 rpm homomixer.
Thus, six coating compositions were prepared. In Tables 6 to 11, “Dymalec
Su "(trade name of Hazuki Yures Co., Ltd.) is a polymerized rosin,
"Dayspalon A630-20X", "Dayspalon 4
300 ”(brand name manufactured by Kusumoto Kasei Co., Ltd.) and“ Vent
SD-2 "[trade name of National Red Co., Ltd.]
Are all additives for preventing sagging, "KMP590"
Oe Kagaku Kogyo Co., Ltd.] is a silicone resin powder
─, “Tinuvin 900” [product made by Ciba-Geigy Corporation
Is an ultraviolet absorber. [0063] [Table 6][0064] [Table 7][0065] [Table 8][0066] [Table 9][0067] [Table 10][0068] [Table 11]The above Experiments 1 to 20 and Comparative Examples 1 to 6
For each coating composition, follow the procedure below to
Layer confirmation test, paint film wear test, antifouling performance test, adhesion test
Test, crack resistance test, recoil test and outfitting period
A corresponding marine organism adhesion prevention performance test was performed. These results
Was as shown in Tables 12-20. <Test for confirming residual layer of coating film surface> Blasted steel plate
(100mm x 200mm x 1mm) with tar epoxy rust prevention
Spray the paint to a dry film thickness of 125 μm each time.
Apply twice with pre-coating, and then use a tar vinyl sealer
The coat was applied so that the dry film thickness was 70 μm.
On this, each coating composition was dried at a dry film thickness of 10 times.
Spray paint twice so that the thickness becomes 0 μm.
Dry for 1 week in a constant temperature and humidity room at a temperature of 20 ° C and a humidity of 75%.
Then, six test pieces were prepared for each coating composition. The test piece prepared in this manner was placed in artificial seawater.
3 months, 6 months, 12 months, 18 months
After 24 months, the test piece was pulled up and cut. Off
After polishing the cross section, observe the painted cross section with a stereoscopic microscope
Thereby, the residual layer formed on the coating film surface was measured. <Coating film wear test> Each coating composition was applied to both sides.
Surface of rust-proof painted steel plate (100mm x 100mm x 1mm)
Spray so that the thickness of one dry coating is 200 μm.
-Apply twice with paint and dry in a room at a temperature of 20 ° C for 1 week
Then, a test piece was prepared. On the outer surface of a cylindrical drum having a diameter of 50 cm,
After fixing the test piece, 1 below sea level in Yura Bay, Sumoto City, Hyogo Prefecture
m so that the peripheral speed of the drum becomes 16 knots.
Rotate with a motor to reduce the consumed coating thickness by 2 every 3 months.
It was measured for four months. In addition, the average thickness consumption rate of the coating film (μm
Month) for a period of up to six months, and six months to 24 months
The period was calculated. The average speed of consumption of the coating film thickness was 3 μm /
If it is a month, it correlates with good antifouling performance. Another six months
The average consumption rate of the coating thickness up to 24 months
If it is within the range of average film thickness consumption rate ± 1 (μm / month),
This indicates that the coating film is consumed at a constant speed. <Anti-fouling performance test>
Pre-applied tar vinyl rust preventive paint to blasted steel sheet
Both sides of painted plate (100mm × 200mm × 1mm)
Spray-coated so that the dry film thickness is 240 μm on one side.
2 coats with a constant temperature and constant temperature of 20 ° C and humidity of 75%
The specimen was dried in a wet chamber for one week to prepare a test piece. This trial
The test piece was subjected to 24 months of seawater at Aioi Bay, Aioi City, Hyogo Prefecture.
After immersion, the proportion of the area occupied by attached organisms on the test coating
(Attached area) was measured over time. <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 top of this, dry each coating composition
Spray coating twice so that the film thickness becomes 100 μm
Apply for 1 week in a constant temperature and humidity room at a temperature of 20 ° C and a humidity of 75%
It was dried to prepare a test piece. The test piece was immersed in artificial seawater for 3 months.
6 months later, 12 months later, 18 months later and 24 months later
It was lifted up later and a Goban test at 2 mm intervals was performed.
The evaluation of the adhesion was such that the number of peeled pieces by this test was 0 pieces / 25.
○ (Passed) when the number of peeling is 1 or more / 25
Was evaluated as x (fail). <Crack Resistance Test> Adhesion test
When lifting the test piece from artificial seawater,
It was visually observed to check for the occurrence of cracks. Crack
○ (pass) if there is no, × (fail) if there is
Was. <Recoatability test> Each coating composition was coated on both sides.
Of steel plates (100mm x 100mm x 1mm) with anti-rust coating on the surface
So that the dry film thickness per time is 100 μm
Spray coating twice, 1 week in a room with a temperature of 20 ° C
For two hours for each coating composition.
Produced. This test piece was immersed in artificial seawater, and 12
After the month and 24 months, lift, wash with distilled water,
It was dried in a room at a temperature of 20 ° C. for one week. Then each trial
The same coating composition was applied on the surface of the test piece,
Spray-painted twice to 100μm
Then, it was dried in a room at a temperature of 20 ° C. for one week. these
The test piece was fixed on the outer surface of a cylindrical drum with a diameter of 50 cm.
Dipped in Yura Bay, Sumoto City, Hyogo Prefecture
Rotate with a motor so that the peripheral speed of the
Was. One week later, pull it up and peel it between the new coating and the old coating.
The presence or absence of separation was confirmed. ○ (passed) without peeling
Were evaluated as x (fail). <Performance test for marine organism adhesion prevention corresponding to outfitting period
> Apply each paint composition to sandblasted steel sheet in advance.
Painted plate coated with ruvinyl-based anticorrosive paint (100mm ×
(300mm x 1mm) Both sides have a dry film thickness of 240μm on one side
Spray paint twice so that the temperature becomes 20
Dry in a constant temperature and humidity room at 75 ° C and 75% humidity for 1 week.
Specimens were prepared. This test specimen was placed in Owase Bay, Mie Prefecture.
1m below the water surface so that it is horizontal to the sea surface
Immersion in seawater for three months from July to September 1996
The percentage of the area occupied by attached organisms on the test coating (adhered surface
Product) was measured over time. In addition, the biofouling during the above period in Owase Bay, Mie Prefecture
To compare the loss level with Aioi Bay in Hyogo Prefecture,
To compare vertical and horizontal immersion directions
Test specimens coated with tar vinyl-based rust preventive paint only.
Immerse in both immersion directions in both sea areas above,
Were compared by weight. [0082] [Table 12][0083] [Table 13] [0084] [Table 14][0085] [Table 15][0086] [Table 16] [0087] [Table 17][0088] [Table 18] [0089] [Table 19][0090]                               (All adhesion areas are 100%) It is clear from the results of Tables 12 to 20 above that
As a blend polymer with rosin, vinyl chloride
Paint composition of Comparative Example 1 using styrene-based resin, styrene pig
Diene rubber, chlorinated paraffin resin, ethylene-acetic acid vinyl
Coating compositions of Comparative Examples 2, 3, and 6 using benzyl copolymer
(Each of the examples described in JP-A-60-28456
Equivalent), paint composition of Comparative Example 5 using polyisobutylene
(Refer to the examples of JP-A-50-135125).
To) and polymer solution S₇Antifouling agent and rosin
The coating composition of Comparative Example 4 which was not compatible (JP-A-7-102)
No. 193), all of them
Some of them show good paint consumption for several months after pickling starts
However, after immersion for a long time, a residual layer is formed on the coating film surface,
Unsatisfactory results for both coating film wear rate and antifouling performance
Resistance, crack resistance, adhesion, recoilability and outfitting period
Defects were also found in the corresponding marine organism adhesion prevention performance. On the other hand, various rosin compounds and hydrolysates
Decomposition type organic silyl ester group-containing polymer solution S₁~ S
₁₂In each of the coating compositions of Experiments 1 to 20 in which
Even after immersion, no residual layer is formed on the coating surface,
Antifouling performance, crack resistance, adhesion, recoatability and outfitting
In any test of the marine life adhesion prevention performance corresponding to the wearing period
Shows satisfactory results, and the coating composition of the present invention
It can be seen that the sample has excellent performance. [0093] As described above, the coating composition of the present invention comprises:
Bottom, fish nets and cooling water pipes that need to prevent underwater biofouling
Prevention of sludge diffusion in underwater structures, such as underwater civil engineering works
The coating can be applied even after prolonged immersion.
Since there is no residual layer on the film surface,
No defects such as cracks, peeling, etc.
The speed is higher than a certain speed, and the marine organism adhesion prevention performance is long.
Marine organisms that can be used for
Excellent prevention performance, better recoating
It also exerts its properties.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Masayasu Ito             296 Shimokurata-cho, Totsuka-ku, Yokohama, Japan             Oil and fat Co., Ltd. (72) Inventor Shigeo Fukuda             296 Shimokurata-cho, Totsuka-ku, Yokohama, Japan             Oil and fat Co., Ltd. (72) Inventor Yoshihisa Kawakami             296 Shimokurata-cho, Totsuka-ku, Yokohama, Japan             Oil and fat Co., Ltd. (72) Inventor Yoshiro Matsubara             296 Shimokurata-cho, Totsuka-ku, Yokohama, Japan             Oil and fat Co., Ltd. (72) Inventor Yasushi Kawamura             296 Shimokurata-cho, Totsuka-ku, Yokohama, Japan             Oil and fat Co., Ltd. (72) Inventor Shigeru Masuzoka             296 Shimokurata-cho, Totsuka-ku, Yokohama, Japan             Oil and fat Co., Ltd. (72) Inventor Yoshihiro Honda             296 Shimokurata-cho, Totsuka-ku, Yokohama, Japan             Oil and fat Co., Ltd. F term (reference) 4J038 BA231 BA232 CL001 CL002                       GA15 HA066 HA106 HA216                       HA246 HA296 HA376 JA47                       JC06 JC14 KA02 NA05 NA11                       NA12

Claims (1)

Claims: 1. A) one or more rosin compounds comprising a rosin, a rosin derivative or a rosin metal salt, and B) the following general formula: (Wherein, R ^{1 to} R ³ each represent an alkyl group or an aryl group)
And may be the same or different, but at least one of R ^{1 to} R ³ is a group having 3 or more carbon atoms. X represents an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group,
It is a fumaroyloxy group, an itaconoyloxy group or a citraconoyloxy group. 1) of the monomer M represented by
An organic silyl ester group-containing polymer comprising a polymer of at least one or two or more polymerizable monomers other than the above-mentioned monomer M essentially containing acrylic acid or methacrylic acid; A) a coating composition comprising an antifouling agent as an essential component.