JPH08104831A - Antifouling coating composition - Google Patents

Abstract

PURPOSE: To obtain an antifouling coating composition which comprises a segmented polymer bearing both hydrophilic and hydrophobic segments and is effective in both sea and fresh water without use of high-toxicity compounds. CONSTITUTION: This composition comprises (A) a segmented polymer of 1,000-50,000 number-average molecular weight comprising at least two segments of (i) a polyoxyalkylene segment including more than 10-wt.% of ethylene oxide units of 200-10,000 number-average molecular weight, preferably polyoxyethylene segment, poly(oxyethylene-oxypropylene) segment and (ii) a polydiorganosiloxane segment of 300-10,000 number-average molecular weight, preferably polydimethylsiloxane segment and (B) a moisture-curing type silicone rubber and/or a polymer from an ethylenically unsaturated monomer of 1,000-100,000 molecular weight, preferably an acrylic resin at a weight ratio of 99/1-1/99.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antifouling coating composition effective in seawater and freshwater without using highly toxic compounds due to the effect of a segmented polymer having both hydrophilic / hydrophobic segments. It is a thing.

[0002]

2. Description of the Related Art In water, structures are generally polluted by attached organisms. Usually, antifouling agents (organic compounds,
An antifouling paint containing a heavy metal compound) is applied to the structure surface. In recent years, environmental pollution problems due to excessively released antifouling agents have become apparent, and it is desired to regulate their use.

On the other hand, silicone antifouling paints have appeared as antifouling paints that do not depend on toxicity such as the above antifouling agents (Japanese Patent Publication No. 63-2995; JP-A-3-255169).
However, there are drawbacks that the coating method is complicated, for example, pretreatment for painting is indispensable, and repainting is extremely difficult.

Therefore, an underwater biofouling preventing coating composition comprising a copolymer resin having a large number of polyoxyalkylene chains such as polyoxyethylene chains in its side chains has appeared (Japanese Patent Laid-Open No. 320205/1993/320540). ). JP-A-5-320539 states that a large number of polyoxyethylene chains are oriented on the surface of a coating composition coating film in water to prevent the attachment of aquatic organisms. However, since the polyoxyethylene chain is bonded to the copolymer resin, when attempting to introduce a large amount of polyoxyethylene chain in an attempt to increase hydrophilicity, the paint film is easily hydrogelized in water, As a result, a coating film that can withstand long-term use cannot be obtained. JP-A-5-320
In 540, the polyoxyethylene chain for imparting hydrophilicity is bonded only to one end of the copolymer resin. In this case as well, in order to increase the hydrophilicity of the coating film surface, it is necessary to increase the proportion of the polyoxyethylene chain in the total polymer, and as a result, hydrogel is easily formed. In addition, since the mercapto compound having an offensive odor is used as an essential raw material, the offensive odor due to the unreacted substance becomes a problem in use.

[0005]

The present invention uses a segmented polymer containing a hydrophilic polyoxyalkylene chain and a hydrophobic polydiorganosiloxane chain, each containing at least two segments in the same molecule. Since the segmented polymer alone does not have sufficient durability, a moisture-curable silicone rubber and / or a polymer of an ethylenically unsaturated monomer is used in combination as a film forming resin component.

More specifically, the present invention relates to (a) a polyoxyalkylene segment having a number average molecular weight of 200 to 10,000 and an ethylene oxide unit content of 10% by weight or more, and a polydiorganosiloxane having a number average molecular weight of 300 to 10,000. Number average molecular weight of 1,000 to 50,000 each containing at least two segments
0 segmented polymer, (b) moisture-curable silicone rubber and / or number average molecular weight 1,000 to 10
The present invention relates to an antifouling coating composition containing 50,000 ethylenically unsaturated monomer polymers in a weight ratio of 99/1 to 1/99. The weight ratio of the segmented polymer to the moisture-curable silicone rubber and / or the ethylenically unsaturated monomer polymer is preferably 80/20 to 5/95.

In the present invention, the component that imparts hydrophilicity to the coating film (= segmented polymer) and the coating film forming resin component (= moisture-curable silicone rubber composition and ethylenically unsaturated monomer polymer) are independent. are doing. Therefore, the hydrophilicity can be arbitrarily controlled without impairing the water resistance of the coating film. Further, since the segmented polymer of the present invention has a surface active action, it has a characteristic of being compatible with many resins. In addition, the segmented polymer, which is the hydrophilicity-imparting component, is easy to move in the paint film due to its flexible structure,
After immersion in water, it is oriented on the surface and promptly forms a hydrophilic film. Therefore, the adsorption of floating substances, bacteria, etc., which is regarded as important as the first stage of fouling, is suppressed, and as a result, the progress of fouling is further slowed down.

Examples of the polyoxyalkylene segment include polyoxymethylene segment, polyoxyethylene segment, polyoxypropylene segment, polyoxytetramethylene segment, and a combination of two or more thereof. In the present invention, polyoxyethylene segment and polyoxyethylene / polyoxypropylene segment are particularly preferable.

The polyoxyalkylene segment contains at least 10% by weight of ethylene oxide units and has a number average molecular weight of 200 to 10,000 (preferably 40).
0 to 5,000) is preferable. When the number average molecular weight is less than 200, the hydrophilicity of the segmented polymer is remarkably reduced and the antifouling performance is not sufficiently exhibited. If the number average molecular weight exceeds 10,000, it is difficult to obtain a uniform segmented polymer, and the antifouling performance of the segmented polymer cannot be expected sufficiently.

A polydimethylsiloxane segment as the polydiorganosiloxane segment, and a part of the methyl group in the polydimethylsiloxane segment has a hydrogen atom, an ethyl group, a propyl group, a butyl group, an isopropyl group, an octyl group, or the like, and a carbon number of 1 to 1. 8 alkyl group; 6-10 carbon atoms such as phenyl group and naphthyl group
An aryl group; a benzyl group, a phenylethyl group, or another aralkyl group having 7 to 9 carbon atoms; an octylphenyl group, a nonylphenyl group, or any other alkaryl group having 7 to 24 carbon atoms; A substituted alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an octyl group substituted with a halogen such as fluorine, bromine, and iodine; 1 to 2 or more alkyl groups having 1 to 8 carbon atoms such as an ethyl group and a propyl group having a polyoxyalkylene segment end-capped with a 1 to 8 carbon alkyl group or phenyl group; Examples thereof include polydiorganosiloxane segments substituted with a group consisting of a combination. In the present invention, a polydimethylsiloxane segment, a polymethylphenylsiloxane segment, a polymethylhydrogensiloxane segment, and a combination of these siloxane segments are particularly preferable.

The polydiorganosiloxane segment has a number average molecular weight of 300 to 10,000 (preferably 8).
00-5,000) is preferable. When the number average molecular weight is out of the range, the antifouling performance of the segmented polymer cannot be expected as in the case of the polyoxyalkylene segment.

The segmented polymer used in the present invention must have at least two segments each of the polyoxyalkylene segment and the polydiorganosiloxane segment in order to exhibit sufficient antifouling performance. The segmented polymer may also be composed of two or more polyoxyalkylene segments and two or more polydiorganosiloxane segments.

In addition to the polyoxyalkylene segment and the polydiorganosiloxane segment, the segmented polymer may contain a copolymerization component capable of copolymerizing with these segments. Examples of such a copolymerization component include 1,6-hexanediol, neopentyl glycol, ethylene glycol, 1,2-
Propylene glycol, 1,4-bis (hydroxymethyl) -cyclohexane, 2,2-bis (4-hydroxycyclohexyl) bropane, 2,2-bis [4- (β-
Hydroxyethoxy) phenyl] propane, 2-methyl-1,3-propanediol, glycerol, 1,8-
Octanediol, 1,3-propanediol, 2,
2,4-trimethyl-1,3-pentanediol, N,
Polyol compounds such as N-bis-2-hydroxypropylaniline, trimethylolpropane, ethylene oxide adduct of bisphenol A, and ethylene oxide adduct of hydrogenated bisphenol A; phthalic anhydride,
Isophthalic acid, terephthalic acid, hexahydrophthalic acid,
Polybasic acid compounds such as dichlorophthalic acid, adipic acid, succinic acid, sebacic acid, and azelaic acid; glycidyl compounds such as bisphenol A diglycidyl ether;
Etc. can be illustrated. Two or more kinds of these copolymerization components may be contained. When the other copolymerization component is thus contained, the sum of the polyoxyalkylene segment and the polydiorganosiloxane segment is set to 50% by weight or more of the total amount of the components necessary for synthesizing the segmented polymer. Is preferred.

The number average molecular weight of the segmented polymer is 1,000 to 50,000 (preferably 3,000 to 2).
10,000). When the number average molecular weight is less than 1,000, it becomes difficult to maintain the water resistance of the coating film for a long period of time. If the number average molecular weight exceeds 50,000, the mechanical strength of the coating film and the like will decrease.

The segmented polymer can be synthesized by, for example, a carboxyl group / hydroxy group polyesterification reaction, a carboxyl group / amino group amidation reaction, an isocyanate group / hydroxyl group urethanization reaction, or an acid / epoxy addition reaction. In this case, the segmented polymer is synthesized by separately preparing a polymer for the polyoxyalkylene segment having a reactive group at both ends of the polymer and a polymer for the polydiorganosiloxane segment, and reacting between the polymer reactive groups for each segment. Done by.
In this case, the polymer for each segment is a carboxyl group,
It has different groups selected from a hydroxyl group, an isocyanate group, an epoxy group, and an amino group and capable of reacting with each other. In addition, it can also have groups such as alkoxysilyl groups, acid anhydride groups, thiol groups, active ester groups, vinyl groups, and acryloyl groups. In the present invention, segmented polymer synthesis by polyesterification reaction and acid / epoxy addition reaction is particularly preferred.

The moisture-curable silicone rubber composition used in the present invention includes various one-component moisture-curable silicone rubber compositions such as deacetic acid type, deoxime type, deacetone type, dealcohol type, and heat curing type. Can be used particularly preferably. Specifically, in the deacetic acid type, KE41, KE41, KE42S, KE420, FE123 and the like (all are trade names of Shin-Etsu Chemical Co., Ltd.); in the deoxime type, KE45, KE44, KE
441, KE445, KE4525, and KE402
Etc. (all are trade names of Shin-Etsu Chemical Co., Ltd.); Deacetone type is KE348, KE347, KE3490, and KE3491 etc. (All are trade names of Shin-Etsu Chemical Co., Ltd.); Dealcohol type is KE48, KE47,
KE471, KE4866, etc. (all are trade names of Shin-Etsu Chemical Co., Ltd.); KE125 for thermosetting type
1, KE1252, KE1253 and the like (all are trade names of Shin-Etsu Chemical Co., Ltd.); and the like. Furthermore, if necessary, various two-component moisture-curable silicone compositions can be used, although they have poor workability.

The number average molecular weight of 100 used in the present invention
Acrylic resins are particularly preferable as the ethylenically unsaturated monomer polymer of 0 to 100,000.

As the acrylic resin, those obtained by radically polymerizing an acrylic monomer and another copolymerizable monomer in an organic solvent by a known technique are used. Here, as the acrylic monomer, methyl (meth) acrylate, ethyl (meth) acrylate,
n-butyl (meth) acrylate, i-butyl (meth)
Acrylate, t-butyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isopropyl (meth) acrylate, cyclohexenyl (meth) acrylate, and (Meth) acrylic acid esters such as isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate And a hydroxyl group-containing (meth) acryl such as an adduct of 2-hydroxyethyl (meth) acrylate and ε-caprolactone (for example, Praxel FM1 manufactured by Daicel Chemical Industries, Ltd.) Esters; N, N-dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N, N-di-t-butylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, and N, N-
Amino group-containing (meth) acrylic acid ester such as dibutylaminoethyl (meth) acrylate; Glycidyl (meth) acrylate, and epoxy group-containing (meth) such as 3,4-epoxycyclohexyl (meth) acrylate
Acrylic esters; (meth) acrylic acid; (meth)
Acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N,
N-dimethylaminoethyl (meth) acrylamide, N
-Isopropylmethacrylamide, N, N-diethylaminohexyl (meth) acrylamide, and N, N-
Methacrylamide derivatives such as dimethylaminopropyl (meth) acrylamide; N-substituted (meth) acrylamide derivatives containing hydroxyl groups such as N-methylol (meth) acrylamide; 3-trimethoxysilylpropyl (meth)
Alkoxysilyl group-containing (meth) acrylic acid esters such as acrylate, 3-triethoxysilylpropyl (meth) acrylate, and dimethoxymethylsilylpropyl (meth) acrylate; isocyanoethyl (meth) acrylate, isocyanomethyl (meth) acrylate , And isocyanate group-containing (meth) acrylic acid esters such as isocyanobutyl (meth) acrylate; 2,2,2-trifluoroethyl (meth) acrylate, and 2,2-difluoroethyl (meth) acrylate Fluorine-modified (meth) acrylates; TSL
9705 (trade name, manufactured by Toshiba Silicone Co., Ltd.), X-
22-5002 (trade name, product of Shin-Etsu Chemical Co., Ltd.),
TM0701, FM0711, FM0721, and F
Examples thereof include polydiorganosiloxane-modified (meth) acrylates such as M0725 (all of which are trade names, manufactured by Chisso Corporation). Further, copolymerizable monomers include styrene, α-methylstyrene, (meth) acrylonitrile, (meth) acrolein, vinyltoluene, vinyl chloride, vinyl butyrate, vinylidene chloride, vinyl propionate, vinyl butyl ether, allyl glycidyl ether, acetic acid. Vinyl, allyl acetate, allylamine, 1
-Vinyl-pyrrolidone, vinyltrimethoxysilane, vinyltriethoxysilane, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, and other unsaturated vinyl compounds other than acrylic are used. If necessary,
Also used are monomers having two or more α, β-unsaturated bonds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol tetra (meth) acrylate. It is possible. However, these copolymerization components are preferably 50% by weight or less based on the total amount of the monomers including the acrylic monomer.

Examples of usable organic solvents include ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate; aromatic hydrocarbon solvents such as xylene, toluene and anisole; methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone, Ketone solvents such as methyl ethyl ketone; isopropyl alcohol, n
Alcohol solvents such as butanol, ethylene glycol, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; saturated hydrocarbon solvents such as mineral spirit, octane, cyclohexane; dioxane, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, And polar solvents containing no active hydrogen groups such as tequilahydrofuran; or mixtures of two or more of these solvents.

Examples of the radical polymerization initiator include azobisisobutyronitrile and 2,2'-azobis (2,4
-Dimethylpareronitrile), azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid),
2,2-Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) 2-hydroxyethyl] propionamide}, and azo-based polymerization initiators such as 2,2′-azobisisobutyramide dihydrate; benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, t-
Butyl-perpivalate, t-butyl-per 3,5,5
-Trimethylhexanoate, di-2-ethylhexyl peroxydicarbonate, 1,1-bis- (t-butylperoxy) -3,5,5-trimethylcyclohexane, cyclohexane peroxide, lauroyl peroxide, t-butyl Peroxy-2-ethylhexanoate, cumene hydroperoxide, and other peroxide-based polymerization initiators; and other polymerization initiators that are commonly used in radical polymerization can be mentioned.

The above polymerization reaction is usually carried out at about 60 ° C to 180 ° C.
It can be carried out at a temperature of ° C (preferably 90 ° C to 120 ° C), and under such conditions for 2 to 10 hours, usually 3 to 6
It can be finished in about time.

The number average molecular weight of the obtained ethylenically unsaturated monomer polymer must be within the range of 1,000 to 100,000. As a method for obtaining the molecular weight within this range, radical polymerization initiation How to adjust the dosage;
2,4-diphenyl-4-methyl-1-pentene (α-
A method using an aromatic chain transfer agent such as methylstyrene dimer); a method using an allyl compound such as allyl alcohol; a mercapto compound having a relatively low odor such as t-dodecanethiol, 2-ethylhexyl thioglycolate, and thioethanol. A method using a chain transfer agent; and the like.

The acrylic resin used in the present invention has a number average molecular weight of 1,000 to 100,000 (preferably 2,
000-50,000). Number average molecular weight is 1,0
When it is less than 00, it is difficult to obtain a coating film having good durability. Further, when the number average molecular weight exceeds 100,000, the workability of paint coating is significantly deteriorated.

The number average molecular weight in the present invention is GPC (gel permeation chromatography).
Is the value calculated in terms of polystyrene.

The antifouling coating composition of the present invention contains 1 to 99% by weight, preferably 5 to 80% by weight of the above-mentioned segmented polymer as an essential component, a moisture-curable silicone rubber and / or an ethylenically unsaturated monomer weight. Coalesce 99 to 1
%, Preferably 95 to 20% by weight as a vehicle component. When the content of the segmented polymer is low, the antifouling performance is not exhibited at all or the antifouling period is very short. If the content of the segmented polymer is high, the general coating properties such as adhesion, water resistance and workability of the coating are deteriorated.

When the ethylenically unsaturated monomer polymer has a cross-linking reactive group, a cross-linking agent is used to combine the ethylenically unsaturated monomer polymers with each other, and / or between the ethylenically unsaturated monomer polymer / segmented polymer, And / or the segmented polymers can be cross-linked with a cross-linking agent.

Examples of the cross-linking agent used include hexamethylene diisocyanate, an adduct of hexamethylene diisocyanate and trimethylolpropane, tolylene diisocyanate, an adduct of tolylene diisocyanate and trimethylolpropane, and phenylenediene. Isocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, lysine diisocyanate,
And a polyisocyanate compound such as isophorone diisocyanate; composed of the above polyisocyanate compound and the like and a blocking agent such as phenol, thiourea, methanol, propanol, t-butanol, ethyl acetoacetate, dimethyl malonate, and ε-caprolactam. A so-called block isocyanate compound; a melamine formaldehyde resin such as a methylated melamine resin and a butylated melamine resin; a dibasic anhydride-containing resin such as a maleic anhydride / styrene alternating copolymer; a polyepoxy compound such as polyglycidyl methacrylate And the like can be exemplified.

The coating composition of the present invention contains petrolatum and petroleum wax (eg, petroleum wax) for the purpose of further improving antifouling functionality.
Solid paraffin wax, chlorinated paraffin wax,
Slacks wax and modified wax) and animal and plant waxes (eg, wood wax, white wax, carnauba wax, castor wax, etc.)
In addition to waxes such as liquid paraffin, process oils, lubricating oils (eg, machine oils, sewing oils, etc.), vegetable oils (castor oil, salad oils, etc.), animal oils (lards, etc.) and mineral oils; silicone rubber and Fluorine-based resin (for example, polyvinylidene fluoride, fluorine-based acrylic resin,
And a water repellent resin such as polyfluoroethylene) can be added. If necessary, titanium oxide,
Coloring pigments such as zinc oxide, carbon black, graphite, red iron oxide, chromium oxide, and cobalt blue;
Extender pigments such as calcium carbonate, barium sulfate, talc, clay, silica, gypsum; tricresyl phosphate,
Plasticizers such as chlorinated paraffin and dioctyl phthalate; additives for paints such as anti-sagging agents, defoaming agents, anti-settling agents, and surface conditioners; various agents permitted under the Food Sanitation Act (for example, Preservatives, fungicides, antioxidants, bactericides, fragrances, etc.); enzyme activity inhibitors (alkylphenols, alkylresorcinols, etc.); However, the use of heavy metal compounds such as cuprous oxide and conventionally used organic antifouling agents does not impair the performance of the present invention, but is not preferable in view of the possibility of environmental pollution and ecosystem destruction.

The method for forming a coating film using the coating composition of the present invention is not particularly limited, and the same method as in the conventional organic solvent type antifouling coating can be used. For example, the antifouling coating composition of the present invention is used for underwater structures (for example, ship bottoms, port facilities, buoys, pipelines, bridges, submarine bases, aquaculture fishing nets, fixed nets, undersea oilfield related facilities, electric power plant water pipes and water intakes. Facilities, breakwaters, ship mooring facilities, etc.) or directly on the surface of base materials such as wash primer, zinc epoxy type primer, etc .; oil-based rust preventive, chlorinated rubber type, epoxy type, and silicone rubber type undercoat Primers; multi-layer coatings and primers formed by applying a combination of intermediate-coat paints or top-coat paints such as long-oil phthalic acid resin-based, chlorinated rubber-based, silicone rubber-based, epoxy-based paints, undercoat primers, Brush coating, spray coating, low coating on the surface of the base material with the multilayer coating film formed by sequentially coating the intermediate coating material and the top coating material. Over painting, electrostatic painting, can be coated by a means of dipping. The coating amount is generally 5 to 500 μm (preferably 10 μm) as a dry film thickness.
˜300 microns). The coating film can be dried under a warming condition, but in some cases, it can be dried under a heating condition or under a room temperature.

[0030]

The coating film obtained from the coating composition of the present invention has a hydrophilic property due to the effect of the segmented polymer, in which the polyoxyethylene chains are oriented on the surface of the coating film very rapidly with immersion in water, and Since the coating film itself is strong and water resistant, it does not contain highly toxic conventional antifouling agents, and does not distinguish between seawater; brackish water; and freshwater, and adheres to crustaceans such as barnacles; mussels, etc. Prevents the adhesion of aquatic organisms such as freshwater adhesive bivalves such as marine adhesive bivalves and river mussels; adhesive plants such as Ulva; In addition, the present invention solves the drawbacks of antifouling paints using a silicone resin, such as the inability to repaint, the high cost, and the repelling of other paints.

[0031]

The present invention will be described in detail below with reference to examples. In the examples and comparative examples, "part" means "part by weight" and "%" means "% by weight".

Preparation Example 1: Synthesis of segmented polymer solution (A) α, β-hydroxydimethylsiloxane was added to a reaction vessel equipped with a heating device, a stirrer, a reflux device, a water separator, a rectification column and a thermometer. X-22-160AS (number average molecular weight 9
00; manufactured by Shin-Etsu Chemical Co., Ltd.) 68.9 parts, α, ω-
Carboxypolyoxyethylene PEO acid No. Four
00 (number average molecular weight 400; Kawaken Fine Chemicals Co., Ltd.) 30.2 parts and trimethylolpropane 1.
0 parts and 0.05 parts of dimethyltin oxide were charged and heated to 200 ° C. for 3 hours. At this time, about 17
The dehydration reaction started at 0 ° C and the reaction system showed a clear appearance at 200 ° C.

Then, from the reaction system 200 ° C. to 210 ° C., 4
After raising the temperature over time, the acid value of the reaction system was measured and found to be 13.3 mgKOH / g solid content. Then, the reaction system was cooled to 120 ° C., 2 parts of xylene was added, and a dehydration reaction under reflux was carried out for about 5 hours. When the acid value of the reaction system reached 5.0, the reaction was terminated and segmented. A polymer solution (A) was obtained. The amount of dehydration here was 2.4 parts, and the hydroxyl value of the segmented polymer was 13.5.
It was mg KOH / g solids. The segmented polymer solution (A) had a nonvolatile concentration of 93.0% and a segmented polymer number average molecular weight of 5,6 as determined by GPC.
It was a clear solution having a viscosity of 00 and a viscosity of 3,830 cp (25 ° C.).

Preparation Example 2: Synthesis of segmented polymer solution (B) In a reaction vessel similar to that used in the synthesis of segmented polymer solution (A), 48.7 parts of X-22-160AS and P
EO acid No. 10.4 (number average molecular weight 1,000; manufactured by Kawaken Fine Chemicals Co., Ltd.), 50.4 parts, trimethylolpropane 1.0 part, and dimethyltin oxide 0.05 part were charged to prepare a segmented polymer solution ( A polymer with a clear appearance was obtained by the same method as in the synthesis of A). After the reaction was completed, 35 parts of xylene was charged into the reaction system to obtain a segmented polymer solution (B). In this reaction, the dehydration amount was 1.7 parts and the hydroxyl value of the segmented polymer was 15.4 mgKOH / g solid content. The number average molecular weight of the segmented polymer is 6,8.
40, and the polymer solution (B) has a nonvolatile content of 6
The viscosity was 9.9% and the viscosity was 563 cp (25 ° C).

Preparation Example 3: Synthesis of Segmented Polymer (C) In a reaction vessel similar to that used in the synthesis of segmented polymer solution (A), α-ω-carboxydimethylsiloxane X-22-162A (number) Average molecular weight 1,840; Shin-Etsu Chemical Co., Ltd. 43.1 parts and polyethylene glycol 1,000 (number average molecular weight 950-1050;
Wako Pure Chemical Industries, Ltd.) 46.9 parts and isophthalic acid 3.9
And 0.05 parts of dibutyltin oxide were charged,
A polymer having a slightly cloudy appearance was obtained by the same synthesis method as that of the segmented polymer solution (A).

After completion of the reaction, 35 parts of xylene was charged into the reaction system to obtain a segmented polymer solution (C). In this reaction, the dehydration amount was 1.7 parts, the hydroxyl value of the obtained segmented polymer solution was 8.8 mgKOH / g solid content, and the number average molecular weight was 13,500. Further, the polymer solution (C) has a non-volatile content of 70.1% and a viscosity of 1,28.
It was 0 cp (25 ° C).

Preparation Example 4: Synthesis of Segmented Polymer Solution (D) PEO acid No. 400 to 12.7
And 0.5 part of dimethylbenzylamine were charged, 1
Heated to 50 ° C. Then, KF-105 (number average molecular weight 9
80; Shin-Etsu Chemical Co., Ltd. 62.0 parts was added dropwise at a constant rate over 3 hours, and after the addition was completed, 25.3 parts were further added.
Part PEO acid No. 400 was dropped for 1 hour at a constant rate. Then, when the reaction system was kept warm at 150 ° C. for 2 hours, a segmented polymer solution (D) having a clear appearance was obtained.
was gotten. The hydroxyl value of the obtained segmented polymer was 36.1 mgKOH / g solid content, and the number average molecular weight was 3,150. The polymer solution (D) has a non-volatile content temperature of 96.2% and a viscosity of 1,230 cp.
(25 ° C).

Preparation Example 5: Synthesis of acrylic resin solution (A) 38 parts of xylene and methyl isobutyl ketone (MIBK) were placed in a reaction tank equipped with a heating device, a stirrer, a reflux device, a water separator, a rectification and the like and a thermometer. ) 20 parts are charged and 110 ° C
Heated to. Thereafter, 2.3 parts of methacrylic acid, 13.9 parts of 2-hydroxyethyl methacrylate, 10 parts of methyl methacrylate, and 2-ethylhexyl methacrylate of 3
5.5 parts, t-butyl methacrylate 38.3 parts, t
-Butylperoxy-2-ethylhexanoate 1.2
The mixed solution with 1 part was added dropwise at a constant rate over 3 hours. After the reaction system was aged for 1 hour, 0.2 parts of t-butylperoxy-2-ethylhexanoate and 20 parts of xylene were added dropwise over 30 minutes and aged for 2 hours to obtain an acrylic resin solution (A ) Got. The obtained resin solution (A) had a nonvolatile concentration of 58.0% and the acrylic resin had a number average molecular weight of 11,500.

Preparation Example 6: Preparation of Acrylic Resin Solution (B) 57.1 parts of segmented polymer solution (A) and 0.75 parts of itaconic anhydride were added to the reaction vessel used in the preparation of acrylic resin solution (A). , Dibutyltin dilaurate 0.0
2 parts and 10 parts of xylene were charged, heated to 110 ° C. and held for 1 hour. After that, 2.3 parts of methacrylic acid,
2-Hydroxyethyl methacrylate 13.9 parts, methyl methacrylate 10 parts, 2-ethylhexyl methacrylate 35.5 parts, t-butyl methacrylate 38.3 parts, and t-butyl peroxy-2-ethyl. A mixed solution of 1.2 parts of hexanoate was added dropwise at a constant rate over 3 hours, and 1
Aged for hours. Then, 30 parts of 0.2 part of t-butylperoxy-2-ethylhexanoate and 20 parts of xylene are added.
The solution was added dropwise at a constant rate over a period of time and aged for 2 hours to obtain an acrylic resin solution (B). The obtained resin solution (B) had a nonvolatile concentration of 59.0%, and the acrylic resin had a number average molecular weight of 9,960. The resin solution (B) contains a graft polymer in which an acrylic resin is graft-polymerized on a part of the segmented polymer.

Examples 1 to 5 and Comparative Examples 1 and 2 Resins and the like were dispersed with a ball mill in the blending amounts shown in Table 1, and then a cross-linking agent was added if necessary to obtain antifouling coating compositions. Prepared. The obtained coating composition was coated on a steel sheet coated with a commercially available vinyl tar-based rust preventive coating so that the average dry film thickness was 100 μm, and the coating composition was applied at room temperature under 1
It was cured for a week and used as an evaluation test plate.

Antifouling performance evaluation test method In the performance evaluation test, the evaluation test plate was immersed for 1 year in the seawater depth of 1 m at a depth of 30 m offshore from the Critical Research Institute of Nippon Paint Co., Ltd. (Tamano City, Okayama Prefecture), and the ratio of the attached area of organisms The antifouling performance was evaluated by. The results are shown in Table 1.

[0042]

[Table 1]

As is clear from Table 1, the coating films using the resin compositions of the examples according to the present invention have antifouling performance. Therefore, the antifouling coating composition of the example using the resin composition of the preparation example according to the present invention exhibits excellent antifouling performance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C09D 183/12 PMM

Claims (7)

[Claims] 1. A number average molecular weight of 200 to 1 in (a) molecule.
A segment having a number average molecular weight of 1,000 to 50,000 containing at least two polyoxyalkylene segments having an ethylene oxide unit content of 10% by weight or more and a polydiorganosiloxane segment having a number average molecular weight of 300 to 10,000. Polymer and (b) a moisture-curable silicone rubber and / or an ethylenically unsaturated monomer polymer having a number average molecular weight of 1,000 to 100,000 in a weight ratio of 99/1 to 1/99. An antifouling coating composition which is characterized in that 2. The antifouling coating composition according to claim 1, wherein the polyoxyalkylene segment is a polyoxyethylene segment or a poly (oxyethyleneoxypropylene) segment. 3. The polydiorganosiloxane segment comprises
The antifouling paint composition according to claim 1, which is a polydimethylsiloxane segment, a polymethylhydrogensiloxane segment, or a polymethylphenylsiloxane segment. 4. The antifouling coating composition according to claim 1, wherein the moisture-curable silicone rubber is a one-component moisture-curable silicone rubber. 5. The antifouling coating composition according to claim 1, wherein the ethylenically unsaturated monomer polymer is an acrylic resin. 6. The antifouling coating composition according to claim 5, wherein the acrylic resin is grafted onto the segmented polymer. 7. The ratio of the segmented polymer to the moisture-curable silicone rubber and / or the ethylenically unsaturated monomer polymer is 80/20 to 5/95 by weight. Antifouling paint composition.