JPH01161071A - Antifouling film-forming agent - Google Patents

Abstract

PURPOSE:To obtain an antifouling film-forming agent which is suitable for fishing nets, ship bottoms or general underwater structures, causes neither accumulation nor environmental pollution and gives a tough film excellent in an antifouling performance to a surface, by using a polymer having specified unsymmetrical triorganotin bonding units. CONSTITUTION:An unsaturated organotin compound monomer of formula I [wherein R<1> is H or -COOZ, R<2> is H, CR3 or -CH2COOZ, Z is formula II (wherein Bz is a benzyl group, R is an alkyl or an aryl, and a is 1 or 2)], e.g., benzylbutyltin acrylate, is polymerized or copolymerized with, optionally, other polymerizable unsaturated compounds such as (meth)acrylic acid (ester) to obtain a polymer having 35-100wt.% unsymmetrical triorganotin bonding units of formula III in the main chain of the polymer. This polymer is dissolved in an organic solvent such as a (halo)hydrocarbon in a concentration of 5-70wt.%, and other antifouling poisons such as cuprous oxide or a dialkyl dithiocarbamate (salt) are optionally added to the solution.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to an antifouling coating film forming agent.

Glue on the bottom of ships, fishing nets, or general underwater structures.

Contaminant organisms such as Fujibbo and Serpura adhere to the surface and cause various types of damage, and various antifouling agents are used to prevent the attachment of these contaminant organisms.

[Conventional technology]

In order to prevent the adhesion of contaminant organisms, tri-tin compounds (1) such as tributyl compounds and triphenyltin compounds (
Antifouling agents containing oxides, chlorides, fluorides, etc.) have been used, but because it is difficult to control the elution of antifouling components, long-term antifouling is not possible. Therefore, the group -COO3nR3 (R is alkyl) V in the polymer side chain
A triorganotin-containing polymer type antifouling agent having a phenyl group or a phenyl group is used, and gradually hydrolyzes in seawater to form R3S.
n compounds are eluted and provides long-term stain resistance.

[Problem that the invention seeks to solve]

However, the above-mentioned R3Sn compound does not necessarily have good degradability in the environment and may accumulate over time depending on the place where it is used, so there are restrictions on the amount and method of use.

[Means for solving problems]

As a result of various studies, the inventors of the present invention found that by using a polymer having an asymmetric tri-organotin group, which is completely different from the conventionally used organotin group, it is extremely easy to decompose in the environment after application. This discovery led to the present invention.

That is, 1 the present invention has general formula CI, 1 [
In the formula, R1 is a hydrogen atom or a group -cooz, R2 is a hydrogen atom, a methyl group or a group -CH2COOZ' (5, Z is the general formula % formula % (in the formula, Bz is a benzyl group, R is an alkyl group or an aryl group) , a represents an integer of 1 or 2), and a is an integer of 1 or 2, respectively. It is an antifouling film forming agent.

The asymmetric triorganotin-containing polymer of the present invention represented by the above general formula [I] is an unsaturated organotin compound represented by the general formula [■] I HC00Z (wherein R1, R2 and Z have the same meanings as above). The compound can be obtained by homopolymerizing a monomer or copolymerizing this monomer with one or more other polymerizable unsaturated compounds.Also, a carboxyl group is added to the side chain obtained in advance.

Asymmetric triorganotin hydroxide, bis(asymmetric triorganotin) oxide or asymmetric triorganotin hydroxide having an asymmetric triorganotin group represented by Z in the above general formula [■] in a polymer having an acid anhydride group or an alkali salt thereof. It can also be obtained by reacting triorganotin halide by a conventional method.

The unsaturated organotin compound monomer represented by the above general formula [■] is obtained by dehydrating 9 usually by reacting a polymerizable unsaturated monocarboxylic acid or dicarboxylic acid with asymmetric triorganotin hydroxide or bis(asymmetric triorganic 8) oxide. Alternatively, it can be obtained by treating an asymmetric triorganotin halide with an alkali salt of a polymerizable unsaturated monocarboxylic acid or dicarboxylic acid to dealkalkify the halide.

Examples of such polymerizable unsaturated monocarboxylic acids or dicarboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid, and acid anhydrides of itaconic acid and maleic acid can also be used in the reaction. used.

Examples of the unsaturated organic tin compound monomer produced in this manner and represented by the general formula [■] include 1, for example, pencil diptyltin methacrylate [colorless liquid].

NMR: 0.8-2.0 (m, 18H), 2.
1 (t, 3H), 2.9 (s, 2H).

5.7-6.2 (d, 2H), 7.2 (s, 5
H)), benzyldibutyltin acrylate (melting point 76~
77°C), dibenzylbutyltin acrylate (melting point 60°C), dibenzylbutyltin acrylate (melting point 60°C),
~61°C), pencil diphenyl/l/tin acrylate (
melting point lO4~105℃), bis(pencil dibuti/I/
tin) itaconate (viscous liquid) bis(benzyldibutyltin) malate (FdA point 38-40°C), bis(benzyldiphenyltin) malate (melting point 109-110°C)
), and other unsaturated organotin compound monomers can be produced in the same manner.

Examples of other polymerizable unsaturated compounds to be copolymerized with the unsaturated organotin compound represented by the above general formula [■] include acrylic acid, methacrylic acid, and maleic acid (or acid anhydride).
, polymerizable unsaturated acids such as itaconic acid (or acid anhydride); polymerizable unsaturated acid esters such as alkyl esters, cycloalkyl esters, aralkyl esters, and aryl esters of these acids; acid amides; diorganotin salts Vinyl compounds such as acrylonitrile, vinyl acid, and styrene; Monomers such as olefin compounds such as ethylene, propylene, and butadiene. Furthermore, in order to increase the water solubility or hydrophilicity of the copolymer, vinylpyrrolidone, hydroxyethyl (meth)acrylate, etc. may be used. Two or more types of the above monomers may be used.

In addition, polymers having a carboxy group, an acid anhydride group, or an alkali salt thereof in the side chain can be obtained by homopolymerizing an unsaturated carboxylic acid or a derivative thereof or by polymerizing one or more of the other polymerizable unsaturated compounds listed above. It can be obtained by copolymerization or by further hydrolyzing the obtained polymer or copolymer. Examples of such unsaturated carboxylic acids or derivatives thereof include acrylic acid, methacrylic acid, maleic acid, and itaconic acid.

Examples include maleic anhydride, itaconic anhydride, maleic acid monoester, and itaconic acid monoester. Carboxy groups of the homopolymer or copolymer thus obtained,
'By reacting the acid anhydride group or its alkali salt with asymmetric triorganotin hydroxide, binu (asymmetric triorganotin) oxide or asymmetric triorganotin halide having an organotin group in the general formula [u] above, The polymer of the present invention may contain an asymmetric triorganotin bond unit represented by the general formula CI).

The homopolymer or copolymer of the present invention containing a bonding unit represented by the general formula [1] in the linear polymer chain is an unsaturated organotin compound monomer represented by the general formula [■] or other polymerizable monomers. It can be easily obtained by bulk, solution, emulsion, suspension, etc. polymerization methods by adding unsaturated compounds in the presence of a suitable vinyl polymerization catalyst, preferably a radical catalyst such as benzoyl peroxide or azohisisobutyronitrile. Can be done.

In another method, a polymerizable unsaturated carboxylic acid or a derivative thereof, or the other polymerizable unsaturated compound described above is polymerized using the catalyst and polymerization method described above.

The homopolymer or copolymer of the present invention can be obtained by introducing an asymmetric triorganotin group into the obtained homopolymer or copolymer.

Radical polymerization is usually carried out in the presence of a solvent.

For example, benzene, toluene, xylene natonoaromatic hydrocarbons: petroleum hydrocarbons such as ligroin 2 petroleum benzine, mi, traral spirit; saturated aliphatic hydrocarbons such as cyclohexane, n-hexane, heptane, octane: methyl ethyl ketone.

Solution polymerization is generally carried out in the presence of a solvent or mixed solvent such as ketones such as methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol and ethyl cellosolve. Similar solvents can be used to introduce asymmetric triorganotin groups into the polymer.

The asymmetric triorganotin-containing polymer solution obtained by polymerization or reaction in a solvent in this manner is a colorless to pale yellow viscous liquid. Further, the asymmetric triorganotin-containing polymer of the present invention can be dissolved in almost all organic solvents. When an organic solvent solution containing these polymers was applied to a wooden board, a metal board, a synthetic fiber rope, and a net and dried, a coating film of the asymmetric tri-organotin-containing polymer with good flexibility and adhesion was obtained. was formed.

In the asymmetric triorganotin-containing polymer of the present invention, it is necessary that 85 to 100% by weight of the asymmetric triorganotin bond unit represented by the general formula CI) be present in the linear polymer chain. If the amount is less than 35% by weight, sufficient antifouling performance cannot be exhibited.

The antifouling coating film-forming agent of the present invention is produced using the asymmetric triorganotin-containing polymer in one of various embodiments depending on the antifouling purpose.

That is, the asymmetric triorganotin-containing polymer of the present invention is dissolved in an organic solvent such as a hydrocarbon, halogenated hydrocarbon, ketone, ester, or alcohol.

Alternatively, use the asymmetric tri-organotin-containing polymer solution obtained by each of the above production methods as is! Or dilute it.

It can be used as an anti-β5 film forming agent, and if necessary, other known antifouling poisons, such as cuprous oxide.

dialkyldithiocarbame-trachloroisophthalonitrile, N-7 lylmaleimide, other organotin compounds. Pigments, dyes. An antifouling agent can be produced by optionally adding fillers and other additives. There is no particular restriction on the proportion of the polymer in the asymmetric triorganotin-containing polymer solution thus obtained. It can be from 5 to 70% by weight.

In the present invention, the asymmetric tri-organotin-containing polymer itself serves as an F5 711 barrier and as a coating film at the same time. In principle, other color vehicles (Vihiku/L/), such as oil-based face, vinyl resin varnish, Acrylic/L/ViJ oil-based varnish, and chlorinated rubber-based face, are not required, but anti-f9
Of course, these may be used depending on the purpose.

When the antifouling coating film-forming agent of the present invention thus produced is treated on a substrate material to be antifouled by a conventional method 9 such as coating, spraying, dipping, etc., the following characteristics can be exhibited.

[Action and effect]

First, the asymmetric triorganotin component in the polymer of the present invention has the feature that it easily decomposes in the environment and becomes a non-toxic tin compound. Therefore, on fishing nets and boat bottoms to which the antifouling film-forming agent of the present invention is applied, the adhesion of contaminant organisms is prevented by the asymmetric tri-organotin compound eluted by hydrolysis, and the compound is subsequently decomposed by seawater, resulting in accumulation. It has the effect of not polluting the environment. This is thought to be due to the presence of benzyl groups in the asymmetric triorganotin molecules in the polymer of the present invention. It has also been found that the antifouling effect is not lost even when up to two benzyl groups are present in the molecule.

Secondly, since the asymmetric triorganotin-containing polymer of the present invention itself is a polymer that has strong adhesive properties to the substrate material to be treated, it forms a strong coating film on the surface and has excellent antifouling properties. The substrate can be protected for a long time by its physical and chemical resistance.

Furthermore, in the present invention, since an asymmetric triorganotin group is introduced into the polymer or copolymer, the physiological effects on humans and animals are further reduced. Manufacturing of antifouling film forming agent,
9. There is virtually no skin disorder such as rash or respiratory disorder due to irritation during the application process.9. Work can be done extremely safely.

The antifouling film-forming agent of the present invention is particularly advantageously used to protect objects that come into contact with seawater, such as steel ships, the bottoms of reinforced plastic ships, fishing nets, underwater structures, and seawater introduction pipes.
It also applies to the protection of rivers, lakes, and other bodies that are susceptible to damage from contaminant organisms due to long-term use of water.

〔Example〕

Next, the present invention will be explained with reference to Examples and Test Examples, where % in each example indicates weight %.

Example 1 300 equipped with a stirrer, a thermometer, a dropping funnel and a condenser
Benzyldiptyltin methacrylate 651. Methyl methacrylate 202.2-ethylhexyl acrylate 5y, xylene 90f2H
After charging J'benzoyl peroxide 11 and mixing well at room temperature, half of the total solution amount (<909) was transferred to the dropping funnel. After replacing the inside of the container with nitrogen gas, heat it to 90°C,
Prepolymerization was carried out for 1 hour. Next, while keeping the same temperature, 1
The mixture was added dropwise through the dropping funnel over about 30 minutes. After that 9
The mixture was heated and stirred at 0°C for 1 hour and then at 100°C for 20 minutes. The obtained pencil dibutyltin-containing polymer solution (referred to as Polymer Solution I&A) was a pale yellow liquid having a viscosity (25° C.) of 500 cps, and the heating residue was 50.0%.

Example 2 Bis(benzyl dib) was added to the same reaction vessel as in Example 1.
V tin) itaconate 582. Methyl methacrylate 36
7. n-butyl acrylate 62. Charge 0.8 y of azobisisobutyronitrile and 1009 y/l of azobisisobutyronitrile and mix well at room temperature.
y) was transferred to the dropping funnel. After purging the inside of the container with nitrogen gas, it was heated to 75° C. and prepolymerized for 1 hour. Subsequently, the mixture was added dropwise from a 9-dropping funnel over a period of about 80 minutes while maintaining the same temperature. After that, it was heated to 75℃ for 1 hour, and then heated to 100℃ for 20 minutes.
The mixture was heated and stirred for a minute. The obtained tin-containing polymer solution (referred to as polymer solution B) has a viscosity (at 25°C)
Pale yellow liquid with 380 cps, heating residue is 49
．． It was 8%.

Example 3 In a reaction vessel similar to Example 1, 30.39 g of methacrylic acid was added.
(0.35 mol), methyl methacrylate 46 mol.

n-Zotyl acrylate 102. Pennzoil peroxidide 22. n-Butyl alcohol-yV50? and xylene 502, and after mixing well at room temperature, half of the total solution amount (93.2f) was transferred to the dropping funnel.

After purging the inside of the container with nitrogen gas, prepolymerization was performed at 75 to 80°C for 1 hour. Subsequently, while maintaining the same temperature, the mixture was added dropwise into the flask over a period of about 30 minutes. Thereafter, the mixture was heated and stirred at the same temperature for 1 hour, and then at 110° C. for 20 minutes. The polymer was cooled in a trench at 50°C, and added with bis(benzylcyphylε).
Easy) Oxide 116. fl(0,176mo)Ly)
and xylene 1002 were added and reacted at the same temperature for 30 minutes. The obtained benzyldibutyltin-containing polymer solution (referred to as polymer solution C) was a pale yellow viscous liquid having a viscosity (25° C.) of 650 cps, and the heating residue was 50.2%.

Example 4 Maleic anhydride 165' (
0.16 mo/L/), methyl methacrylate 232
゜vinylpyrrolidone 10, 2-ethylhexyl acrylate 57. 1.02 of benzoyl peroxide and 0.01 of xylene were charged, the inside of the container was replaced with nitrogen gas, and slow heating was started, followed by heating and stirring at 85 to 90° C. for 1 hour. Methyl methacrylate 231i' in the dropping funnel,
Vinylpyrrolidone 10? , 2-ethylhexy/L'5
f? A mixed solution of 1.07 g of benzoyl peroxide and benzoyl peroxide was added dropwise at the same temperature over about 1 hour. Thereafter, the mixture was heated and stirred at the same temperature for 1 hour, and then at 110° C. for 20 minutes. The polymer was cooled to 50°C, and bis(benzyldibutyltin) oxide 108r (0,163 mol) and xylene 10°C were added thereto. was added and reacted at the same temperature for 20 minutes. The obtained benzyldibutyltin-containing polymer solution (polymer solution i!i
D) is a pale yellow viscous liquid with a viscosity (25°C) of 720 cps.

The heating residue was 51.0%.

Example 5 FC50 equipped with a stirrer, a thermometer, 1 dropping funnel, and a cooler
In a 0 ml Yotsuro flask, add 1409 pencil dipyltin methacrylate and 465' methyl methacrylate.
and 2-ethylhexyl acrylate 14? mixture and surfactant (Emulgit 16. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 2
01 and polyethylene glyco-/l/(average molecular ff1
4000) 8F ion exchange water 1862
was charged and stirred at room temperature for 1 hour to emulsify the monomer mixture. Half of the obtained emulsion (1902) was transferred to a dropping funnel, the inside of the reaction vessel was replaced with nitrogen gas, and 2.3 g of an 8% aqueous solution of ammonium persulfate was charged therein, heated and stirred, and the internal temperature was brought to 75 to 80°C. The emulsion in the 9-dropping funnel was added dropwise over 40 minutes while maintaining the temperature. Thereafter, the mixture was stirred at the same temperature for 2 hours to complete one reaction. The obtained benzyldibutyltin-containing polymer solution (referred to as polymer solution E) had a viscosity (25°C
) Milky white liquid with 98 cps, heating residue is 49%
Met.

Examples 6 to 14 According to the same polymerization method as in Examples 1 to 5, reactions were carried out under polymerization reaction conditions using the polymerization components, solvents, and catalysts shown in Table 1 below, and asymmetric triorganotin-containing polymers were obtained. Solution #: (Polymer solution MF to N) was obtained.

A method of polymerizing a tin compound or other polymerizable unsaturated compounds.

Method b: Polymerize a monopolymerizable unsaturated carboxylic acid compound or this with another polymerizable unsaturated compound in the same manner as in Examples 3 to 4,
A method in which triorganotin hydroxide or bis(triorganotin) oxide is then applied.

Method C, a method in which a nine-polymerizable unsaturated organotin compound or this and another polymerizable unsaturated compound are subjected to emulsion polymerization in the same manner as in Example 5.

The above is shown in Table 1.

Reference Example A In a reaction vessel similar to Example 1, add 14.9 g of maleic anhydride.
y (0,15 mo/L/), methyl methacrylate 25y.

2-ethylhexyl acrylate 13 and xylene 1
702 was charged and stirred at 50° C. or below to dissolve maleic anhydride and form a uniform solution. To this was added benzoyl peroxide 1f dissolved in xylene 302, heated slowly, and after the internal temperature reached 95° C., heating and stirring was continued at the same temperature for 1 hour. After that, 25 ml of methyl methacrylate and 1 ml of 2-ethylhexyl acrylate were added from the dropping funnel.
32 and benzoyl peroxide 12.
It was added dropwise at the same temperature in 0 minutes. After the dropwise addition, the mixture was heated and stirred at 95 to 100°C for 2 hours and then at 125 to 130°C for 30 minutes. The polymer was cooled to 60°C, and bis(triphenyltin) oxide 109? (0.15 mo/I/) was added and stirred at the same temperature for 1 hour, then allowed to cool and the viscosity (25°C) was 340.
A cloudy and viscous triphenyltin-containing polymer solution (referred to as the polymer solution of Reference Example A) having cps was obtained.

Reference Example B Into the same reaction vessel as in Example 1, 130 F of tributyltin methacrylate, 602 °F of methyl methacrylate, 10 parts of n-butyl acrylate, and 2 parts of azobisisobutyronitrile were charged, mixed well, and half (100
5') was transferred to the dropping funnel. xylene 100 in a container
1 was added, and after purging with nitrogen gas, polymerization was carried out at 80° C. for 1 hour. The remaining half was added dropwise from the dropping funnel at the same temperature over 1 hour. Continue stirring at the same temperature for 2 hours, and then
The temperature was raised to ℃ and allowed to react for 30 minutes. Leave to cool and reduce the viscosity (2
A colorless and viscous tributyl-containing polymer solution (referred to as the polymer solution of Reference Example B) having a tributyl content of 650 cps (5°C) was obtained.

Examples 15 to 26 Using each of the asymmetric triorganotin-containing polymer solutions obtained in Examples 1 to 14, the ingredients listed in Table 2 below were added to the antifouling solution for boat bottoms of the present invention. Got the paint.

The above is summarized in Table 2. Note that the numbers in Table 1 indicate parts by weight.

(I) Antifouling test (clear coating) The antifouling agent of the present invention (polymer solution A-N) obtained in Examples 1 to 1-L was treated with 17 x 9 x 0.3 crn of hard vinyl chloride/l/resin. The film was applied to both concave areas to a dry film thickness of approximately 1501z. Each coated plate was submerged underwater in Owase Bay, Mie Prefecture, for 6 months, and its contamination state was observed.

The results are shown in Table 3.

The symbols in the table indicate the following (the same applies to subsequent tables).

O: No adhesion of marine animals and plants △: 〃 5% or less adhesion ×: 〃 5-20% adhesion XX: /
/ 20-50% adhesion XXX: //
Adhesion of 50% or more (c) % indicates the adhesion area.

Table 3 (ID Antifouling Test (Fishing Nets) Xylene 20
0 parts and also the antifouling agents of the present invention (polymer solutions E and N) obtained in Example 5 and Example 14 (24 bottles, 8 sections)
was immersed, taken out after 3 minutes, air-dried, and then attached to an iron frame. The amount of coating was approximately 20% based on the weight of the fishing net. These were submerged underwater for three months in Owase Bay, Mie Prefecture, and their contamination status was observed every month.

The results are shown in Table 4.

4th surface antifouling test (ship bottom paint) The antifouling paint of the present invention obtained in Examples 15 to 26 was
It was applied to both sides of a 10×0.3 crn hard vinyl chloride resin plate to a dry film thickness of about 200 μm. Each coated plate was submerged in the sea for 12 months in Owase Bay, Mie Prefecture, and its contamination state was periodically observed.

The results are shown in Table 5.

5th Table: Compound Degradability Test The polymer solutions A-N obtained in Examples 1 to 14 were tested at 20X
It was coated on one side of a 10×0.3 crn vinyl chloride resin plate to a dry film thickness of about 50 μm, and after drying, it was immersed in 1 ton of seawater for 4 hours to elute the asymmetric triorganotin content. A 100 m portion of the sample was collected, extracted with benzene, and the initial asymmetric triorganotin content was measured. The remaining eluted seawater liquid was placed under an ultraviolet lamp (253.7 nm mercury lamp) at 30 t-rn, and 100 ml was collected over time, extracted with 10 ml of benzene, and subjected to ECD-GC (gas chromatography with an electron capture detector). ) The remaining asymmetric tri-organotin content was quantified. As a comparative example, the tri-organotin content was determined in the same manner for a triphenylene/I/trifluoride-containing polymer solution (polymer solution of Reference Example A) and a tributyltin-containing polymer solution (polymer solution of Reference Example B). did.

The results are shown in Table 6.

Note that the numbers in Table 6 indicate the residual rate (%) of the triorganotin content.

Claims (1)

[Claims] General formula [I] ▲ Numerical formula, chemical formula, table, etc. are present in the linear chain of the polymer [I] [In the formula, R^1 is a hydrogen atom or a group -COOZ, and R^2 is hydrogen atom, methyl group or group -CH_2COOZ, Z is the general formula -Sn(Bz)_aR_3_-_a (in the formula, Bz represents a benzyl group, R represents an alkyl group or an aryl group, and a represents an integer of 1 or 2) An antifouling coating film-forming agent characterized by using a polymer comprising 35 to 100% by weight of asymmetric triorganotin bonding units represented by the following formulas.