JPH0254869B2 - - Google Patents

Description

Claim 1 a 1 An organotin compound selected from the group consisting of triorganotin halide, thioalkoxide, alkoxide, hydroxide; bis(triorganotin) oxide and bis(triorganotin) sulfide; and 2 General formula [In the formula, R ¹ and R ² are respectively a hydrocarbyl group, a substituted hydrocarbyl group (CH ₂ ) nOH, hydrogen and

[Formula] (R ³ is a hydrocarbyl group), provided that both R ¹ and R ² cannot be hydrogen; n is 0
or an integer from 1 to 4]; and (b) at least one of the reaction products of the organotin compound and the nitrogen compound. a solubilized polymeric triorganotin carboxylate derived from at least one triorganotin derivative of an ethylenically unsaturated carboxylic acid; and (2) cuprous oxide, zinc oxide, or cuprous oxide and zinc oxide. A viscosity stabilizer for use in an antifouling paint composition comprising a mixture of 2. The stabilizer according to claim 1, wherein the ratio of organotin compound to nitrogen compound is 1:1 to 10:1. 3. The stabilizer according to claim 2, wherein the ratio of organotin compound to nitrogen compound is 3:1 to 6:1. 4. The stabilizer of claim 1, wherein R ¹ and R ² are each selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, (CH ₂ )nOH, hydrogen, and an acyl group. 5. The stabilizer according to claim 4, wherein ^R1 and ^R2 are alkyl groups having 1 to 20 carbon atoms, and n is 0. 6. The stabilizer according to claim 5, wherein R ¹ and R ² are lower alkyl groups having 1 to 8 carbon atoms. 7. The stabilizer according to claim 6, wherein R ¹ and R ² are ethyl groups. 8. The stabilizer according to claim ¹ , wherein R 1 is (CH ₂ )nOH, R ² is H or (CH ₂ )nOH, and n is 2. 9. The stabilizer according to claim 1, wherein the triorganotin derivative is a tri(lower alkyl)tin derivative or a triphenyltin derivative in which each alkyl group contains 1 to 4 carbon atoms. 10. The stabilizer according to claim 9, wherein the tri(lower alkyl)tin derivative is a tributyltin derivative. 11 Claim 1, wherein the ethylenically unsaturated carboxylic acid is acrylic acid or methacrylic acid
Stabilizers listed in section. 12. The stabilizer according to claim 1, wherein the polymer is at least partially derived from at least one tin-free ethylenically unsaturated compound. 13. Claim 12, wherein the tin-free ethylenically unsaturated compound is an ester of acrylic acid or methacrylic acid and an alcohol having 1 to 8 carbon atoms.
Stabilizers listed in section. 14. The stabilizer according to claim 1, wherein R ¹ and R ² are lower alkyl groups having 1 to 8 carbon atoms, and n is 0 or 2. 15. The stabilizer according to claim 14, wherein R ¹ and R ² are a methyl group, an ethyl group or an n-propyl group. 16 The organotin compound has the general formula: R ⁴ ₃ SnX or R ⁴ ₃ Sn) ₂ Y [wherein R ⁴ is a hydrocarbyl group or a substituted hydrocarbyl group, ^and or −OR ⁵ (R ⁵ is carbon number 1 to 20
The stabilizer according to claim 1, wherein the stabilizer is a compound represented by the following formula: Y is oxygen or sulfur. 17 Claim 16, wherein R ⁴ is a phenyl group, an inertly substituted phenyl group, a cycloalkyl group having 6 to 8 carbon atoms, a lower alkyl group having 1 to 4 carbon atoms, or a substituted lower alkyl group. Stabilizers listed in section. 18 The organotin compound is bis(tri-n-butyltin) oxide, triphenyltin hydroxide or bis(triphenyltin) oxide,
Stabilizer according to claim 16. 19 (1) a solubilizing polymer at least partially derived from at least one triorganotin derivative of an ethylenically unsaturated acid; and (2) cuprous oxide, zinc oxide, or cuprous oxide and zinc oxide. a pigment consisting of a mixture; (3) a) 1) an organotin compound selected from the group consisting of 1) triorganotin halides, thioalkoxides, alkoxides, hydroxides; bis(triorganotin) oxides and bis(triorganotin) sulfides; and 2. formula: [In the formula, R ¹ and R ² are respectively a hydrocarbyl group, a substituted hydrocarbyl group (CH ₂ ) nOH, hydrogen and

[Formula] (R ³ is a hydrocarbyl group), provided that both R ¹ and R ² cannot be hydrogen; n is or 0 or an integer from 1 to 4 ]; and (b) a viscosity stabilizer consisting of one or both of the reaction products of the organotin compound and the nitrogen compound. 20. The paint according to claim 19, wherein the concentration of the viscosity stabilizer is from 0.1 to 10% by weight based on the weight of the polymer solids. 21. The coating of claim 20, wherein the concentration of viscosity stabilizer is from about 0.5 to about 6% by weight, based on the weight of polymer solids. 22. The paint according to claim 19, which contains a non-reactive solvent. BACKGROUND OF THE INVENTION Field of the Invention This invention relates to antifouling coating compositions. In particular, the present invention addresses the viscosity that often occurs upon long-term storage of antifouling coatings containing cuprous oxide and polymers in which at least a portion of the repeating units are derived from triorganotin salts of ethylenically unsaturated acids. The invention relates to stabilizer compositions that prevent the increase in viscosity and, in some cases, gelation. DESCRIPTION OF THE PRIOR ART Organisms such as sinews and algae attach to and grow on submerged portions of a ship's hull, thereby substantially increasing the resistance to passage of the ship's hull through the water. As a result, the vessel's fuel efficiency and maximum speed are reduced, requiring periodic removal of accumulated contaminants. This operation is expensive and typically requires the vessel to be docked for a significant period of time to remove the contaminants. A commonly used method to prevent the attachment and growth of contaminant organisms on the hull, thereby extending the cleaning and repainting period, is to apply a finish coat containing an antifouling agent to the hull water. This method involves applying it to the entire area to be immersed. Triorganotin compounds, such as (tri-n-butyltin) fluoride, have long been recognized as particularly effective antifouling agents. US Patent No.
No. 3,167,473 describes a number of disadvantages of triorganotin compounds, such as high toxicity to mammals and high extractability of triorganotin compounds from coatings by seawater. It is stated that it can be removed by adding it to In the process described in the above-mentioned U.S. patent, triorganotin derivatives of ethylenically unsaturated acids such as acrylic acid or methacrylic acid are polymerized alone or other ethylenically unsaturated compounds which can be copolymerized with said triorganotin derivatives. , preferably in the presence of a lower alkyl ester of acrylic acid or methacrylic acid. U.S. Pat. No. 4,191,579 discloses that when a pigment that is water-insoluble and reactive with seawater and a pigment that is water-insoluble and non-reactive with seawater are present in an antifouling finish paint applied to a ship's hull, , it is stated that this pigment combination imparts self-leveling properties to the paint as the ship moves through the water. The rate of dissolution is sufficient to release an effective concentration of the poison, while preventing premature dissolution of the finish coating and the triorganotin-containing polymer used as a binder and antifouling agent. According to the above US patent specifications, cuprous oxide and zinc oxide are preferred as seawater-reactive pigments. Paints containing cuprous oxide and a polymer at least partially derived from a triorganotin salt of an ethylenically unsaturated acid are preferred from the standpoint of the antifouling activity of cuprous oxide; cannot be stored for more than 6 months because the polymer gels early. The patent specification states that if a longer shelf life is required, the triorganotin-containing polymer and cuprous oxide must be packaged as separate components. Such two-component coatings are unsuitable for commercial applications because it is difficult to mix large quantities of the two components to a reasonable degree of uniformity. If the final composition is not homogeneous, coatings applied using this composition may not contain the same concentration of toxicant throughout.
Presumably, early contamination occurs in zones with relatively low toxicant concentrations. U.S. Pat. No. 4,187,211 discloses that the aforementioned U.S. Pat.
The storage stability of the antifouling paint specified in the specification of No. 4191579 is as follows:
By including in the composition relatively inert and water-insoluble dehydrating agents such as calcium sulfate in anhydrous and hemihydrate forms or various water-reactive organic compounds such as aliphatic isocyanates, It is stated that it can be increased significantly.
However, experimental data shows that in accelerated aging tests conducted at a temperature of 50°C, the viscosity of paints containing anhydrous calcium sulfate, polymeric triorganotin toxicants, and cuprous oxide is lower than that of control samples in which calcium sulfate is omitted. It was observed that it increased at a fast rate. SUMMARY OF THE INVENTION It has now been proposed that gelation of paints of the type described in U.S. Pat. It has been found that this can be prevented even when stored for 3 months or more at a temperature of .degree. Additionally, the viscosity of the paint remains within the acceptable range for application to ship hulls by any conventional method. According to the present invention, a stabilizer composition is provided which effectively retards the gradual increase in viscosity and eventual gelation of antifouling coatings containing polymeric triorganotin carboxylates and cuprous oxide. provided. This stabilizer composition comprises (1) a mixture of (a) a monomeric triorganotin compound and (b) a secondary or tertiary hydroxylamine or alkanolamine;
It consists of one or both of the reaction products of and (b).

[Detailed description of the invention]

According to the present invention, 1) (a) a triorganotin compound;
(b) General formula [In the formula, R ₁ and R ₂ are each a hydrocarbyl group, a substituted hydrocarbyl group, (CH ₂ ) _o OH, hydrogen and

[Formula] (R ³ is a hydrocarbyl group), but with the proviso that
R ¹ and R ² cannot both be hydrogen, and n is 0 or an integer from 1 to 4] or 2)
A stabilizer composition for an antifouling paint containing a solubilized polymeric triorganotin carboxylate, cuprous oxide, and/or zinc oxide, which is composed of one or both of the reaction products of the above triorganotin compound and a nitrogen compound. things are provided. In a narrower embodiment of the invention, the triorganotin compound has the general formula R ⁴ _{3 So} X or (R ⁴ _{3 So} ) ₂ Y
[In the formula, R ⁴ is a hydrocarbyl group, and X is a residue obtained by removing easily mobile hydrogen from a halogen, pseudohalogen, alcohol, phenol, mercaptan, carboxylic acid, or mineral acid, -
OR ⁵ or -SR ⁵ (R ⁵ is an alkyl group having 1 to 20 carbon atoms, a phenyl group or a benzyl group), and Y is oxygen or sulfur.
R ¹ and R ² in the above formula for nitrogen compounds are hydrogen, an alkyl group, (CH ₂ ) _o OH, a cycloalkyl group or an aryl group or an acyl group and n is 0, 2, 3 or 4; , or one or both of R ¹ and R ² is (CH ₂ ) _o OH,
Any of the remaining R ¹ and R ² is hydrogen, and n
is 2 or 3, and the weight ratio of triorganotin compound to nitrogen compound is 1:1 to 10:1. Triorganotin compounds in which R ⁴ is lower alkyl, substituted lower alkyl, phenyl or substituted phenyl group having 1 to 4 carbon atoms are effective antifouling agents. In this case, the nitrogen compound is N,N-dialkyl, mixed aryl alkyl, aryl acyl or alkyl acyl hydroxyl amine or of the general formula [HO(CH ₂ ) _o ] _n NH _3-n (m is 2 or 3 and n is 2 or 3), and the weight ratio of the triorganotin compound to the nitrogen compound is preferably 3:1 to 6:1. the triorganotin compound is bis(tri-2-butyltin) oxide and the nitrogen compound is N,N-di(lower alkyl)hydroxylamine such as N,N-diethylhydroxylamine;
or most preferably an alkanolamine such as diethanolamine or triethanolamine. The weight ratio of the triorganotin compound to the nitrogen compound is about 5:1 when the nitrogen compound is hydroxylamine, and from 4:1 to 6:1 when the nitrogen compound is alkanolamine. According to another aspect of the invention, there is provided an antifouling paint containing one of the above stabilizer compositions, cuprous oxide, and at least one polymeric triorganotin carboxylate. In a narrower embodiment of the invention, the triorganotin carboxylate is a homopolymer of tri(lower alkyl)tin or triphenyltin salts of ethylenically unsaturated acids or copolymerizable ethylene salts with at least one other It is a copolymer with a sexually unsaturated compound. In a preferred embodiment, the ethylenically unsaturated acid is acrylic or methacrylic acid, and the comonomer used to prepare the polymer is an ester of acrylic or methacrylic acid with an alcohol containing 1 to 8 carbon atoms. be. Triorganotin (R ⁴ ₃ Sn−)
The repeating units containing residues range from 20 to 20 of the repeating units present in the polymeric triorganotin carboxylate.
It makes up about 80%. The weight ratio of polymeric triorganotin carboxylate to cuprous oxide and/or zinc oxide is about 3:1 to 1:7, and R ⁴ is butyl or phenyl. Nitrogen Compounds One of the components of the stabilizer composition of the present invention is hydroxylamine or di- or trialkanolamine. These compounds have the general formula It is expressed as When the nitrogen compound is hydroxylamine, n is 0 and R ¹ and R ² are the same or different hydrocarbyl groups, substituted hydrocarbyl groups, (CH ₂ ) _o OH, hydrogen or acyl.

[Formula] group (R ³ is a hydrocarbyl group), provided that both R ¹ and R ² cannot be hydrogen. It is preferable that R ¹ and R ² are the same and are a linear or branched alkyl group having 1 to 20 carbon atoms, a benzyl group, a phenyl group, or a benzoyl group. When R ¹ and R ² are alkyl groups, they most preferably contain 1 to 4 carbon atoms. As used herein, the term "hydrocarbyl" refers to straight or branched alkyl groups of 1 to 20 carbon atoms, cycloalkyl groups of 5 to 8 carbon atoms, aryl, tolyl, and xylyl groups. Includes alkyl-substituted aryl groups such as alkaryl groups (referred to as alkaryl groups) and aryl-substituted alkyl groups such as benzyl and phenylethyl groups (referred to as aralkyl groups). In the above formula
The hydrocarbyl groups represented by R ¹ and R ² can be unsubstituted or have one or more substituents. When substituents are present, these include hydrocarbyloxy, cyano,
Relatively unreactive groups such as carboxyl (RCOO-, R is a hydrocarbyl group) and nitro groups or halogens, hydroxyl, mercapto (-SH), carboxy (-COOH) and isocyanato (-N=C It can be a reactive group such as a =O) group. Preferably, the substituents present are those that do not react with any of the components of the final coating composition containing the stabilizer composition of the present invention, since such reaction would have a detrimental effect on the stability of the coating composition. Because it gives. Commercially available hydroxylamine and its salts include N,N-diethylhydroxylamine and N,N-dimethylhydroxylammonium hydrochloride. Typical hydroxylamines that can be used in the present invention include the following. ; N-phenyl, N-benzoylhydroxylamine N-benzoylhydroxylamine N, N-dibenzoylhydroxylamine N-methylhydroxylamine N-butylhydroxylamine N, N-dibutylhydroxylamine N, N-trifluoromethylhydroxylamine N -benzyl-N-o-trihydroxylamine N-fluoroyl-N-phenylhydroxylamine N,N-dimethylhydroxylamine N-ethylhydroxylamine When the nitrogen compound is di- or trialkanolamine, the formula n is an integer from 1 to 4, R ¹ is -(CH ₂ ) _o OH, R ² is -(CH ₂ ) _o OH,
Hydrocarbyl group or hydrogen. n is 2, R ¹ is -CH ₂ CH ₂ OH, and R ² is -
CH ₂ CH ₂ OH or hydrogen is preferred, but this suitability is based on the efficiency of stabilization. The following may be mentioned as alkanolamines which can be used in the present invention: dimethylethanolamine diethylethanolamine ethylethanolamine diisopropylethanolamine butyldiethanolamine methyldiethanolamine methyldiethanolamine ethyldiethanolamine isopropylethanolamine n-butylethanolamine dimethylisopropanolamine cyclohexyl Diethanolamine phenylethanolamine N-cyanoethyl-N-hydroxyethylaniline m-tolyldiethanolamine o-methoxyphenyldiethanolamine triorganotin compound The triorganotin compound present in the stabilizer composition of the present invention has three atoms bonded to a tin atom. It contains a hydrocarbyl group. The fourth valence of the tin atom is oxygen, sulfur, halogen atom, pseudohalogen, organic or inorganic acid, alcohol, phenol, mercaptan, mercaptoalcohol or its ester, mercaptocarboxylic acid or its ester, or easily mobile hydrogen. It is satisfied by the residue remaining after removing the mobile hydrogen from any other organic or inorganic compounds it contains. When oxygen or sulfur is bonded to the tin atom, the compound is a bis(triorganotin) oxide or a sulfide, respectively. Preferably, the three hydrocarbyl groups bonded to the tin atom are lower alkyl groups having 1 to about 6 carbon atoms or phenyl groups. This suitability is based on the relatively high level of activity against contaminant organisms exhibited by compounds of this type.
This activity complements the antifouling activity of the polymeric triorganotin compounds and stannous oxide that constitute the toxic components of antifouling paints containing the stabilizer compositions of the present invention. The three hydrocarbyl groups attached to the tin atom can be the same or different.
Triorganotin compounds in which two or three different hydrocarbyl groups are attached to the tin atom have been described in the literature. When the fourth group attached to the tin atom is halogen, it can be fluorine, chlorine, iodine or bromine. The term “pseudohalogen”
The following inorganic groups, i.e., when in anionic form, have chemical properties similar to halogen ions in that they combine with hydrogen to form acids and react with silver to form water-insoluble salts. means the inorganic group shown. Proid halogen ions include cyanide, thiocyanate (SCN ^- ), cyanate (OCN ^- ), isocyanate (NCO ^- ) and isothiocyanate (NCS). Suitable carboxylic acids that can be reacted with triorganotin halides, hydroxy or bis(triorganotin) oxides to form triorganotin compounds suitable for use in preparing the compositions of the invention include acetic acid, propionic acid, Mention may be made of butyric acid, caproic acid, caprylic acid, dodecanoic acid, 2-ethylhexoic acid, eicosane, benzoic acid and cyclohexanecarboxylic acid. Suitable inorganic acids can be monofunctional or polyfunctional and include in particular nitric acid, phosphoric acid, phosphorous acid and sulfuric acid. Example 1 This example demonstrates the reduction in viscosity increase exhibited by antifouling paints containing stabilizer compositions of the present invention as compared to unstabilized paint compositions. The preparation of the paint was carried out as follows:
0.8g bentonite clay (Bentone27,
Bentone is a registered trademark) and 0.9g of methanol.
5.2 g of colloidal silica (Cab-O-Sil-PTG) in a mixture of 33.7 g of methyl isobutyl ketone and 65.2 g of xylene were mixed in a stainless steel container for about 5 minutes. To this vessel was added 250.4 g of organotin acrylate copolymer solution, 229.6 g of zinc oxide, and 164.2 g of cuprous oxide (Glidden) along with about 400 ml of a steel shot about 1/8 inch in diameter. The paint was shaken on a Red Davisil Paint Shaker for approximately 1 hour. The paint had a fineness of grind 5 (approximately 30 microns) as measured by a Hegman gauge. Steel shot was removed by passing the paint through a fine tooth strainer. A solution of 4.17 g of bis(tri-n-butyltin) oxide, 0.83 g of N,N-diethylhydroxylamine and 5.0 g of methyl isobutyl ketone was added to the above coating under high speed stirring. After complete dispersion, stirring was continued for an additional 5 minutes. The viscosity was measured at 25° C. using a Bruckfield viscometer model RVF-100 and a No. 4 spindle rotating at a speed of 20 rpm. The organotin acrylate copolymer solution used in the above composition was prepared by the method described in US Pat. No. 4,260,535. Relevant portions of the above patent specifications are incorporated herein by reference. After measuring the viscosity, an accelerated aging test was performed by placing the paint into a thermostatically controlled oven maintained at a temperature of 50°C. After 12 weeks, the viscosity increased from 800 to 1500 centipoise, which is considered acceptable for a commercial antifouling paint. In comparison, a paint with the same composition, except that bis(tri-n-butyl)tin oxide and N,N-diethylhydroxylamine were omitted, had an initial viscosity of 3100 centipoise. After 12 weeks at 50°C the viscosity increased to 22000 centipoise. The relationship between the viscosity increase observed in accelerated aging tests conducted at elevated temperatures and the viscosity increase observed at ambient temperature is such that 12 weeks at 50° C. is equivalent to one year at room temperature. Additional examples of stabilizer compositions of the present invention are shown in Table 1. These stabilizers exhibit a significant viscosity stabilizing effect compared to systems containing only solvent. It has been observed that the effectiveness of stabilizers having the same composition varies depending on the method of preparing the paint. As shown in Table 1, the viscosity stability of the coating is affected by the amount of polymer and stabilizer and the milling time during the milling and let-down steps in preparing the coating. If the processing conditions of the paint are taken into account, the TBTO/DEHA stabilizer system and
The comparison of the effects of TBTO is clearly shown in the table.

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