WO2002051951A1

WO2002051951A1 - Antifouling paint composition

Info

Publication number: WO2002051951A1
Application number: PCT/JP2001/011092
Authority: WO
Inventors: Sadakazu Hokamura; Kazuyoshi Tuneta; Toshiya Takahashi; Hiroki Hayashi; Tomohiro Tanabe; Hiroyuki Tanabe; Tohru Taki; Yoshiyuki Iwase
Original assignee: Dai Nippon Toryo Co., Ltd.
Priority date: 2000-12-22
Filing date: 2001-12-18
Publication date: 2002-07-04
Also published as: JP2002194268A

Abstract

An antifouling paint composition containing as the binder a polymer comprising a silyl monomer of the general formula (1) as a constituent: (1) [wherein R1 is hydrogen or methyl; R?2, R3, and R4¿ are each independently C¿1-25? alkylene, phenylene, or the like; R?5, R6, and R7¿ are each independently C¿1-25? alkyl, aryl, or the like; m, n, and y are each an integer of 0 to 20; and x is an integer of 1 to 15, with the proviso that m, n and y satisfy the relationship: (m + n + y) ≥ 1]. This composition can give a paint film capable of exhibiting an antifouling effect in seawater over a long period.

Description

Specification

Antifouling paint composition Technical field

TECHNICAL FIELD The present invention relates to an antifouling paint composition for preventing marine organisms from adhering to the surface of a marine object for a long period of time. Background art

Various types of marine organisms adhere to the bottom skin of ships below the sea level, marine structures, and the surface of fishing nets, which hinders efficient operation of ships. Anti-fouling paints containing various anti-fouling agents have been applied as a countermeasure against problems such as a significantly shortened service life of fishing nets. Typical antifouling paints that have been used in the past include binders consisting of resins such as vinyl resins, alkyd resins, and chlorinated rubber that are insoluble in seawater, and rosins that are soluble in seawater. Insoluble matrix-type antifouling paint containing an antifouling agent, and a dissolved matrix type antifouling paint containing a tin-containing resin that gradually hydrolyzes in seawater as a binder and containing an antifouling agent as necessary.

However, in the insoluble matrix type antifouling paint, since the antifouling agent is eluted together with rosin in seawater, a stable antifouling effect cannot be expected for a long time, and the insoluble resin component remaining in the coating film However, since the skeleton structure is formed, especially when applied to ships, there is a problem that frictional resistance increases between seawater and the paint film surface, resulting in a decrease in speed, an increase in fuel consumption, and the like. On the other hand, the dissolution-matrix antifouling paint containing the tin-containing resin as a binder component has an excellent antifouling effect, but has a serious problem in terms of safety and health and environmental protection.

Thus, as a dissolving matrix type antifouling paint which has solved the above problems of the tin-containing resin, an antifouling paint using a silyl group-containing resin as a binder is disclosed, for example, in Japanese Patent Application Laid-Open No. 63-215780 / 1988. These are disclosed in Japanese Unexamined Patent Publications Nos. 63-31414805, JP-A-Heisei 4-264169, JP-A-Hei41-264170, and the like. However, the silyl group-containing resins described in these patent publications have a high hydrolyzability, and a free carboxyl group is generated upon hydrolysis, which forms a complex with a metal-containing antifouling agent such as cuprous oxide. As a result, during storage, the antifouling paint tends to thicken or gel, resulting in poor storage stability of the antifouling paint. In addition, in order to improve the antifouling property, it is usually sufficient to contain a large amount of silyl groups, but if it is contained in a large amount, the formed coating film will be cracked after the silyl group-containing resin is hydrolyzed. There was a problem that peeling was easily caused.

The present invention has been made in view of such problems of the prior art, and contains no organotin, so that there are few problems in health and safety and environmental preservation, and the storage stability is excellent, and the cracks are improved. It is an object of the present invention to provide an antifouling paint which forms a coating film having excellent long-term antifouling property, which hardly causes a stain. Disclosure of the invention

According to the present invention, as a result of intensive studies to achieve the above object, as a binder of an antifouling paint, a homopolymer or a polymer containing a silyl monomer having a specific structure as a component is used. As a result, the present inventors have found that the above object can be achieved, and have reached the present invention.

That is, the present invention relates to the following inventions.

Equation (1),

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are each independently an alkylene group having 1 to 25 carbon atoms, a phenylene group, a cyclohexylene group, , Expression,

(In the formula, R ⁸ is an alkylene group having 1 to 25 carbon atoms, a phenylene group, or a cyclohexylene group.)

Wherein R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 25 carbon atoms, an aryl group, a cycloalkyl group and A hydrocarbon group selected from the group consisting of an aralkyl group, m, n and y are integers from 0 to 20; X is an integer from 1 to 15; and (m + n + y) ≥1. ] An antifouling paint composition comprising a polymer containing the silyl monomer (A) represented by the formula (1) as a component. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The antifouling paint of the present invention comprises the binder, an optional antifouling agent and a solvent as constituent components, and further includes a dehydrating agent, an antifoaming agent, an anti-settling agent, an anti-gelling agent, Components containing various additives such as belling agents and thixotropic agents, pigments, rosin or its derivatives or metal salts thereof, modified resins such as acrylic resins and polyvinyl ether resins, plasticizers, fibrous materials, etc. Consists of

The binder is

Equation (1), 6

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are each independently an alkylene group having 1 to 25 carbon atoms, a phenylene group, a cyclohexylene group,ぴ, expression,

(Wherein R ⁸ is an alkylene group having 1 to 25 carbon atoms, a phenylene group or a cyclohexylene group.) RR ⁶ is a hydrocarbon group selected from the group consisting of And R ⁷ are each independently a hydrocarbon group selected from the group consisting of an alkyl group having 1 to 25 carbon atoms, an aryl group, a cycloalkyl group and an aralkyl group, and m, n, and y are 0 to 20. X is an integer from 1 to 15; and

(m + n + y) ≥1. Or a vinyl monomer copolymerizable with one or more of the silyl monomers (A) represented by

(B) is a polymer comprising the copolymer.

The silyl monomer (A) is typically synthesized, for example, by the following method.

A compound having one polymerizable double bond and a hydroxyl group (a) and a saturated acid anhydride (b) are combined with a polymerization inhibitor such as hydroquinone, a quaternary ammonium salt compound, In the presence or absence of a catalyst such as a sulfonium salt compound or a phosphonium salt compound, for example, the reaction is carried out at a reaction temperature of 100 to 150 for 1 to 5 hours to obtain a polymerizable double bond and a carboxyl group. Is synthesized. Next, the product is reacted with the triorganosilane compound (c) in an organic solvent, for example, at a reaction temperature of 50 to 120 ° C. for 2 to 8 hours, thereby obtaining a silyl monomer. Body (A) can be manufactured. When the triorganosilane compound (c) is a hydrosilane-based compound, the dehydrogenation reaction is carried out in the presence of a metal catalyst such as palladium, aluminum, rhodium, or ruthenium-based compound. A dehydrochlorination reaction is carried out in the presence of a basic compound such as sol to obtain a silyl monomer (

A) to manufacture.

The compound (a) having a polymerizable double bond and a hydroxyl group is, for example, a compound represented by the following formula:

It is a compound shown by these.

R ¹ in the formula is a hydrogen atom or a methyl group.

R ² and R ³ in the formula are each independently an alkylene group having 1 to 25 carbon atoms, a phenylene group, a cyclohexylene group and a formula,

(In the formula, R ⁸ is an alkylene group having 1 to 25 carbon atoms, a phenylene group or a cyclohexylene group.)

Here, the alkylene group preferably includes, for example, an alkylene group such as an ethylene group, a propylene group, a butylene group, an amylene group, a hexylene group, and a trimethylene group. Particularly preferred alkylene groups are those having, for example, 2 to 10 carbon atoms.

Further, m, n, and y in the formula are integers of 0 to 20.Preferably, each of 0 to 5 is determined from the balance between the antifouling property of the obtained coating film and the flexibility and adhesion. Preferably, (ffl + n + y) is an integer of 1 or more, and preferably 1 to 10. X in the formula is 1 to 15, preferably 1 to 10.

Specific examples of such a compound (a) include, for example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Acrylate, 1-methyl-2-hydroxyethyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 4- (2-) Hydroxyethyl) Phenyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth) acrylate, and as a commercial product, polyethylene glycol mono (meth) acrylate [trade names: Plenmer PE, AE-350 series; Japan Manufactured by Yushi Yushi Co., Ltd.), polypropylene glycol mono (meth) acrylate [trade name: Brenma AP-400, PP series; manufactured by Nippon Yushi Co., Ltd.], polyethylene glycol polypropylene glycol mono (meth) acrylate [ Product name: Plemma I PEP series; Nippon Yushi Co., Ltd.], polyethylene glycol polytetramethylene glycol mono (meth) acrylate [Product name: Plenmer NKH-5050, PET-800 series; Nippon Yushi Co., Ltd.] ], 2-hydroxyethyl acrylate and ε-force prolac [Product name: Praxel FA1DT, FA2D, FA3, FA4DT, FA5, FA 10L; manufactured by Daicel Chemical Industries, Ltd.], adduct of 2-hydroxyethyl methacrylate and ε-force prolactone [ Product name: Plaxel FM1, FM1D, FM2D, FM3, FM3X, FM4, FM4X, FM4DX, FM5, FM5L, FM6X; manufactured by Daicel Chemical Industries, Ltd.], and one of these. Or the saturated acid anhydride (b) in which two or more kinds can be used is

ぱ),

R ⁴ z ^co \ 0

At 0 no

It is a compound shown by these.

R ⁴ in the formula is an alkylene group having 1 to 25 carbon atoms, a phenylene group, a cyclohexylene group and a formula,

The alkylene group is the same as the alkylene group of the compound (a).

Specific examples of such a saturated acid anhydride (b) include, for example, carboxylic anhydride, dodecenyl succinic anhydride, fluoric anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, Typical examples thereof include methyltetrahydrofluoric anhydride, helic anhydride, trimellitic anhydride and the like, and one or a mixture of two or more thereof can be used.

Further, as the triorganosilane compound (c),

Expression,

R ⁵

H— Si-R ⁶

ύ ^η

A hydrosilane-based compound represented by

Expression,

R ⁵

Cl- Si-R ⁶

There is a chlorosilane-based compound represented by

R ⁵ , R ⁶ and R ⁷ in the formula are each independently a hydrocarbon group selected from the group consisting of alkyl groups having 1 to 25 carbon atoms, aryl groups, cycloalkyl groups and aralkyl groups. Here, the alkyl group may be linear or branched. Archi Examples of the methyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group And an alkyl group such as a cetyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group and an eicosyl group. Particularly preferred alkyl groups have 3 to 9 carbon atoms, for example.

Preferred aryl groups include, for example, a phenyl group and a naphthyl group. Preferred examples of the cycloalkyl group include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group.

Examples of such a triorganosilyl compound (c) include trimethylhydrosilane, triethylhydrosilane, tri-n-propylhydrosilane, tri-i-propylhydrosilane, tri-n-butylhydrosilane, tri-i-butylhydrosilane, Dimethylhexylhydrosilane, triphenylhydrosilane, dibutylhexylhydrosilane, dibutylphenylhydrosilane, t-butyl-di-i-butylhydrosilane, t-butyl-di-i-propylhydrosilane, dimethyloctylhydrosilane, di-t-butylphenylhydrosilane, diphenyl Hydrosilane compounds such as tert-butylhydrosilane, secildi-i-butylhydrosilane, and secildi-i-propylhydrosilane; trimethylchlorosilane, trie Tylchlorosilane, tri-n-propylchlorosilane, tri-i-propylchlorosilane, tri-n-butylchlorosilane, tri-i-butylchlorosilane, tri-t-butylchlorosilane, dibutylhexylchlorosilane, dimethyl n-propylchlorosilane, di-t-butylmethylchlorosilane, dimethylbutylchlorosilane, dimethyloctylchlorosila

Orchid, i-propyloctylchlorosilane,

Orchid, triphenylchlorosilane, t-butyl-

t-butyl di-i-propyl chlorosilane, dibutyl phenyl chlorosilane, di-t-butyl phenyl chlorosilane, t-butyl di-i-propyl chlorosilane, diphenyl methyl chlorosilane, sexilji i-butyl chlorosilane, sexil i-propyl Chlorosilane compounds such as chlorosilane are typical It is mentioned.

Examples of other pinyl monomers (B) copolymerizable with the silyl monomers (A) include various polymerizable unsaturated monomers conventionally used in acryl resins and vinyl resins. Available without restrictions. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, η-butyl (meth) acrylate, i-butyl (meth) acrylate Evening) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, α-cloethyl (meth) acrylate, cyclohexyl (Meth) acrylate-based single substances such as xyl (meth) acrylate, phenyl (meth) acrylate, methoxyshethyl (meth) acrylate, ethoxyshethyl (meth) acrylate, methoxypropyl (meth) acrylate, and ethoxypropyl (meth) acrylate body Styrene monomers such as styrene, methylstyrene, chlorostyrene, and methoxystyrene; carboxyls such as (meth) acrylic acid, crotonic acid, itaconic acid, itaconic acid half ester, maleic acid, and maleic acid half ester Group-containing monomers: diester monomers such as getyl maleate and dibutyl fumarate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl acrylate 1-methyl-1-hydroxyethyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth) Acrylate, 4-hydroxyphenyl (meth) acrylate, 4 (2-Hydroxyethylene) phenyl (methyl) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol polytetramethylene glycol mono (meth) acrylate, polyethylene glycol Hydroxyl-containing monomers such as polytetramethylene glycol (meth) acrylate and 2-hydroxyethyl (meth) acrylate oligomer; (meth) acrylamide ゃ, Ν-methylol acrylamide, Ν-methoxymethyl acrylamide, Amide group-containing monomers such as rainamide; amino acids such as 2-aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 2-butylaminoethyl (meth) acrylate Epoxy group-containing monomers such as dalicidyl (meth) acrylate; vinyl acetate, vinyl chloride, vinyl propionate, vinyl butyrate, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl Vinyl monomers such as isobutyl ether, vinylpyrrolidone, and pinylpyridine; tri-n-butylsilyl (meth) acrylate, tri-i-butylsilyl (meth) acrylate, t-butyldimethylsilyl (meth) acrylate, and sekisyldimethyl Cyril

Representatives of silyl group-containing monomers other than the silyl monomer (A), such as (meth) acrylate and tree i-propylsilyl (meth) acrylate, and further, ethylene, bushogen, (meth) acrylonitrile, etc. It is mentioned as a thing. These monomers can be used alone or in combination of two or more. In the present invention, the polymer serving as the binder is a silyl monomer (A) alone or a vinyl monomer (B) in an organic solvent in the presence of a polymerization initiator. A typical example is an organic solvent-soluble resin produced by a polymerization reaction at 80 to 150 ° C. for 3 to 15 hours according to a conventional method.

The viscosity after the polymerization is suitably about 200 Voids or less, preferably 100 Voids or less at 2 Ot, from the viewpoint of the workability of coating. Therefore, when the viscosity during polymerization is high, or when the viscosity after polymerization is high, the viscosity may be adjusted by changing the resin solid content with an organic solvent.

The solid content of the resin is, for example, 10 to 95% by mass, and preferably 30 to 80% by mass.

Examples of the polymerization initiator include benzoyl peroxide, peroxides such as t-butylperoxybenzoate, di-t-butyl peroxide, azobisisobutyronitrile, azopismethylbutyronitrile, and triphenylmethyl azo. An azo compound such as benzene can be used.

As a solvent for dissolving the organic solvent-soluble resin serving as the binder, Various organic solvents conventionally used for paints can be used without particular limitation as long as they dissolve such resins.

Specifically, for example, hydrocarbon solvents such as toluene, xylene, hexane and heptane; ketone solvents such as methyl ethyl ketone and acetone; ester solvents such as ethyl acetate, propyl acetate and butyl acetate Typical examples include alcohol solvents such as isopropyl alcohol, ether solvents such as ethylene glycol monoethyl ether, ethyl ether, and dioxane. These solvents may be used alone or in combination of two or more. Can be used.

Further, in the present invention, the resin comprising a polymer as a binder may be of a non-aqueous disposable type. The non-aqueous disposable resin is a non-aqueous dispersant comprising a core component substantially dispersed in a hydrocarbon solvent and substantially insoluble in the solvent, and a skin component (dispersion stabilizer) dissolved or swelled in the solvent. A disposable resin having at least one of a core component and a skin component containing a silyl monomer (A) represented by the formula (1) as a constituent component.

Examples of the hydrocarbon-based solvent include aliphatic, alicyclic, and aromatic. In the present invention, the aliphatic hydrocarbon-based solvent and / or an alicyclic hydrocarbon-based solvent, or a mixture thereof. It is desirable to use the main component amount.

Examples of these aliphatic and alicyclic hydrocarbon solvents include n-hexane, i-hexane, n-heptane, n-octane, i_octane, n-decane, n-decane, cyclohexane And methylcyclohexane, cycloheptane and the like. Commercially available products include, for example, Mineral Spirit EC, VM & P Naphtha, Shersol 72 [all manufactured by Shell Chemical Co., Ltd.]; Naphtha 3, Naphtha 5, Naphtha 6, Solvent 7 [external Chemical Company] IP Solvent 106, IP Solvent 1620, IP Solvent 28 35 (Idemitsu Petrochemical Co., Ltd.): Gazol AN-45, Gazol 304 0 [above, manufactured by Mobile Oil Co., Ltd.] and the like.

Examples of the aromatic solvent include, for example, benzene, toluene, xylene, decalin, and the like. Commercially available products include, for example, sol. Besso 100, Solbesso 150, [the above, manufactured by Exxon Chemical Co., Ltd.]; Susol, manufactured by Maruzen Petrochemical Co., Ltd., and the like.

These hydrocarbon solvents can be used alone or in combination of two or more.

The non-aqueous dispersion type resin is produced, for example, by dissolving in a hydrocarbon solvent in the presence of a skin component (dispersion stabilizer) composed of a polymer that dissolves or swells in the hydrocarbon solvent, The polymer to be formed after polymerization (that is, the particulate core component) is suitably subjected to dispersion polymerization of an insoluble polymerizable unsaturated monomer in a conventional manner. The monomer forming the polymer serving as the skin component is not particularly limited as long as it is soluble in the hydrocarbon solvent used and the polymer formed after polymerization can be dissolved or swelled. Vinyl monomer (B) can be used, but a vinyl monomer containing (meth) acrylate monomer in an amount of 5 to 100% by mass, preferably 30 to 95% by mass. A mixture of system monomers is suitable.

As the monomer forming the polymer serving as the core component, the above-mentioned various vinyl monomers may be used as long as they are soluble in the hydrocarbon solvent used and the polymer formed after polymerization becomes insoluble. The body (B) is available.

What is important in the present invention is that at least one of a polymer serving as a skin component and a polymer serving as a core component constituting the non-aqueous dispersion resin includes the above-mentioned silyl monomer (A) as an essential component. Used in combination with the vinyl monomer (B) to contain silyl groups in the resin.

The mass ratio between the core component and the skin component (core component Z skin component) is not particularly limited, but is usually 90 Z 10 to 110, preferably 80 Z 20 to 2 5 Z 75 is appropriate.

Non-aqueous disposable resins have relatively low paint viscosity compared to organic solvent-soluble resins, because fine particles, which are insoluble core components, exist in the organic solvent as part of the resin. Therefore, the amount of organic solvent can be reduced, and high solid differentiation can be achieved. Also, by changing the amount of the silyl monomer (A) contained in the core component and the skin component, it becomes possible to adjust the force B water decomposition rate. That is, for example, a silyl monomer (A) When the amount is increased, the hydrolysis rate is increased.

In the description of the organic solvent-soluble type resin and the non-aqueous dispersion type resin having the silyl monomer (A) represented by the formula (1) used in the present invention, both of the silyl type Although the monomer (A) is used as a starting material, the compound (a) having a hydroxyl group, which is an intermediate of the silyl monomer (A), and a saturated acid anhydride (b) are used. A polymer is synthesized from the lipoxyl group-containing monomer that is the reaction product or the monomer and another vinyl monomer (B), and then the above-mentioned triorganosilane compound (c) is reacted. It is also possible to provide a silyl group in the polymer.

The resin as the binder used in the present invention is typically synthesized by the method described above, but the amount of the silyl-based monomer (A) used is limited to the total amount when the organic solvent-soluble resin is used. In the polymer, 5 to 100% by mass, preferably 10 to 95% by mass is appropriate, and in the case of a non-aqueous dispergion type resin, 5 to 80% by mass, preferably 1 to 90% by mass. 0 to 60% by weight is suitable.

If the amount of the silyl monomer (A) is less than the above range, the long-term antifouling property tends to decrease. On the other hand, when the amount of the silyl monomer (A) is larger than the above range, in the case of a non-aqueous dispersion type resin, it tends to be difficult to produce the resin.

The weight-average molecular weight of the resin as the binder is from 1,000 to 300,000, preferably from 3,000 to: L, 000.

As the antifouling agent used in the present invention, various antifouling agents conventionally used for antifouling paints can be used without particular limitation. Specific examples include cuprous oxide, basic copper carbonate, copper thiocyanate, copper naphthenate, copper hydroxide, cuprous rhodan, copper pyrithione, manganese ethylenebisdithiocarbamate, zinc oxide, zinc pyrithione. Metal-containing antifouling agents, such as zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate; 2-methylthio-141-tert-butylamino-6-cyclopropylamino s-triazine II, 2, 4, 5, 6- Tetraclo mouth isophthalonitrile, N, N-dimethylchlorophenylurea, 4,5-dichloro-2-N-octyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide N, N-dimethyl-N'-phenyl (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, N- (3,4-dichlorophenyl) -N, N-dimethylurea, 2,4, Organic antifouling agents such as 6-trichloromouth phenylmaleimide, dimethyldithi-rich nickel rubamate, dithiocyano compounds, 3-substituted amino-1,3-thiazoline-2-thidione compounds, and N-trihalomethylthiophthalimide compounds. It is mentioned as a typical thing.

As the additives used in the present invention, the above-mentioned various additives conventionally used in antifouling paints can be used as they are.

In the present invention, in particular, a dehydrating agent is desirably blended in order to prevent hydrolysis from proceeding due to the influence of moisture during storage of the antifouling paint.

Examples of the dehydrating agent include synthetic zeolite, sepiolite, anhydrous gypsum, orthopropionate, orthoformate, orthoacetate, trialkyl orthophosphate, alkoxysilane compound, tetraalkyl silicate compound, tetraaryl silicate Compounds, isocyanate compounds, and the like can be used, and the amount of the compound is suitably 0.1 to 20% by mass in the coating material.

The mixing ratio of each component constituting the antifouling coating composition of the present invention is usually such that the resin as the binder is 10 to 50% by mass, preferably 15 to 40% by mass, and the antifouling agent is 0. It is suitably from 50 to 50% by mass, preferably from 10 to 45% by mass, and from 15 to 60% by mass, preferably from 20 to 40% by mass of the solvent.

Pigments, plasticizers, fibrous materials, modified resins, rosin and its derivatives or metal salts thereof, and various additives are not essential constituents, but each is usually 20% by mass. It is appropriate to mix up to.

The antifouling coating composition of the present invention is prepared by mixing or dispersing the above components in a lump or divided manner by using a conventional coating apparatus such as a pole mill or a disperser. The antifouling paint composition of the present invention thus prepared is used as it is or after adjusting the viscosity with a diluting solvent, and then subjected to airless spray painting, air spray painting, roller painting, brush painting, etc. Is applied to painted ships and marine structures. The antifouling paint composition of the present invention has a dry film thickness of about 30 m to 300 m in one application, preferably , 50 to 200 m, and one to three layers of the coating film are preferably formed to a total dry film thickness of about 90 to 500 m.

Examples of the above-mentioned waterproof paint include a combination of an epoxy resin having an epoxy equivalent of about 160 to 600 and a curing agent thereof (for example, an amino resin, a carboxylic acid resin, an acid anhydride resin), and a polyol. Combination of resin and polyisocyanate-based curing agent, or vinyl ester resin, unsaturated polyester resin, etc. as binder, and if necessary, thermoplastic resin (eg, chlorinated rubber, acrylic resin, vinyl chloride resin, etc.) Paints and tars containing a curing accelerator, an anti-pigment, a color pigment, an extender, a solvent, a trialkoxysilane compound, a plasticizer, an additive (eg, a sagging inhibitor, an anti-settling agent, etc.) Epoxy resin paints and the like can be used as typical ones.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. During implementation, “parts” and “%” are shown on a mass basis.

[Preparation of organic solvent soluble resin solution (A) to (I)]

A reaction vessel equipped with a stirrer, a thermometer, a condenser, etc., was charged with 33.5 parts of xylene. While maintaining the temperature at 100, the polymerization initiator [2, 2'-a A dropping monomer mixture containing zobis (2-methylbutyronitrile)] was added dropwise with stirring over 3 hours. Then, at the same temperature, 0.25 part of the above-mentioned polymerization initiator was charged in three portions, reacted for 2 hours, and further reacted for 1 hour. Then, 17.5 parts of xylene was added to prepare resin solutions (A) to (I).

Organic solvent soluble resin solution

Note 1) ₃ Note 2) (CH (CH ₃ > ₂ ) ₃ Note 3)

(CH ₃ ) ₂ ] ₂ [CH (CH ₃ ) ₂ ]

Note 4)

CHs

(CH (CH ₃ ) ₂ ) 3

Note 5)

CH ₂ = CH-C-0- (CH ₂ ) ₂ -0-C- (CH ₂ ) ₂ -C- 0-Si 〖(CH ₂ ) ₃ CH ₃ ] ₃

O I J 0 «o

[Examples 1 to 11 and Comparative Example:! ~ Five〕

A composition comprising the organic solvent-soluble resin solution shown in Table 1 and an antifouling agent, an additive, a pigment, and a solvent was kneaded and dispersed in the composition shown in Table 2 below, and Examples 1 to 7 and Comparative Examples 1 to 3 antifouling paints were produced. Each of these antifouling paints was applied to a steel sheet coated with an epoxy resin-based two-component antifouling paint by air spraying so as to have a dry film thickness of 300 / zm, and dried. Each of the obtained test plates was subjected to each of the tests of abrasiveness, antifouling properties, adhesion, and crack resistance. In addition, storage stability tests of the antifouling paints were performed, and the results are shown in the lower part of Table 2, respectively.

Each test was conducted based on the following method.

Abrasiveness test>

After a rotor test (25 ° (:, 15 knots)), the film thickness was measured with a micrometer, and the difference from the film thickness (unit: m) before the test was calculated. Stain resistance test>

At Toba Bay, Mie Prefecture, the test plate was submerged in the sea and the appearance of the coating film was observed. Evaluation criteria

5: No deposit is observed on the test plate.

4: Adhesion of thin slime is observed on the test plate.

3: Thick slime adheres to the test plate.

2: Slight adhesion of large flora and fauna is observed.

1: Large attachment of large animals and plants is observed.

Rotor test A crosscut was put on the coating film surface after 12 months, a cellophane tape was stuck on the surface, and the cellophane tape was peeled off at once, and the appearance of the coating film was observed.

Evaluation criteria

A: No change was observed on the cut ground.

〇: A slight change was observed in the cut ground.

C: Slight peeling was observed on the cut ground.

X: Peeled from the cut surface or peeled off at the end of the test.

Crack resistance test>

Rotor test The coating surface after 12 months was observed with a loupe (magnification: 10 times). Evaluation criteria

A: No crack was observed on the coating film surface.

〇: Slightly small cracks were observed on the coating film surface.

Δ: Slightly large cracks were observed on the coating film surface.

X: The entire coating surface is cracked or peeled.

Paint storage stability test>

After placing each paint in two test tubes (diameter 18 mm) up to a height of 10 cm and sealing, one test tube is at 50 ° C and the other test tube is 20 ° C. For 14 days. Thereafter, both test tubes were simultaneously inverted, and the viscosity comparison was performed by the time required for the bubbles to reach the upper portion. Evaluation criteria

〇: The time is almost the same and the viscosity is the same.

Δ: The paint left at 50 ° C takes some time and thickens. X: Gelled and could not be used as a paint.

Table 2 Organic solvent-soluble antifouling paint

Note 6) rpOLY ACE SlOOOj (manufactured by Nitto Kasei); solid content 49.8%, Sn content in resin 10.5%

Note 7) "MOLECULAR S I EVE TYPE 4A"

(Made by UNION CARB IDE Co)

Note 8) "BENTONE" (made by RHEOX)

[Preparation of Non-aqueous Dispersion Type Resin Ingredient (Dispersion Stabilizer) Solution (K-11)] In a four-necked flask equipped with a stirrer, thermometer and reflux tube, add 50.0 parts of mineral spirits. Charge and maintain the temperature at 100 ° C. There, 15.1 parts of n-butyl methyl acrylate, 12.1 parts of i-butyl methyl acrylate, 722.6 parts of the silyl monomer (A)-172.6 parts and polymerization start A mixture of 0.5 part of 2,2′-azobis (2-methylbutyronitrile) was added dropwise with stirring over 3 hours. Next, a mixture of 19.0 parts of mineral spirit and 0.3 part of the polymerization initiator was added dropwise with stirring over 2 hours. Thereafter, the mixture was reacted at the same temperature for 90 minutes. After cooling, 31 parts of mineral spirits were added to prepare a skin component liquid (K-11) having a solid content of 51%.

[Preparation of non-aqueous dispersion type resin skin component liquids (K-12), (K-3) and (K-4)]

From the components shown in Table 3, a skin component solution (K-12), a skin component solution (K-13), and a skin component solution (K-14) were prepared in the same manner as the skin component solution (K-11).

Table 3 Skin component liquid of non-aqueous disposable resin

[Preparation of non-aqueous dispersion resin solution (NAD-l)]

In a four-necked flask equipped with a stirrer, thermometer and reflux tube, put the skin component liquid (K-1) 133.4 咅 [5, keep the temperature at 105 ° C, and then add 19.5 parts of methyl methyl acrylate, 13.8 parts of ethyl acrylate, a polymerization initiator “Nipar BMT-K40” (manufactured by NOF Corporation) 0.83 parts and a mixture of 1 part of mineral spirit were added dropwise with stirring over 3 hours. . Next, a mixture of 4 parts of mineral spirit and 0.42 part of the polymerization initiator was added dropwise with stirring over 2 hours. Thereafter, the mixture was reacted at the same temperature for 90 minutes. After cooling, 28 parts of mineral spirits were added. ) Was prepared.

[Non-aqueous dispersion resin liquid (NAD-2), (NAD-3), (NAD-4 Preparation of), (NAD-5), (NAD-6)

In the same manner as the non-aqueous dispersion resin solution (NAD-1), based on the formulation shown in Table 4, the non-aqueous dispersion resin solutions (NAD-2), (NAD-3), (NAD-4 ), (NAD-5) and (NAD-6) were prepared. Table 4 Non-aqueous dispersion type resin liquid (skin component Z core component)

A composition comprising the non-aqueous disposable resin liquid shown in Table 4, an antifouling agent, an additive, a pigment, and a solvent, was kneaded and dispersed in the composition shown in Table 5 below. Examples 8 to 11 and Comparative Examples 4 to 5 antifouling paints were produced.

Each of these paints was tested in the same manner as in Example 1. The results are shown in the lower part of Table 5.

Table 5 Non-aqueous dispersion type antifouling paints Examples Comparative examples ίΗ ^ ,, /? ^ · &&, Ι 口

Prevention? Fortress

8 9 1 0 1 1 4 5 Non-aqueous dispersion type resin liquid NAD-1 4 0

Non-aqueous dispersion type resin liquid NAD-2 40

Non-aqueous dispersion type resin liquid NAD-3 4 0

Non-aqueous dispersion type resin liquid NAD-4440

Non-aqueous dispersion type resin liquid NAD-540 Non-aqueous dispersion type resin liquid NAD 6400 Copper oxide 400 4 0 4 0 4 0 4 0 4 0 Copper pyrithion 2 2 2 2 2 2 Dewatering agent ^{S 7)} 3 3 3 3 3 3 Fluctuation agent ^{S 8)} 1 1 1 1 1 1 Valve handle 7 7 7 7 7 7 Evening 3 3 3 3 3 3 Mineral spirit 6 6 6 6 6 6

3 months 2 1 1 7 1 8 1 6 1 7 3

6 months 4 0 3 5 3 9 3 5 3 5 5 Abrasiveness

9 months 5 8 5 3 5 3 4 9 5 3 6

1 2 months 7 3 6 2 6 8 5 9 5 6 8

3 months 5 5 5 5 5 3 Antifouling 3 months 5 5 5 5 4 2

1 2 months 5 5 5 5 4 1 Adhesion ◎ ◎ ◎ ◎ △ △ Crack resistance ◎ ◎ ◎ ◎ Δ 塗料 Paint storage stability 〇〇〇〇 Δ 〇 As shown in Table 2, Examples 1 to 7, which are organic solvent-soluble antifouling paint compositions of the present invention, have performance equivalent to or higher than Comparative Example 3 containing tin which is problematic in terms of safety and health. I was On the other hand, in Comparative Example 1 in which a resin containing no silyl monomer was blended, there was almost no antifouling property, and a conventional silylated monomer other than the silyl monomer (A) used in the present invention was used. In Comparative Example 2 using, the antifouling property, adhesion, crack resistance, and storage stability were slightly inferior.

Further, as shown in Table 5, Examples 8 to 11, which are the non-aqueous dispersion type antifouling paint compositions of the present invention, had excellent coating film performance. On the other hand, in Comparative Example 4 using a silylated monomer other than the silyl monomer (A) used in the present invention, antifouling properties, adhesion properties, crack resistance, and paint storage stability were slightly inferior. . In Comparative Example 5 in which no silyl monomer was used, there was almost no antifouling property. Industrial applicability

According to the present invention, an antifouling paint having excellent polishing properties, long-term antifouling properties, adhesion, crack resistance, and storage stability can be obtained.

Claims

The scope of the claims

1. Equations (1) and 6

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are each independently an alkylene group having 1 to 25 carbon atoms, a phenylene group, a cyclohexylene group,

(In the formula, R ⁸ is an alkylene group having 1 to 25 carbon atoms, a phenylene group or a cyclohexylene group.) R ⁵ is a hydrocarbon group selected from the group consisting of R ⁶ and R ⁷ are each independently a hydrocarbon group selected from the group consisting of an alkyl group having 1 to 25 carbon atoms, an aryl group, a cycloalkyl group and an aralkyl group, and m, n, and y are 0 to 20. X is an integer from 1 to 15, and

(m + n + y) ≥. ]

An antifouling paint composition comprising, as a binder, a polymer containing the silyl-based monomer (A) represented by the formula (1) as a constituent.

(2) The polymer contains, as constituent components, 5 to 100% by mass of the silyl-based monomer (A) and 95 to 0% by mass of another copolymerizable vinyl-based monomer (B), and The antifouling paint composition according to claim 1, wherein the resin has a weight average molecular weight of 1,000 to 300,000.

3. The antifouling coating composition according to claim 1, wherein the polymer is an organic solvent-soluble resin or a non-aqueous disposable resin.

4. The antifouling agent according to claim 1, 2 or 3, wherein the binder resin contains 10 to 50% by mass, the antifouling agent contains 0 to 50% by mass, and the solvent contains 15 to 60% by mass. Soil paint composition.

5. The antifouling paint composition according to any one of claims 1 to 5, comprising an antifouling agent and a dehydrating agent.