JP2003277680A - Aqueous pollution-preventing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aqueous pollution-preventing resin composition remarkably reducing the amount of an organic solvent or not using the organic solvent, excellent in storage stability and forming a pollution-preventing coating film enabling control of elution speed of the coating film and capable of exhibiting pollution-preventing property over a long period. <P>SOLUTION: This aqueous pollution-preventing resin composition comprises an aqueous resin emulsion as a binder having pollution-preventing property obtained by dispersing (A) a resin having 1,000-50,000 number-average molecular weight and obtained by copolymerizing (a) a triorganosilyl group-containing unsaturated monomer with (b) the other polymerizable unsaturated monomer copolymerizable with the monomer (a) in an organic solvent containing ≥5 wt.% alcoholic solvent into water by using (c) an emulsifying agent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous antifouling resin composition for preventing adhesion of aquatic organisms to ships, underwater structures, fishing gear, fishnets and the like.

[0002]

2. Description of the Related Art Conventionally, resins having tin carboxylate have been widely used as binders for antifouling paints, but in recent years, due to toxicity problems, conversion to other resin systems has been strongly demanded, and copper and Various resins having zinc carboxylate or triorganosilyl have been studied. As the resin having a carboxylate of copper or zinc, for example, JP-A-62-5746 is known.
No. 4, JP-A-8-209005 and the like, and resins containing triorganosilyl include, for example, JP-A-9-048946 and JP-A-9-0.
48947, JP-A-9-048948, JP-A-9-
It is proposed in Japanese Patent Publication No. 048949.

Of these, resins having triorganosilyl are excellent in abrasion resistance and antifouling performance as binders for antifouling paints, but are organic solvent diluted types,
In recent years, a water-based material has been desired from the viewpoint of environmental protection and improvement of working environment.

The object of the present invention is to significantly reduce or eliminate the amount of organic solvent, have excellent storage stability, control the elution rate of the coating film, and exhibit antifouling properties for a long period of time. It is intended to provide an aqueous antifouling resin composition capable of forming a coating film.

[0005]

The present invention includes: 5% by weight or more of an alcohol solvent of (a) a triorganosilyl group-containing unsaturated monomer and (b) another polymerizable unsaturated monomer copolymerizable with the monomer (a) The resin (A) having a number average molecular weight of 1,000 to 50,000 obtained by copolymerization in an organic solvent containing it is dispersed in water using an emulsifier (c) to give an antifouling property to an aqueous resin emulsion. 1. A water-based antifouling resin composition which is contained as a binder having 1. 2. The water-based antifouling resin composition according to 1, wherein the triorganosilyl group of the monomer (a) has at least one of three hydrocarbon groups bonded to a silicon atom having 3 or more carbon atoms. Monomer (a) is triisopropylsilyl (meth)
3. The water-based antifouling resin composition according to 1 or 2, which is an acrylate. The resin (A) contains 10 to 95% by weight of the monomer (a),
And an aqueous antifouling resin composition according to claim 1, which is obtained by copolymerizing the monomer (b) at a ratio of 5 to 90% by weight, and an aqueous antifouling resin composition according to any one of 5.1 to 4. And an aqueous antifouling coating composition containing the antifouling agent (B).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The water-based antifouling resin composition of the present invention comprises
Resin obtained by copolymerizing a triorganosilyl group-containing unsaturated monomer (a) and another polymerizable unsaturated monomer (b) copolymerizable with the monomer (a) (A ) Is dispersed in water using an emulsifier (c) to contain an aqueous resin emulsion.

The above-mentioned unsaturated monomer (a) containing a triorganosilyl group is usually represented by the following formula (1)

[0008]

[Chemical 1]

(Wherein R ¹ is a hydrogen atom or a methyl group, R ¹ is
² , R ³ and R ⁴ each represent a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group and a phenyl group). In the above formula, the number of carbon atoms in R ² , R ³ and R ⁴ is 1 to
The alkyl group of 18 may be linear or branched,
Specific examples include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group,
A decyl group, a dodecyl group, a myristyl group, a stearyl group and the like can be mentioned, and specific examples of the cycloalkyl group of R ² , R ³ and R ⁴ include a cyclopentyl group, a cyclohexyl group and the like. It is preferable that at least one of R ² , R ³ and R ⁴ has 3 or more carbon atoms from the viewpoint of imparting appropriate hydrolyzability and controlling the self-polishing property of the obtained coating film.

Specific examples of the monomer (a) include dimethylbutylsilyl (meth) acrylate, dimethylhexylsilyl (meth) acrylate, dimethyloctylsilyl (meth) acrylate, dimethyldecylsilyl (meth) acrylate and dimethyl. Dodecylsilyl (meth) acrylate, dimethylcyclohexylsilyl (meth) acrylate, dimethylphenylsilyl (meth) acrylate, dimethyldibutylsilyl (meth) acrylate, ethyldibutylsilyl (meth) acrylate, dibutylhexylsilyl (meth) acrylate, dibutylphenylsilyl (Meth) acrylate, tributylsilyl (meth) acrylate, triphenylsilyl (meth)
Examples thereof include acrylates, and these can be used alone or in combination of two or more.

In the present specification, "(meth) acrylate" and "(meth) acrylic" represent "acrylate or methacrylate" and "acrylic or methacrylic", respectively.

Of these, R ² and R such as dimethylhexylsilyl (meth) acrylate and dimethyldecylsilyl (meth) acrylate are taken from the viewpoints of proper hydrolysis rate, easy synthesis, and film-forming property. Those in which two of ³ and R ⁴ are methyl groups and the other one is a long-chain alkyl group having 6 or more carbon atoms are excellent, and particularly, they have a controlled hydrolysis rate in water and obtain an appropriate sustained solubility. From the viewpoint, triisopropylsilyl (meth) acrylate is preferable.

The above-mentioned monomer (b) includes the monomer (a)
There is no particular limitation as long as it can be copolymerized with
Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
C1-24 alkyl or cycloalkyl ester of (meth) acrylic acid such as octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, (meth) Hydroxypropyl acrylate, (meth)
(Meth) acrylic acid C such as hydroxybutyl acrylate
2-6 hydroxyalkyl ester Polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and other hydroxyl group-containing monomers; methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate; glycidyl (meth) acrylate, allyl glycidyl ether, etc. Glycidyl-containing monomers of (meth) acrylic acid, itaconic acid, crotonic acid and other carboxyl-containing monomers; styrene, α-methylstyrene, vinyltoluene and other vinyl aromatic compounds: (meth) acrylonitrile, dimethylaminoethyl acrylate, acrylic amod, Allyl (meth) acrylate, (meth) acrolein, butadiene, isoprene, vinyl acetate, vinyl chloride, vinyl ether compound, vinyl Such as pyrrolidone and the like, which respectively can be used alone or may be used in combination of two or more.

The use ratio of the above-mentioned monomers (a) and (b) is usually 10 to 95% by weight of the monomer (a), preferably 20 to 70% by weight, and 5 of the monomer (b). ~ 90% by weight,
A range of 30 to 80% by weight is preferable. If the monomer (a) is less than 10% by weight (the monomer (b) is more than 90% by weight), the antifouling property is poor, and the monomer (a) is 95% by weight.
When it is more than 5% (monomer (b) is less than 5% by weight), it is difficult to disperse the resulting resin (A) in water and the physical properties of the coating film are deteriorated.

The resin (A) is a radical known per se in an organic solvent containing the above monomers (a) and (b) in an alcoholic solvent in an amount of 5% by weight or more, preferably 15 to 45% by weight. It can be obtained by copolymerization according to a polymerization method. If the amount of the alcohol solvent is less than 5% by weight, it may be difficult to form an emulsion when dispersed in water, which is not preferable.

Examples of alcohol solvents that can be used in the copolymerization include isopropyl alcohol, butanol, pentanol, 2-methyl-1-butanol, hexanol, cyclohexanol, and glycerin. Other organic solvents that can be used in combination with the alcohol solvent include, for example, ester solvents such as ethyl acetate and butyl acetate; aromatic hydrocarbon solvents such as benzene, toluene and xylene; mineral spirits and aromatic petroleum naphtha. Petroleum-based solvent; ketone-based solvent such as methyl ethyl ketone and methyl isobutyl ketone; ether-based solvent such as diethylene glycol monobutyl ether and cellosolve; aprotic polar solvent such as dimethylformamide and dimethyl sulfoxide; or two or more of these solvents A mixture may be mentioned.

Of these, the solvent composition at the time of copolymerization is preferably an alcohol solvent, a hydrocarbon solvent or an ester, taking into consideration the stability (particle size / storage property) of the emulsion when dispersed in water. It is preferable to carry out the polymerization in combination with a system solvent. In addition, a resin solution prepared by polymerizing under a single solvent (eg, xylene only), then distilling the solvent off under reduced pressure and re-dissolving in a mixed solvent of alcohol solvent / hydrocarbon solvent / ester solvent. May be used.

The amount of the organic solvent used during the copolymerization is preferably 20 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total amount of the monomers. If the amount of the organic solvent is less than 20 parts by weight, it becomes difficult to control the reaction, and if it exceeds 200 parts by weight, the stability of the emulsion during water dispersion becomes poor, and an emulsion having a small particle size cannot be obtained, or during water dispersion. In some cases, problems such as the resin not causing phase transition in the water system may occur.

Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, t-butyl perbenzoate, methyl ethyl ketone peroxide, lauroyl peroxide, cumene hydroperoxide, and azobisisobutyronitrile. Examples thereof include polymerization initiators usually used for radical polymerization, such as azo compounds. The amount of the polymerization initiator is generally 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the monomers. The polymerization conditions are not particularly limited, but it is preferable to carry out in a nitrogen stream, and generally 60 to 120 ° C. when the polymerization initiator is an organic peroxide, and 4 in the case of an azo compound.
It is performed at a temperature of 5 to 100 ° C.

The resin (A) produced as described above has a number average molecular weight of 1,000 to 50,000, preferably 5,0.
It is in the range of 00 to 50,000.

The resin composition of the present invention contains, as an active ingredient, an aqueous resin emulsion obtained by dispersing the resin (A) obtained as described above in water using an emulsifier (c). As the emulsifier (c), known anionic, nonionic,
Nonionic / anionic surfactants may be mentioned. Examples of the anionic surfactant include sodium alkylbenzene sulfonate, sodium lauryl sulfate, sodium dioctyl sulfosuccinate and the like. Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene-polyoxypropylene block copolymer. Examples of nonionic / anionic surfactants include polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene polycyclic phenyl ether sulfate ester salt, polyoxyethylene allyl ether sulfate ester sodium salt, and polyoxyethylene phenyl ether sulfate ester salt. Can be mentioned. These dispersion stabilizers may be used alone or in combination of two or more kinds. Of these, nonionic / anionic surfactants are preferable from the viewpoint of the stability of the resulting emulsion, and particularly, the HLB value is in the range of 5 to 20, and the HLB value is in the range of 10 to 18. Those are preferable. The emulsifier (c) is preferably added in an amount of 2 to 20 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the resin (A) solid content. If the amount added is less than 2 parts by weight, a uniform and stable emulsion cannot be obtained. On the other hand, if the amount added exceeds 20 parts by weight, the resulting coating film tends to swell and the water resistance remarkably decreases, which is not preferable.

The emulsion of the resin (A) is usually produced by mixing the resin (A) and the emulsifier (c), gradually increasing the stirring speed, and adding water under the stirring to disperse the water.
Stirring is carried out by a method using a high-speed stirrer such as a disper-type stirrer, and further, the water dispersion obtained by the high-speed stirrer is atomized for the purpose of further improving the water dispersibility and making the particle diameter smaller. Examples thereof include a method of dispersing in water using an ultrahigh pressure homogenizer (for example, "Ultemizer System", manufactured by Sugino Machine Ltd.).

The resin emulsion thus obtained is a stable emulsion having a particle size of 400 nm or less.
When emulsifying the resin (A), the resin (A) may be mixed with other resin, an antifouling agent or the like, if necessary, and then water-dispersed in the same manner as above to produce a resin emulsion. . As such other resin, for example, rosin or the like can be used from the viewpoint of abrasion resistance control, and 50 parts by weight or less, preferably 1 to 20 parts by weight, based on 100 parts by weight of the resin (A) can be added in solid content. . Further, as the antifouling agent, for example, "Sineine 211" (isothiazoline compound manufactured by Rohm & Haas Co., Ltd.), which is soluble in a solvent, can be used from the viewpoint of imparting antifouling property, and 100 parts by weight of the resin (A) is a solid content. 20 parts by weight or less, preferably 1 to 10 parts by weight can be added.

The resin composition of the present invention contains an emulsion of the above resin (A), and if necessary, other resin emulsions may be used in combination. As the other resin emulsion, conventionally known emulsions can be used without particular limitation, and examples thereof include acrylic emulsion, acrylic-styrene emulsion, vinyl acetate emulsion, ethylene-
Examples thereof include low acid value emulsions such as vinyl acetate emulsion and high acid value emulsions containing zinc ammonia complex salt such as floor polish emulsion “AE175” (manufactured by Japan Synthetic Rubber Co., Ltd.). These are solids and resin (A)
50 parts by weight or less, preferably 1 to 100 parts by weight
20 parts by weight can be added. Such addition amount is 50
If it exceeds the amount by weight, the abrasion resistance of the resulting antifouling coating film decreases, which is not desirable.

The antifouling coating composition of the present invention includes those containing the resin composition and the antifouling agent (B). Examples of the antifouling agent (B) include copper antifouling agents such as zincated copper, thiocyanic copper, and copper powder; nitrogen-containing sulfur antifouling agents such as ethylenebis (dithiocarbamic acid) zinc and tetramethylthiuram disulfide. Fouling agents; such as bis (triphenyltin) oxide, bis (tributyltin) oxide, tributyltin acetate, tributyltin chloride, triphenyltin hydroxide, triphenyltin versatate, bis (tributyltin) α, α′-dibromosuccinate Organotin antifouling agent; nitrile compound, benzothiazole compound, triazine compound,
Urea compounds, isothiazoline compounds, maleimide compounds, N-haloalkylthio compounds, tetracycline compounds, zinc pyrithione, copper pyrithione, fungicides such as pyridine compounds such as triphenylboron pyridine salt, zinc oxide and the like, These can be used alone or in combination of two or more. Of these, triphenylboron pyridine salt, zinc pyrithione, copper pyrithione, and cuprous oxide are preferable.

It is appropriate that the amount of the antifouling agent (B) is about 30 to 200 parts by weight based on 100 parts by weight of the resin solid content. In the case of the above-mentioned antifouling agent powder, it is possible to stir-blend it into the resin composition as it is, but it is usually appropriate to blend the antifouling agent as a paste using a dispersant and water. Further, from the viewpoint of stability, the resin composition may be appropriately added to the antifouling agent and water paste to be kneaded.

The antifouling paint composition of the present invention may further contain pigments, plasticizers, solvents, and other additives commonly used in antifouling paints and water-based paints, if necessary. .
The method for forming a coating film using the coating composition of the present invention is not particularly limited, and a conventionally known method can be used. Specifically, underwater structures (for example, ships, port facilities, buoys, pipelines, bridges, seabeds, aquaculture nets,
Primers such as wash primer, zinc epoxy type shop primer, etc. directly on the surface of the base material such as fixed mesh etc .; undercoat primer such as vinyl tar type, oil rust preventive, chlorinated rubber type, epoxy type; chlorinated rubber System, a single-layer coating film formed by applying an intermediate coating material such as an epoxy-based coating, a multilayer coating film formed by coating the primer and primer primer coating, and a primer,
The primer can be applied to the surface of a base material provided with a multilayer coating film formed by sequentially applying an undercoat primer and an intermediate coating material by means of brush coating, spray coating, roller coating, dipping or the like. The coating amount is generally 40 to 50 as a dry film thickness.
A range of 0 μm, preferably 80 to 300 μm is suitable. The coating film can be dried at room temperature, but if necessary, it may be dried by heating at a temperature of about 100 ° C.

[0028]

EXAMPLES The present invention will be described in more detail with reference to examples. "Parts" and "%" are "parts by weight" respectively.
And "% by weight" are shown.

Production of Resin (A) Solution Production Example 1 A reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, and a heating / cooling jacket was charged with 33 parts of xylene, 25 parts of butyl acetate and 25 parts of butanol, and a nitrogen stream was introduced. The mixture was heated and stirred under the temperature condition of 90 ° C. While maintaining the same temperature, a mixture of 50 parts of tributylsilyl methacrylate, 50 parts of methyl methacrylate, and 2 parts of α, α′-azobis-methylbutyronitrile as a polymerization initiator was placed in the reaction vessel through the dropping device for 4 hours. Was dropped. Then, stirring was continued for 4 hours at the same temperature to obtain a colorless transparent resin solution (A-1). The number average molecular weight (Mn) of this resin measured by GPC was 12,000, and the weight average molecular weight (Mw) was 23,000.

Production Examples 2 to 8 In Production Example 1, the amount of solvent and the composition of the monomer mixture are shown in Table 1.
Resin solutions (A-2) to (A-8) were obtained in the same manner as in Production Example 1 except that the above procedure was performed.

Production Example 9 The resin solution (A-8) obtained in Production Example 8 was partially desolvated to give xylene / butyl acetate / butanol = 33/25.
The resin solution (A-9) was diluted with a mixed solvent of / 25.

[0032]

[Table 1]

Preparation Example 1 of Resin Emulsion Preparation Example 1 To 83.3 parts of the resin solution (A-1) obtained above, 6.3 parts of "Eleminol ES-70" (manufactured by Sanyo Kasei Co., Ltd., an emulsifier) was added and strongly mixed. Dilute with water with stirring to a solid content of 35.
8% of resin emulsion (Em-1) was obtained. The particle size immediately after preparation of the emulsion was 194 nm.

Preparation Examples 2 to 12 Each of the resin emulsions (Em-2) to (Em-12) was prepared in the same manner as in Preparation Example 1 except that the composition of the resin solution and the emulsifier was as shown in Table 2. ) Got.

Each of the resin emulsions (Em-1) to (Em-12) obtained as described above was sealed and stored at 40 ° C. for 1 month, and the emulsion particle size and viscosity were measured immediately after emulsification and after 1 month storage. did. The results are also shown in Table 2.

Preparation Example 13 83.3 parts of the resin solution (A-8) was mixed with "ELEMINOL ES".
-70 "(manufactured by Sanyo Kasei Co., Ltd., emulsifier) 6.3 parts were added,
It was diluted with water while stirring vigorously, but could not be emulsified.

[0037]

[Table 2]

Preparation of Antifouling Paint Example 1 25 parts deionized water and a pigment dispersant "BYK-19" in a container.
0 "(manufactured by Big Chemie) 3 parts, zinc pyrithione 1
0 parts, "PK" (manufactured by Hokuko Chemical Co., Ltd., triphenylboron pyridine salt) 30 parts by weight, and 20 parts titanium white were charged and mixed and dispersed by a paint conditioner to prepare a dispersion paste of an antifouling agent. 278 parts by weight of the resin emulsion (Em-1) prepared above was added and mixed with stirring to obtain an antifouling paint.

Examples 2 to 24 and Comparative Examples 1 to 4 Each antifouling coating material was obtained in the same manner as in Example 1 except that the compounding compositions were as shown in Tables 3 to 5.

[Note] in the table is as follows. (Note) "Disparlon A603-20XN": Kusumoto Kasei Co., fatty acid amide wax

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

Coating test 100 × 3 with anti-corrosion coating with vinyl tar paint
Each of the antifouling paints obtained above was coated on a test plate having a size of 00 × 3.2 mm so as to have a dry thick film thickness of 100 μm, and dried at room temperature to obtain each test coated plate.

Each test coated plate was immersed in seawater at a depth of 1 m in Osaka Bay, and the antifouling property after 6 months and 12 months was evaluated by the biological adhesion area ratio (%). Further, each test coated plate was immersed in a raft in the Suruga Bay by half immersion, and after 3 and 6 months, the cracking property of the coating film on the exposed part, the draft part and the submerged part was evaluated (○: no abnormality, Δ: There is a slight crack, ×: There is a crack on the entire surface). The results are shown in Tables 6 and 7.

[0046]

EFFECTS OF THE INVENTION According to the present invention, a resin having a triorganosilyl group can be stably made aqueous, the amount of organic solvent can be greatly reduced, and the coating film formed has an elution rate equivalent to that of the solvent type. Can be controlled, and the antifouling property can be exhibited for a long period of time. In the present invention, the antifouling property can be exhibited for a long period of time because the binder aqueous resin emulsion has a triorganosilyl group having high self-polishing property in the emulsion particles, and the emulsion particles are fused. It is because it is what is formed into a film. Therefore, the obtained coating film has excellent water resistance, and when the coating film comes into contact with seawater, the silylcarboxylate portion in the particles only on the coating film surface is solubilized and eluted.

[0047]

[Table 6]

[0048]

[Table 7]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kei Ito             Seki, 4-17-1, Higashi-Hachiman, Hiratsuka City, Kanagawa Prefecture             West Paint Co., Ltd. F-term (reference) 4J038 CC031 CC032 CC081 CC082                       CG031 CG032 CG141 CG142                       CG161 CG162 CH031 CH032                       CH041 CH042 CH071 CH072                       CH121 CH122 CH171 CH172                       CL011 CL012 MA08 MA10                       NA05 NA26 PB05 PB07                 4J100 AB02Q AB03Q AB04Q AC03Q                       AE01Q AE18Q AF06Q AG04Q                       AJ01Q AJ02Q AJ08Q AL03Q                       AL04Q AL05Q AL08P AL08Q                       AL09Q AL10Q AL75Q AM02Q                       AM15Q AQ08Q AS02Q AS03Q                       BA05Q BA08Q BA31Q BA72P                       BC04P BC04Q BC43P BC54Q                       CA04 DA01 DA36 FA19 FA30                       JA01

Claims (5)

[Claims] 1. An alcohol-based solvent comprising (a) a triorganosilyl group-containing unsaturated monomer, and (b) another polymerizable unsaturated monomer copolymerizable with the monomer (a). Of a resin (A) having a number average molecular weight of 1,000 to 50,000, obtained by copolymerization in an organic solvent containing 5% by weight or more of
An aqueous antifouling resin composition comprising an aqueous resin emulsion obtained by water dispersion using an emulsifier (c) as a binder having antifouling properties. 2. The triorganosilyl group of the monomer (a) is
The aqueous antifouling resin composition according to claim 1, wherein at least one of the three hydrocarbon groups bonded to the silicon atom has 3 or more carbon atoms. 3. The aqueous antifouling resin composition according to claim 1 or 2, wherein the monomer (a) is triisopropylsilyl (meth) acrylate. 4. The resin (A) comprises the monomer (a) in an amount of 10 to 95.
The water-based antifouling resin composition according to claim 1, which is obtained by copolymerizing the monomer (b) in an amount of 5 to 90% by weight. 5. An aqueous antifouling coating composition comprising the aqueous antifouling resin composition according to any one of claims 1 to 4 and an antifouling agent (B).