A coating composition for marine structures containing a soluble acrylic organotin polymer and a soluble metal-free acrylic polymer, in combination with an insoluble crosslinked organotin polymer, and an insoluble filler in a coating composition solvent can provide a tough, durable flexible coating and can provide extended protection to marine structures from the growth or accumulation of marine organisms.
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10. A marine structure having a durable, tough, flexible film that can release an effective amount of a marine biocide for a year or more wherein the film comprises:
(a) in a continuous phase, an effective film-forming, biocidal amount of a hydrophobic organotin acrylic polymer composition, and a film-forming metal-free acrylic polymer composition; and (b) dispersed in the continuous phase an effective biocidal amount of a discrete particles having a sufficiently small dispersable particle size of a crosslinked organotin acrylic composition and an effective biocide releasing amount discrete particles of an inorganic filler selected from the group consisting of a byorite, a silica, a silicate, a clay, or a mixture thereof.
21. A coating composition that can be applied to marine surfaces to form a durable, tough, flexible film and can release an effective amount of a marine biocide, which comprises:
(a) about 48 to 53 parts of the coating composition solvent; (b) a portion soluble in the solvent comprising 12 to 16 parts of a hydrophobic film-forming tri-n-butyl tin acrylic polymer, about 2 to 5 parts of the tin-free acrylic film-forming composition; and (c) a portion insoluble in the solvent comprising about 8 to 20 parts of a crosslinked tri-n-butyl tin acrylic composition and about 5 to 22 parts of an organic inorganic filler selected from the group consisting of a byorite, a silica, a silicate, a clay, or mixtures thereof; each component present per one hundred parts of the coating composition.
1. A coating composition that can be applied to marine surfaces to form a durable, tough, flexible film and can release an effective amount of a marine biocide, which comprises:
(a) an effective amount of a coating composition solvent; (b) a portion soluble in the solvent comprising an effective biocidal amount of a film-forming organotin acrylic polymer composition and an effective film-forming amount of a metal-free acrylic polymer composition and; (c) portion insoluble in the solvent comprising an effective biocidal amount of a crosslinked organotin acrylic polymer composition having sufficiently small suspendable particle size and an effective biocide releasing amount of an inorganic filler selected from the group consisting of a byorite, a silica, a silicate, a clay, or a mixture thereof.
24. A coating composition that can be applied to marine surfaces to form a durable, tough, flexible film and can release an effective amount of marine biocide, which comprises:
(a) an effective amount of a coating composition solvent comprising a mixture of mineral spirits and methanol; (b) a portion soluble in the solvent comprising about 10 to 15 parts of a copolymer of tri-n-butyl tin methacrylate and methyl methacrylate and about 3 to 4 parts of a film-forming methyl methacrylate; and (c) a portion insoluble in the solvent comprising a hydrophobic crosslinked tri-n-butyl tin acrylic composition; about 16 to 18 parts of an inorganic silicate filler; about 1 to 3 parts of a clay thickener and about 1 to 4 parts of carbon black; each component present per one hundred parts of the coating composition.
19. A coating composition that can be applied to marine surfaces to form a durable, tough, flexible film and can release an effective amount of a marine biocide, which comprises:
(a) about 45 to 56 parts of a coating composition solvent; (b) a portion soluble in the solvent comprising about 8 to 28 parts of a film-forming hydrophobic triorganotin acrylic polymer and about 1 to 6 parts of a metal-free film-forming acrylic polymer; and (c) a portion insoluble in the solvent comprising about 6 to 30 parts of the crosslinked organotin acrylic polymer composition having a particle size of about 1 to 250 microns and about 3 to 24 parts of the inorganic filler composition an inorganic filler selected from the group consisting of a byorite, a silica, a silicate, a clay, or a mixture thereof: each component present per one hundred parts of the coating composition.
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18. A method of inhibiting marine growth which comprises applying the coating composition of
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This invention was made with Government support under Contract N0060-76-C-1002theclays byorites, silica, and silicate compositions which can be dispersed in the coating composition solvent and which can cooperate with the hydrophobic triorganotin-containing acrylic and the film-forming acrylic in forming a hard durable marine coating. Typical silica or silicate fillers include silica (silicon dioxide), aluminum silicate, calcium silicate, magnesium silicate, mixed metal silicates, etc. Further information regarding silica fillers which can be used in the coatings of this invention can be found in Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edition, Volume 18, pp. 46-105, which discloses a great deal of information regrading silica, amorphous silica, vitreous silica, silicates and their associated properties.
The anti-fouling coating composition of the invention can also contain thickeners such as commonly available clays and modified clays which can be used to modify the viscosity of the composition in order to ease application. A commercial example is the Bentone family of products of NL Industries, Inc. Information regarding clays and their uses can be found in Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edition, volume 5, pp. 541-586.
The anti-fouling coating compositions can also contain pigments which can aid in indicating the amount and location of the coating composition, can aid in military camouflage and can aid in locating the marine structure. Such pigments can include titanium dioxide, black ferric oxide, carbon black, and others depending on the desired color. Further information regarding the nature and composition of other pigment compositions can be found in Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edition, Volume 15, pp. 495-605.
The anti-fouling coating compositions of the invention can contain a variety of other compositions such as surfactants, perfumes, preservatives, anti-foam agents, etc. which aid in the blending, handling and application of the coating composition.
The anti-fouling coating compositions of the invention commonly contain about 8 to 28 parts of a film-forming hydrophobic tri-organotin acrylic polymer, about 6 to 30 parts of the crosslinked hydrophobic organotin acrylate composition, about 3 to 24 parts of the inorganic filler composition, about 1 to 6 parts of the metal free film forming acrylic polymer, and about 45 to 56 parts of the coating composition. The preferred anti-fouling coating compositions of the invention commonly contain about 12 to 16 parts of the hydrophobic film-forming triorganotin acrylic polymer, about 8 to 20 parts of the acrylic hydrophobic crosslinked triorganotin acrylic composition, about 2 to 5 parts of the tin free acrylic film-forming composition, about 5 to 22 parts of the inorganic filler, and about 48 to 53 parts of the coating composition solvent. The most preferred anti-fouling coating composition of the invention contains about 10 to 15 parts of a hydrophobic organotin copolymer of tri-n-butyl tin methacrylate, and methylmethacrylate, about 8 to 9 parts of the acrylic hydrophobic crosslinked tri-n-alkyl tin acrylic composition, about 3 to 4 parts of a film-forming polymer of butylmethylmethacrylate, about 16 to 18 parts of an inorganic silicate filler, and about 50 to 55 parts of a coating composition solvent containing about 100 parts of mineral spirits with about 1 to 10 parts of methanol. The most preferred anti-fouling coating compositions can contain about 1 to 3 parts of a clay thickener, and about 1 to 4 parts of a pigment.
Into a number 2 Roalox mill jar was placed two quarts of small borundum grinding media (cylinders having 3/8 inch O.D. and 3/8 in length) and two quarts of medium grinding media (cylinders 1/2 inch O.D. and 1/2 in length). Into a separate number 3 Roalox mill jar was placed three quarts of small grinding media along with three quarts of medium grinding media. Into the number two jar was placed 75 grams of carbon black, 264.0 grams of an insoluble tri-n-butyl tin containing crosslinked resin made by reacting tri-n-butyl tin oxide with a copolymer of about 87 to 93 mole % methacrylic acid and 7 to 13 mole % of divinyl benzene, 528.0 grams of silica, 44.0 grams of a fumed silica, 880.0 grams of a 45 wt. % solution in mineral spirits of a tin containing acrylic polymer comprising a copolymer of tri-n-butyl tin methacrylate and methamethacrylate having 50 mole % tin containing monomer, 293.0 grams of a 40 wt. % solution in an aromatic naphtha solvent (90% mineral thinner and 10% ansco F.) homopolymer of butyl methacrylate having a molecular weight of about 75,000 and 441.0 grams of mineral spirits. The identical ingredients were placed in the number 3 Roalox jar except that the amounts were doubled. Into a separate 100 mL container was place 22.0 grams of a bentonite clay (Bentone 38) and 7.0 grams of 95 percent methanol. The mixture was blended until a paste was formed and the mixture was placed in the number 2 Roalox mill jar. After the paste was added, the mill jar was closed and sealed. A dry paste containing bentonite clay and methanol was prepared as exactly as above except that the amounts of the ingredients were exactly doubled. The dry paste was added to the #3 Roalox milljar. The mill jars were closed and sealed. Both Roalox were milled until the contents of the mill jar attained a Hagman number 5 fineness of grind (about 72 hours). The mill jars were opened and the resulting composition was emptied from each jar into a suitable container, retaining the grinding media in each jar. Into the number 2 Roalox jar was placed 500 grams of mineral spirits and into the number 3 Roalox was placed 1,000 grams of mineral spirits. The jars were rinsed with the mineral spirits and the contents of the jars and the coating compositions were combined and mixed until a uniform well disposed coating composition was formed.
Coating compositions of the Examples were tested on cold rolled steel panels having dimensions of 1/8 inch thickness, 10 inch width, 12 inch length with a 1/4 inch hole, 1 inch from 174 and a 1 inch hole centered along the top 10 inch edge. The panels were primed and two primed panels were coated with a 2 to 4 mill dry film of the coatings Examples I through IV.
The coatings of the application were also applied in stripes on ships hulls from the water line to the keel. The ships were operated in the Pacific and Indian Oceans, in the Atlantic Ocean and in the Mediterranean Sea in the ordinary course of naval operation. The results of the testing of the coated panels and ships is shown in Tables II and III.
| TABLE I |
| ______________________________________ |
| The method of Example I was repeated except that |
| the following amounts of ingredients were substituted |
| for the ingredients recited in Example I. |
| Example II |
| Example III Example IV |
| #2 Jar |
| #3 Jar #2 Jar #3 Jar |
| #2 Jar |
| #3 Jar |
| ______________________________________ |
| Carbon 75 150 80 160 15.6 31.2 |
| Black |
| Insoluble |
| 340 680 418 836 780 1560 |
| Tin Con- |
| taining |
| Resin |
| Silica 510 1020 501 1004 117 234 |
| Cabosil 20 40 25 50 -- -- |
| (silica- |
| fumed) |
| Bentonite |
| 21.25 42.5 21 42 19.5 39 |
| (Clay) |
| Soluble 850 1700 864 1728 1014 2028 |
| Tin Con- |
| taining |
| Resin* |
| Soluble Film |
| 283 566 209 418 195 390 |
| Forming |
| Metal |
| Free |
| Resin** |
| Mineral 910 1820 945 1890 516 1032 |
| Spirits |
| Methanol 8.5 17.0 7 14 7.8 15.6 |
| (95%) |
| Xylol*** -- -- -- -- 40 80 |
| Methyl-n- |
| -- -- -- -- 117 234 |
| butyl |
| Keton*** |
| ______________________________________ |
| *45 wt. % in mineral spirits |
| **40 wt. % in aromatic naphtha solvent |
| ***Added with mineral spirits |
| TABLE II |
| __________________________________________________________________________ |
| PANEL TEST OF COATINGS |
| Example No. |
| IV IV IV I I I IV I IV I |
| __________________________________________________________________________ |
| Number of |
| 1 1 1 1 1 1 1 1 1 1 |
| Panels |
| Site Miami |
| Pearl |
| Annapolis |
| Miami |
| Pearl |
| Annapolis |
| Pearl |
| Pearl |
| Pearl |
| Pearl |
| Film 2 to 3 |
| 2 to 3 |
| 4 2 to 3 |
| 2 to 3 |
| 4 4 4 4 4 |
| thickness |
| (mil) |
| Total Fouling |
| resistance (% free |
| of fouling) @ |
| 6 mos. 100 100 100 100 100 100 100 100 100 100 |
| 12 mos. 100 100 100 100 100 100 100 100 100 Lost |
| 18 mos. 100 95 100 100 100 100 100 100 100 |
| 24 mos. 100 80 100 100 100 100 100 100 -- |
| 30 mos. 100 eroded |
| 100 Lost |
| eroded |
| 100 100 -- -- |
| 36 mos. Lost 100 100 -- -- -- |
| 42 mos. 100 100 -- -- -- |
| 46 mos. -- -- -- -- -- |
| 52 mos. 100 100 100 100 100 |
| __________________________________________________________________________ |
| TABLE III |
| ______________________________________ |
| SHIP TEST OF COATINGS |
| WATER LINE TO KEEL STRIDE |
| Example No. |
| IV I |
| USS USS IV I |
| OUEL- OUEL- USS USS |
| Ship Name |
| LETTE LETTE INGRAM INGRAM |
| Stripe # |
| 1 2 1 2 1 2 1 2 |
| ______________________________________ |
| Area of 100 100 100 100 100 100 100 |
| Test |
| Stripe |
| (ft2) |
| ______________________________________ |
We have found that the ratio, in the most preferred compositions, between the amount of soluble tin containing resin and the amount of the insoluble tin containing resin, and the ratio between the total amount of tin containing resin (soluble and insoluble) and the nontoxic binder materials (the tin-free acrylic resins) are important to forming a high performance coating composition. We have also found that, in the most preferred compositions, the type and amount of inorganic filler is important to insure the effective diffusion of sufficient tin compound to the surface of the coating to produce a sufficient bioavailable amount of toxic tin compound. The ratio of the amount of soluble tin containing resin to insoluble tin containing resin is about 0.5 to 1.8 parts by weight of the soluble tin containing resin per each part by weight by of the insoluble tin containing resin. The ratio of tin containing resin (both soluble and insoluble) to metal free resin is about 5 to 16 parts by weight of the tin containing resins per each part by weight of the metal free resin. The amount of silica in the coating can range from about 4 to 18 weight percent.
The anti-fouling coating compositions of the invention are commonly compounded using commonly available mixing equipment. While the order of addition of components is not critical, typically the organic and the inorganic constituents of the coating composition are added to a mixer followed by the solvent. The blending equipment is operated until the mixture obtains a uniform appearance and the coating composition can be withdrawn from the mixing equipment and drummed.
The fully compounded anti-fouling coating compositions of the invention typically contain about 8.5 to 9.5 lbs. of coating composition per gallon, has a viscosity according to Federal Standard 141-A Method 4281 of about 50 to 100 KU, a tin content based on solids of about 5 to 25 wt-%, and can be applied at a rate such that the final dry film thickness ranges from about 1 to 15 mils or more. Commonly the coating compositions of the invention can be applied to generally metallic surfaces with a sprayer, a brush or a roller.
An examination of the data recorded in Tables II and III reveals that the novel, unique coating composition prepared in the Examples can provide protection to ships bottoms in the marine environment and can prevent fouling (85% to 100% resistance to fouling) for up to six years. Applicant's coating compositions were tested along with coating compositions made by others from tri-n-alkyl-methacrylate containing coating compositions prepared by others. However, we understand, from the navy, that only the coating compositions disclosed in this application produced a hard-tough coating that could provide resistance to fouling for more than one year.
The above specification Examples and data are provided to illustrate and to promote an understanding of the invention. However, since many embodiments of the invention can be made without departing from the spirit of or the scope of the invention, the invention resides in the claims hereinafter appended.
Castelli, Vincent J., Chappelow, Jr., Cecil C., Kimmel, Albert L.
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