KR20000015831A - Antifouling paint - Google Patents

Abstract

PURPOSE: Self-polishing marine antifouling paint compositions are provided, which have improved mechanical properties such as strength and resistance towards weathering. CONSTITUTION: The composition comprises rosin or rosin equivalent(s); one or more polymeric flexibilizer component(s); and optionally fibers. The rosin part preferably comprises ammonium or metal salts of rosin and/or rosin qualities having a low content of conjugated double bonds, i. e. a low degree of unsaturation. The flexibilizer components are non-crystalline, have a glass transition temperature (Tg) in the range of -45 to 25°C, and are selected from poly(meth)acrylates, polyacrylamides, copolymers and terpolymers thereof, acrylamide resins, acrylic acrylamide resins, polyvinyl ethers, polyvinyl esters, polyesters, polyoxy-C1,5-alkylenes, polyurethanes and epoxy esters. The fibers are natural or synthetic inorganic or organic fibers, metal fibers, or their mixtures, and preferably mineral fibers.

Description

Antifouling paint

In the shells of aquatic structures and vessels exposed to seawater and / or freshwater, green algae such as Enteromorpha spp. And Ulva spp., Diatoms such as Amphora spp, cocci, balanus ( Marine organisms, such as scallops, seaweeds, sponges, and hydros, such as Balanus spp.) Grow to increase friction (and thus increase fuel consumption), and to increase resistance to waves and currents (suspended structures such as coastal rigging equipment). Causes a significant economic loss due to the reduction of un-docking.

In order to solve such a pollution problem, several antifouling paint techniques have been developed. Some techniques are based on the principle of mixing biologically active agents into paints. However, in order to adequately control the satisfactory mixing and release of biologically active agents, the mechanical properties of the antifouling paint, such as the mechanical strength of the paint and the ability to adhere to other paints, may be compromised.

Another antifouling paint technique studied for many years is the use of self-wearing antifouling paint compositions, which contain trialkyltin derivatives of polymers containing carboxylic acids in the monomer moiety, i.e. alkyltin groups located at carboxylic acid groups. Included. However, many research efforts have been made to provide auto-wear antifouling paints that do not contain tin, due to the increased problem of port contamination caused by tin compounds. Self-wearing antifouling paints, on the one hand, have the inherent properties of self-wearing and the ability to mix well with biologically active agents, while on the other hand the mechanical strength of the paint film must be good, thus a binder system for self-wearing antifouling paints containing no tin. Research was a difficult task.

One way to obtain a binder system of antifouling paint, such as tin-free, antiwear antifouling paint, is to employ materials such as rosin or rosin equivalents as part of the binding system. Rosin or rosin equivalents have many desirable properties for antifouling paints; Because of their solubility in water, biologically active agents can be released into the water at a controlled rate. It is also compatible with many binder components; This facilitates the preparation of the final coating product. In addition, it is derived from natural resources that are readily available, relatively inexpensive, and self-renewable. Specifically, when a rosin or rosin equivalent is included in a high content, a rosin-containing paint having a high wear rate can be obtained because of the solubility of the rosin or rosin equivalent in water. However, the inclusion of rosin or rosin equivalents at high rates in order to ensure a suitable wear rate for practical purposes results in serious mechanical defects such as low cracking tendency and low resistance to weathering.

Therefore, due to the inherent mechanical deficiencies of such self-wearing binder systems, the wear characteristics of the binder system cannot be fully exhibited. Applicant's prior application, WO 96/15198, provides a solution to this problem, but as a result of further research, the present applicant has found significant improvements and alternatives to the invention described previously.

The present invention encompasses submerged structures which come into contact with water, in particular sea water, such as ships (boats, yachts, motorboats, motor launches, liners, tugs, tankers, container ships, submarines and all kinds of warships) Undesired contaminant organisms such as pipes, coastal and offshore machinery, and all kinds of structures and objects such as docks, stakes, bridge substructures, oil reservoirs under water, nets and other aquaculture facilities and buoys. Relates to anti-fouling paints that prevent the growth of adhesion.

The present invention relates to marine antifouling paints consisting of rosin or rosin equivalents, one or more polymer softener component (s) and fibers.

Marine antifouling paints according to the invention are preferably self-wearing antifouling paints.

The paints of the present invention contain rosin or rosin equivalents in a 15% proportion, even up to 80% by volume of solids of the paint and at the same time have satisfactory mechanical properties, so that they can be subjected to normal or even prolonged exposure to sunlight. It is intended to provide a practical antifouling paint for adoption for the purpose of preventing contamination, such as repetition of exposure / sun exposure that may occur on the surface of the ship.

Thus, the present invention utilizes the desirable properties of rosin or rosin equivalents in anti-fouling paints and is capable of improving anti-fouling properties, since the rosin or rosin equivalents are mixed while retaining or substantially retaining the important anti-fouling properties of the paint. The content of rosin or rosin equivalent can be increased. This may be accomplished by using polymeric softener component (s) in admixture with reinforcing fibers and rosin or rosin equivalents. Thus, by adjusting special requirements for the quality of the rosin or rosin equivalent and the polymer softener component, the properties of the antifouling paint may be improved.

As used herein, the terms "self-polishing" and "polishing" refer to the coating or paint in question when coated and dried under the test conditions of the abrasion rate test described herein. The removal of the coating material from the surface is intended to mean that the relative motion between the coated surface and the surrounding aqueous medium reduces the thickness of the coating at least 1 μm per 10,000 nautical miles (18,520 km).

As used herein, the terms "mechanically weak" and "mechanical defect" refer to (a) a small crack or a large crack when stretched 4 mm in the steel sheet elongation test of this specification, and (b) a laboratory cracking test of the present specification. It's about paint that is rated less than five.

Alternatively, the mechanical weakness or defect of the paint can also be identified by testing the paint with the direct impact test or the Mendel Test described herein; That is, the mandrel test of the present specification showing failure by testing the paint using a mandrel of 20 mm, or the direct impact test of the present specification where the test fails when the standard weight is dropped at a height of 40 cm. You can check it.

As used herein, the term "marine" refers to any kind of aquatic environment, such as salt, salty or fresh water. The term "locked" relates to a structure in contact with the marine environment.

As used herein, the term "% solids" is intended to mean the volume / volume percentage of the dry matter of the paint.

According to the invention, the paint contains not only fibers but also polymer softeners. The fibers may in principle be natural fibers or surface modifications, and any may be mixed into a mechanically defective antifouling paint, but preferably the machine of the antifouling paint tested in the laboratory cracking test herein. It is a fiber that can improve mechanical strength. As will be evident from the following manufacturing process techniques, the fibers may be added together with the remaining paint ingredients before or after grinding.

As used herein, the term "fiber" means any of the groups consisting of natural inorganic fibers, synthetic inorganic fibers, natural organic fibers, synthetic organic fibers and metal fibers or mixtures thereof, preferably inorganic or organic fibers or mixtures thereof. do. Moreover, the term "fiber" is meant to include both monofilaments, split fibers and stable fibers of any cross section. Thus, the term also includes bands, needles, whiskers and strips. The fibers may or may not be surface treated or coated.

However, the term "fiber" does not include materials used as fillers (e.g., asbestos-filled thixotropic agents and worn types of fillers, such as asbestos) (Hawley's condensed Chemical Dictionary, 11th Ed (Sax and Lewis, eds.), Van Nostrand Reinhold Company, New York, 1987, page 521).

Therefore, the ratio between the maximum unit (generally the average length of the fiber) and the minimum unit (generally the average thickness of the fiber) of the "fiber" used in the paint of the present invention is preferably at least 5, such as at least 10.

Examples of the inorganic fibers include carbide fibers such as silicon carbide fibers, boron carbide fibers and niobium carbide fibers; Nitride fibers such as silicon nitride fibers; Boron-containing fibers such as boron fibers and boroid fibers; Silicone fiber, alumina-boron-silica fiber, E-glass (non-alkaline marmoborosilicate) fiber, C-glass (non-alkaline or low-alkaline slaked lime-alumoborosilicate) fiber, A-glass (alkaline slaked lime- Silicate) fiber, S-glass fiber, CDMFIL-glass fiber, mineral-glass fiber, non-alkaline magnesium aluminosilicate fiber, quartz fiber, silicic acid fiber, silica fiber, high silica fiber, alumina high-silica fiber, alumino Silicate fiber, aluminum silicate fiber, magnesium aluminosilicate fiber, soda borosilicate fiber, soda silicate fiber, polycarbosilane fiber, polytitanocarbosilane fiber, polysilane glass, hydridopolysilazane fiber, tobermogite fiber Silicone-containing fibers such as samarium silicate fibers, olastonite fibers, potassium aluminum silicate fibers; Metal fibers such as iron fibers, aluminum fibers, bismuth fibers, martensium fibers, olfram fibers, molybdenum fibers, chromium fibers, copper fibers, germanium fibers, rhodium fibers, beryllium fibers, bronze fibers, aluminum nickel alloy fibers Their alloy fibers, such as copper, tin alloy fibers, steel fibers; Oxide fibers such as zircona fibers, alumina fibers, magnesium fibers, lead oxide fibers, indium oxide fibers, titanium oxide fibers, beryllium oxide fibers, nickel oxide fibers, sodium oxide fibers, yttrium oxide fibers and potassium tinate fibers; Carbon fibers such as pure carbon fibers, graphite fibers, slag wool fibers and charcoal fibers; Sulfide fibers such as zinc sulfide fibers and cadmium sulfide fibers; Phosphate fibers such as hydroxyapatite fibers, calcium hydrogen phosphate (brute) fibers, neodymium pentaphosphate fibers and silver phosphate fibers; Calcium aodite fibers; Calcium fluoride fiber; Mica fibers such as muscobit fibers, phlogofit fibers, and biotite fibers; Sodium aluminum hydroxycarbonate fibers; Rock wool fibers such as pure rock wool fibers and basalt rock wool fibers; Processed mineral fibers from mineral wool; Volcanic rock fibers; Montmorillonite fibers; Attapulgite fiber; Calcined bauxic fiber; Etc; Modified by any chemical or physical processing; And mixtures thereof.

Examples of natural and synthetic organic fibers include poly (p-benzamide) fibers, poly (p-phenylene-terephthalamide) fibers, poly (p-phenylene-2,6-naphthalamide) fibers, poly (3, 4-diphenylether-terephthalamide) fiber, poly (p-phenylene- (p-benzamide) -terephthalamide) fiber, poly (p-benzhydrazide terephthalamide) fiber, poly (m-phenylene-isope Deamide) Fiber, Poly (N, N'-m-phenylene-bis (m-benzamide) -terephthalamide) Fiber, Poly (N, N'-m-phenylene-bis (m-benzamide)- 2,6-naphthalamide) fiber, poly (N, N'-m-phenylene-bis (m-benzamide) -4,4-biphenyl-dicarboxamide) fiber, poly (4,4-bis (p-aminophenyl) -2,2'-bithiazole-isophthalamide) fiber, poly (2,5-bis (p-aminophenyl) -1,3,4-oxa-diazole-isophthalamide) Fiber, poly (4,4'-diaminobenzanilide-isophthalamide) fiber, poly (2-methyl-p-phenylene-2,6-naphthalamide) fiber, poly (2,6-dichloro-p Aromatic polyamide fibers such as -phenylene-2,6-naphthalamide) fibers; Aromatic polyhydrazide fibers such as poly (terephthalic-m-phenylene-hydrazide) fibers, poly (terephthalic-hydrazide) fibers, poly (p-phenylene-N-methyl-hydrazide) fibers; Poly (chloro-1,4-phenylene-ethylene-dioxy-4,4'-phenylene-4,4'-benzoate-co-terephthalate) fiber, poly (chloro-1,4-phenylene- Aromatics such as 4,4'-oxydibenzoate) fibers, poly (methyl-1,4-phenylene-4,4'-oxydibenzoate) fibers, poly (chlorophenylene-hexahydroterephthalate) fibers Polyester fibers; Aromatic polyazomethine fibers such as poly (nitrilo- (2-menyl-1,4-phenylene) nitrilomethylidine-1,4-phenylenemethylidine) fibers; Aromatic polyimide fibers such as aromatic polypyrromelitimide fibers and aromatic polyyltrimelitimide fibers; Polybenzimidazole fibers, such as poly- (2,2 '-(m-phenylene) -5,5'-bibenzimidazole) fibers, poly (2- (1,4-phenylene) -2'- Polybenzothiazole fibers such as (6,6'-bibenzothiazole)) fibers and poly (2- (1,8-phenylene) -2 '-(6,6'-bibenzothiazole)) fibers , Poly ((1,7-dihydrobenzo (1,2-d: 4,5-d ') dioxazole-2,6-diyl) -1,4-phenylene) fiber and poly ((benzo ( Polybenzoxazole fibers, such as 1,2-d: 4,5-d ') rapidazole-2,6-diyl) -1,4-phenylene) fibers, polyarylene-1,3,4-oxadia Aromatic heterocyclic polymeric fibers, such as polyoxadiazole fibers such as sol fibers; Alpha-cellulose fiber, beta-cellulose fiber, mineral cellulose fiber, methyl cellulose fiber, cellulose cotton, regenerated cellulose (laon) fiber, cellulose acetate fiber, jute fiber, cotton fiber, linen fiber, Ranie fiber, sisal fiber, heme fiber Cellulose fibers such as flex fibers, cyanoethylated cellulose fibers and acetylated cellulose fibers; Wood fibers such as pine, spruce and fir fibers, lignin fibers and lignin derivative fibers; Rubber fibers and rubber derivative fibers; Polyolefin fibers such as polyethylene fibers, polypropylene fibers, polytetrafluoroethylene fibers, polybutadiene fibers; Polyacetylene fiber; Polyester fibers; Modified acrylic fibers such as acrylic fibers and acrylic acid fibers, styrol / acrylate fibers; Acrylonitrile fibers such as acrylonitrile fibers and polyacrylonitrile fibers; Elastomeric fibers; Protein fibers such as casein fiber, mage protein fiber, soy protein fiber and peanut protein fiber; Alginate fibers; Poly (ethylene terephthalate) fibers; Polyvinyl alcohol fibers; Aliphatic polyamide fibers such as nylon fibers such as 6.6 nylon fibers, 6 nylon fibers, 6.10 nylon fibers; Polyvinylchloride fibers; Polychloroethene fibers; Poly (bisbenzimidazolebenzophenanthroline) fibers; Polyoxymethylene fiber; Polyurethane fibers; Vinyl polymer fibers; Viscose fiber; Modified by any chemical or physical processing; And mixtures thereof.

Preferred examples of the fibers are as follows: silicone containing fibers; Metal fibers; Oxide fibers; Carbon fiber; Rock wool fiber; Processed mineral fibers of mineral wool; Volcanic rock fibers; Olatonitite fiber; Montmorillonite fibers; Tobermorite fiber; Biotite fibers; Attapulgite fiber; Calcinede bowsheet fiber; Aromatic polyamide fibers; Aromatic polyester fibers; Aromatic polyimide fibers; Cellulose fiber; Wood fibers; Rubber fibers and derivative fibers of rubber; Polyolefin fibers; Polyacetylene fiber; Polyester fiber; Acrylic fibers and modified acrylic fibers; Acrylonitrile fibers; Elastomeric fibers; Protein fibers; alginate fibers; Poly (ethylene terephthalate) fibers; polyvinyl alcohol fibers; Aliphatic polyimide fibers; Polyvinyl chloride fibers; Polyurethane fiber; Vinyl polymer fibers; And viscose fibers; Fibers modified with chemical or physical treatments; And mixtures thereof.

Examples of particularly preferred fibers include E-glass (non-alkaline aluminoborosilicate) fibers; C-glass (non-alkaline or low-alkaline soda lime-alumoborosilicate) fibers; mineral-glass fibers; Olatonitite fiber; Montmorillonite fibers; Tobermorite fiber; Biotite fibers; Atulgitate fibers; Potassium aluminum silicate fiber; Metal oxide fibers; Rock wool fiber; Volcanic rock fibers; Calcined bauxite fibers and bauxite fibers; Aromatic polyamide fibers; aromatic polyester fibers; Cellulose fibers; Wood fibers; Fibers of rubber fibers and rubber derivatives; Polyolefin fibers; Polyacetylene fiber; Polyester fibers; Acrylonitrile fibers; Aliphatic polyamide fibers; And polyvinylchloride fibers; Ceramic fibers; Silicone fibers and aramid fibers; Fibers modified by chemical or physical treatments; And mixtures thereof.

Particularly preferred mineral fibers include mineral-glass fibers, olastonite fibers, montmorillonite fibers, tobermorite fibers, biotite fibers, atarulgit fibers, calcined bauxite fibers, volcanic rock fibers, bauxite fibers Mineral rock processed from rock wool, and mineral wool.

For example, examples of commercially available fiber types that improve the mechanical properties of model paint A in this specification (average fiber length is μm; average fiber thickness is μm):

1.Innorfil 061-10 ex Laxa Bruk AB (Sweden), synthetic mineral fiber (140: 4)

2. Innorfil 161-10 ex Laxa Bruk AB (Sweden), synthetic mineral fiber (140: 4)

3. Innorfil 361-10 ex Laxa Bruk AB (Sweden), synthetic mineral fiber (140: 4)

4. Innorfil 061-20 ex Laxa Bruk AB (Sweden), synthetic mineral fiber (160: 4)

5. Innorfil 461-20 ex Laxa Bruk AB (Sweden), synthetic mineral fiber (160: 4)

6. Innorfil 061-30 ex Laxa Bruk AB (Sweden), synthetic mineral fiber (200: 4)

7. Innorfil 061-60 ex Laxa Bruk AB (Sweden), synthetic mineral fiber (300: 4)

RF 5104 ex Kapinus Fibers BV (Netherlands), volcanic rock fibers (125: 5)

9.RF 5118 ex Kapinus Fibers BV (Netherlands), volcanic rock fibers (650: 5)

10.F PA 222/040 ex Schwarzwalder Textile-Werke (Germany), polyamide (500; 15-30)

11.F PA 240/040 ex Schwarzwalder Textile-Werke (Germany), polyamide (500; 15-30)

12. F PA 230/040 ex Schwarzwalder Textile-Werke (Germany), polyamide (500; 15-35)

13.F PAC 288/040 ex Schwarzwalder Textile-Werke (Germany), polyacrylonitrile (500 ;-)

14.F PES 231/040 ex Schwarzwalder Textile-Werke (Germany), polyester / polyamide (500; 10-20)

15.F PP 261/040 ex Schwarzwalder Textile-Werke (Germany), Polypropylene (500; -21

16.FB 1/035 ex Schwarzwalder Textile-Werke (Germany), cotton (400,3-12 / 10-40)

17.FZ 320/040 ex Schwarzwalder Textile-Werke (Germany), Paper Cellulose (400; 20-100)

18. F PAC O 245/040 ex Schwarzwalder Textile-Werke (Germany), pre-oxidized polyacrylonitrile (500; 10-12)

19.F 501/050 ex Schwarzwalder Textile-Werke (Germany), Jute (500; 30-500)

20.FG 400/060 ex Schwarzwalder Textile-Werke (Germany), E-Glass (230; 9-14)

21.FG 400/300 ex Schwarzwalder Textile-Werke (Germany), E-Glass (400; 9-14)

22.FG 400/100 ex Schwarzwalder Textile-Werke (Germany), E-glass (250; 9-14)

23.FG 440/040 ex Schwarzwalder Textile-Werke (Germany), E-Glass (150; 9-14)

24.F 500/1 S ex Schwarzwalder Textile-Werke (Germany), mineral glass (500; 4.4)

F 554/1 SR ex Schwarzwalder Textile-Werke (Germany), Rock Wool (500; 5)

26.F 580/1 S ex Schwarzwalder Textile-Werke (Germany), ceramics (500; 2.8)

27.Hostapulp ex Schwarzwalder Textile-Werke (Germany), polyethylene (500; 4.4)

28.Sylothix 51 ex Grace AB (Germany), polyethylene (200 ;-)

29.Sylothix 52 ex Grace AB (Germany), polyethylene + silica (400 ;-)

30.Sylothix 53 ex Grace AB (Germany), polyethylene + silica (100 ;-)

31.Arbocel BE 00 ex J. Rettenmaier & Sohne GmbH + Co. (Germany), Cellulose (120; 20)

32.Arbocel BC 1000 ex J. Rettenmaier & Sohne GmbH + Co. (Germany), cellulose (700; 20)

33.Arbocel BWW-40 ex J. Rettenmaier & Sohne GmbH + Co. (Germany), Cellulose (200; 20)

34.Lignocel C 120 ex J. Rettenmaier & Sohne GmbH + Co. (Germany), conifers (70-150 ;-)

35.Lignocel C 250 ex J. Rettenmaier & Sohne GmbH + Co. (Germany), conifers (150; 250)

36. Technocel 300 ex C.F.F. Cellulose-Fullstoff-Fabrik (Germany), Cellulose (65% <90 :-)

37. Technocel 300 ex C.F.F. Cellulose-Fullstoff-Fabrik (Germany), Cellulose (80% <90 :-)

38. Technocel 150 DU ex C.F.F. Cellulose-Fullstoff-Fabrik (Germany), Cellulose (95% <90 :-)

39. Technocel 90 Du ex C.F.F. Cellulose-Fullstoff-Fabrik (Germany), cellulose (65% <32 :-)

40. Technocel 400 C ex C.F.F. Cellulose-Fullstoff-Fabrik (Germany), Cellulose (-;-)

41.Recen PC ex Montefibre (Italy), acrylonitrile (-;-)

42.Nyad G ex Nyco Minerals (USA), Olastonite (length / diameter metaphor 15: 1)

43.M 40 ex Mesalles (Spain), rubber (60 ;-)

44.Tixal 102 ex Tixal (Germany), C-glass (-;-)

45.Tixal 202 ex Tixal (Germany), C-glass (-;-)

46.RCF-600 ex Sumitomo (Japan), C-glass (820 ;-)

47.CFR-160 ex Sumitomo (Japan), C-Glass (250 ;-)

48.RCF-140 ex Sumitomo (Japan), C-glass (175 ;-)

49.RCF-140 G ex Sumitomo (Japan), C-Glass (175 ;-)

50.RCF-140 N ex Sumitomo (Japan), C-glass (175 ;-)

51.Kevlar Txp (6F542) ex Du Pont (Sweden), (800; 12)

52.Kevlar Txp (6F539) ex Du Pont (Sweden), (1200; 12)

In view of the various fiber-containing compositions known in the coatings art, epoxy materials such as marine cladding compositions are characterized by E-glass fibers, C-glass fibers, A-glass fibers, S-glass fibers and ARG-glass fibers, which are not recognized within the scope of this invention. This is due in particular to the fact that epoxy materials are themselves recognized as "strong" mechanically.

The surface of the fiber may or may not be modified by chemical or physical processes. Examples of such deformations used in fibers to enhance the beneficial effects are: carbonization; Silylation; Corrosion such as treatment of alkali metal hydroxides, treatment of hydrofluoric acid; coating; Collection into a polyelectrolyte with a porous surface structure; Adsorption treatment; Hydrogen-bonding processes; Esterification process; Cationic bonding process; Anion bonding process; Copolymerization process; Crosslinking process; In addition, any deformation process included in the textile field, and the like.

When water soluble fibers are mixed with the autowear paint, the surface of the paint coating containing the water soluble fibers is smoother than the coating paint containing the insoluble fibers. As used herein, the term "water soluble fiber" is intended to mean a material having a solubility in water of at least about 1 mg / kg at least 25 ° C. as measured by ASTM Designation E1148. Examples of such water-soluble fibers include, but are not limited to, zinc oxide fibers, polyvinyl alcohol fibers, protein fibers, acrylic acid fibers, cellulose, and the like.

Without wishing to be bound by any theory, the above mentioned inorganic fibers, in particular mineral fibers, are the most important properties related to the ease of mixing in paints, i.e. in both the modified and the natural form, the fibers are not only rotatable as well as polymeric softeners. Preferred are mineral fibers having compatibility with the binder system based on the substrate.

Preferred fibers for the paints of the present invention may be significantly thicker than the paint additives or fillers commonly used in antifouling paints. The present invention is not limited to any theory, and it is believed that the relatively low volume concentration of much coarse fibers during the initial drying / curing of the paint can prevent small cracking, and therefore, because the concentration of micro cracking is lower, it is relatively The relatively coarse fibers of low area concentration can effectively prevent small cracking. Regardless of whether this is applied, the most important and valuable thing is that it can offset the known mechanical weaknesses of rosin-like materials as fibers at a concentration that does not interfere with the paint's abrasion or antifouling.

Preferred fibers (added to the paint during manufacture) have an average length of 25-2000 μm, an average thickness of 25 μm, a ratio of average length to average thickness of at least 5, an average thickness of 1-25 μm, average length and average thickness The ratio of is at least 10, preferably the average length is 50-300μm, the average thickness is 2-10μm and the ratio of the average length and the average thickness is at least 15, such as at least 20. It is also most preferable that the average length is 80-200 μm, the average thickness is 2-20 μm, and the ratio of the average length and the average thickness is at least 10.

The concentration of the fiber is generally 0.1-30% by solid volume of the paint, preferably 0.5-10%. In particular, the concentration of the fiber depends on the type and size of the fiber, but the solids volume of the paint is 2-10%, such as 2-7%, or 3-10%, such as 3-8%.

Preferred fibers according to the invention are, in 4 parts by volume, mixed in Model Paint A (without polymer softener or as described in Example 1) so that the cracking results in at least one grade, as a result of the laboratory cracking test described herein. Is preferably at least 2, in particular at least 3.

It can also be mixed with a biologically active agent (see below) to produce an autowear antifouling paint. In such cases, automatic wear resistant antifouling paints must be devised to control the release of the biologically active agent and to dissolve consistently for the entire coating life, typically for about 2-5 years. The optimal design and operation of anti-wear antifouling paints depends on several variables related to the ship's contour and navigational patterns. Temperature, degree of contamination, salinity, dry poison interval, speed, and range of activity are the main factors that improve the work of the paint. Therefore, it is necessary to produce antifouling paints with a wide range of wear rates so that the paint technology can be applied to many different types of boats.

In ships operating at low speeds in areas of high pollution, such as container ships sailing in Singapore, relatively fast self-wearing is required to release a sufficient amount of biologically active agent to keep the ship's shell clean. Antifouling paints, for example antifouling paints with a wear rate in the range of 10-30 μm per 10,000 nautical miles would be needed. On the other hand, ships on the highway have very high activity at moderate levels of pollution, such as those fishing on the beaches of Iceland, and relatively slow auto-wearing pollution with wear rates ranging from 1-3 μm per 10,000 nautical miles. Will need prevent paint.

Other types of rosin and rosin equivalents differ in solubility and relaxation points in seawater, which is apparent in the art. The wear properties of the paints also depend on the hydrophilicity and amount of the polymer softener and the amount of rosin type and its equivalents.

Thus, by relatively varying the amount of binder component (s), in particular rosin and rosin equivalent (s) and softener component (s), the paint technique required by the present invention is for example in the range of 1-50 μm per 10,000 dissociations. Wear rate must be adjusted.

As used herein, the term “rosin-based binding system” is intended to mean a binder phase of paint in which at least 30% of the solids volume of the overall binder system consists of rosin and rosin equivalents. As a subtraction, the rosin-based binding system can comprise one or several additional binding components up to 70% of the solid volume of the overall binder system.

Examples of such additional binder components are as follows:

Oils such as flaxseed oil and derivatives thereof; Castor oil and its derivatives; Soybean oil and its derivatives;

Polymeric binder components such as saturated polyester resins; Polyvinyl acetate, polyvinyl butyrate, polyvinyl chloride-acetate, copolymers of vinyl acetate and vinyl isobutyl ether; Vinyl chloride; Copolymers of vinyl chloride and vinyl isobutyl ether; Alkyd resins or modified alkyd resins; Hydrocarbon resins such as petroleum fractional condensate; Chlorolated polyolefins such as fluorolated rubber, chlorolated polyethylene, chlorolated polypropylene; Styrene copolymers such as styrene / butadiene copolymers, styrene / methacrylate and styrene / butadiene copolymers; Homopolymers and copolymers of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and isobutyl methacrylate; Copolymers of hydroxy-acrylates; Polyamide resins such as polyamides based on dimer tall oil fatty acids; Cyclized rubber; Epoxy esters; Epoxy urethane; Polyurethane; Epoxy polymers; Hydroxy polyether resins; Polyamine resins; Etc. and their polymers in addition to them.

Since the polymeric binder component has certain properties with respect to the glass transition temperature for the present invention, the result is a hard paint film combined with a rosin or rosin equivalent, a polymeric softener and other paint components as needed or desired. Can be formed. Thus, by definition, each of these polymer binder components has a glass transition temperature of at least 25 ° C., and preferably the Tg of each polymer binder component should be at least 30 ° C.

Each of the additional binding components may be auto wearable or insoluble.

As used herein, the term "rosin" is intended to mean gum rosin; Wood rosin of grades B, D, E, F, FF, G, H, I, J, K, L, M, N, W-G, W-W (defined by ASTM D509 standard); Natural rosin; Hard rosin; Yellow dip rosin; NF wood rosin; Tall oil rosin; Or resin or colophonium; In addition, any of the single components having the properties of natural rosin, for example, abietinic acid, abietinic acid, silvinic acid, dihydroxyabitinic acid, tetrahydroavietinic acid, dehydroabietinic acid, Neoabietinic acid, pimaric acid, levopimaric acid, isodextro-pimaric acid, sandarcopimaric acid, lalutrinic acid, dextrose-pimarinal, isodextro-pimarinal, suntro Ferrol, tartarol, grapecarpinic acid, phyllocladene. All other kinds of rosin components based on diterpene skeletons of handols, ferruginol, hemokiols, mannols, aminoyl oxides, ketomanoyl oxides, cativinic acid, eferuanic acid and abietinic acid; Besides their mixtures. The term “rosin” may refer to any of such compounds themselves, as well as mixtures of the abovementioned compounds.

As used herein, the term "rosin equivalent" refers to any type of rosin (mentioned above) that is modified or induced by any of the following chemical reactions or processes: polymerization / oligopolymerization; Esterification; Formation of metal salts / formation of metal resinates; Formation of ammonium salts; Decarboxylation; Hydrogenation; Dehydrogenation-hydrogenation / disproportionation / dismutation; adding; Oxidation; Isomerization; Acylation; Alkylation; Amidation; Ilylation; Diels-Alder reaction of maleinized and fumariated; Addition of 1,3-dipolar; Epoxidation; Formylation; Hydrocarboxylation; Hydroboration; Halogenation; Sign Language; Hydroformylation; Hydroxylation; Hydrometalization; Oxiamination; restoration; Sulfonation; Aminomethylation; Dicarbalcoxylation; Ozonolisis; Besides their mix.

Because the modified rosin's properties, ie water solubility and / or reactivity, have been modified, many of the reactions or processes mentioned above have rosin's that have better paint constituents in terms of improving mechanical properties and / or controlling the wear resistance. It is expected to produce equivalents. Thus, Diels- such as polymerization / oligopolymerization, formation of metal salts / formation of metal resinates, formation of ammonium salts, hydrogenation, dehydrogenation-hydrogenation / disproportionation / dismutation, maleisation and fumarisation Alder reaction; Isomerization is believed to produce rosin equivalents which are particularly advantageous for antifouling paints according to the invention.

Examples of commercially available rosin and equivalents of rosin are as follows:

(a) rosin; chinese Gum rosin WW ex China National Export (China); Colophony la ex Ciech (Poland); Gum Rosin WW ex Resipez (Portugal); Portuguese WW ex Q.V. Pound & Co. Ltd (United Kingdom); Honduras Balsamharz X ex C.E. Roeper (Germany); Breu WW ex Resiprates (Brazil); Breu WW No. 2 ex Markit (Brazil); Colofast Breu WW ex Shell (Brazil); Portuguese Gum Rosin Grade WW ex Calo Chemicals Inc. (United States); China Gum Rosin, Grade X ex Harima Kasei (Japan); Breutex ex Eucartex (Brazil); Colofonia WW ex Adrizyl (Brazil); Brazilian Y.2A Gum Rosin ex A.V. Pound & Co. Ltd (United Kingdom); Breutex Gum Rosin WW.X ex Hermann Ter Hell & Co (Germany); Sailboat Brand Rosin ex Wupoing Country Forest Products Chemical Factory, Qunzhhou, fujing Province (China); Resigral ex DRT (France); Gum Rosin High Grade WW / WG ex Dr. R. A. Stepanian (Austria);

(b) metallic rosin; Terpenato 620 NN 50 ex RESISA (Spain); Terpenato ND-0872 ex RESISA (Spain); Terpenato 670 ex RESISA (Spain); Bevires 130 ex BERGVIK (Sweden); Mangnesiumhartharz V 112 ex Robert Kraemer (Germany); Oulu 362 ex EITSILUOTO OY (Finland); MKK-1678 ex VEITSILUOTO OY (Finland);

(c) polymerized rosin; Erkapol 220 ex REBERT KRAEMER (Germany); Erkapol 209 ex ROBERT KRAWMER (Germany); Colophane Dismutee H ex GRANEL MUNOZ (Spain); Gresinox 578 M ex GRANEL MUNOZ (Spain); K-10 ex DRT (France); Bremar 85/7 ex ROBERT KRAEMER (Germany); Polyharz 9566 A / 60 ex ROBERT KRAEMER (Germany); Plyresin 60/2 REBERT KRAEMER (Germany); Bevitack 95X ex BERGVIK (Sweden); Bevitack 115 ex BERGVIK (Sweden); Bevitack HA ex BERGVIK (Sweden); Bevitack 320 ex BERGVIK (Sweden); Dertopol ex DRT (France); dimerex ex HERCULES (Netherlands); Poly + Pale ex HERCULES (Netherlands); Sylvatac 95 ex ARIZONA CHEMICALS (US); Oulumer 70 ex VEITSULUOTO OY (Finland);

(d) metal resinates of polymerized rosin: Resifor 205 ex URE (Spain); Erkazit L ex ROBERT KRAEMER (Germany);

(e) hydrogenated or partially hydrogenated rosin: Resin SH ex Andreas Jennow (Denmark); Resin H ex Andreas Jennow (Denmark); Foral AX ex HERCULES (Netherlands); Foral AX-E ex HERCULES (United States); Foralyn Resin ex HERCULES (Netherlands); Hydrogral ex DRT (France); Pinecrystal KR-85 ex ARAKAWA CHEMICAL INC (USA); KR-612 ex ARAKAWA CHEMICAL INC (USA); Hypal ex ARAKAWA CHEMICAL (USA); STAYBELITE ex HERCULES (Netherlands); STAYBELITE 570 ex HERCULES (Netherlands); Chinese Hydrogenated Rosin ex A.V. Pound & Co. Ltd. (United Kingdom); Foralyn ex HERCULES (Netherlands); Hydrogenated Gum Rosin ex Necarbo (Netherlands);

(f) esters of hydrogenated rosin: Foralyn 90 ex HERCULES (Netherlands);

(g) disproportionated rosin: Resin 731 D ex HERCULES (Netherlands); Residis ex URE (Spain); Recoldis 455 ex URE (Spain); Gresinox ex DRT (France); Recoldis ex GRANEL YMUNOZ (Spain); Recoldis A ex GRANEL MUNOZ (Spain); Dispro Rosin ex ARAKAWA CHEMICAL INC (USA); Gresinox 511 ex GRANEL MUNOZ (Spain); Gresinox 578 M ex GRANEL MUNOZ (Spain); Unitac 68 ex UNION CAMP (UK); And

(h) other types of modified rosin: Resin B-106, acid modified ester ex HERCULES (Netherlands); Resiester F-110, partially esterified fumaric acid rosin adduct ex URE (Union Resinera) (Spain); Resiester GR-51, adduct of maleic acid rosin esterified with glycerol ex URE (Spain); Resiester MR, monoethylene glycol ester ex URE of rosin (Spain); Resiester R-10, monoethyleneglycol ester of maleic acid rosin adduct ex URE (Spain); Colmodif 295 F, fumaric acid rosin adduct ex URE (Spain); Maleic anhydride rosin adduct ex URE (Spain); Resiester C, partially esterified fumaric acid rosin adduct ex URE (Spain); Colmodif R-330, maleic anhydride rosin adduct ex URE (Spain); Fokrapal SH, modified phenolic rosin ex ROBERT KRAEMER (Germany); Oulumer 75 E, ex VEITSILUOTO OY esterified as partially polymerized tall oil rosin and pentaerythritol; Oulumer 85E, partially polymerized and esterified tall oil rosin ex VEITSILUOTO OY (Finland); Sylvatac RX, stabilized tall oil rosin ex ARIZONA CHEMICALS (United States); Zonester 65, pentaerythritol ester of disproportionated tall oil oil rosin ex ARIZONA CHEMICALS (United States).

Rosin and rosin equivalents with free acidic groups (groups of carboxylic acids) can react with other components of the paint that are susceptible to action with the acidic groups, ie salts. Examples of such possible interactions between the components are inorganic oxides and hydroxides, such as zinc oxide, cuprous oxide and calcium hydroxide, which produce lead, copper, ammonium and calcium salts, respectively. Moreover, rosin or rosin equivalents can also react with ammonia and organic compounds such as amines so that the acid groups of rosin or rosin equivalents can be in the form of ammonium salts. This may occur before mixing the components using metal resins or other resinates, or by reaction between some paint components and the rosin or rosin equivalents, ie after mixing the paint components, whereby a chemical reaction / modification of the rosin or rosin equivalent may occur. Indicates that it may.

Thus, the term “rosin equivalent”, of course, is the product of the reaction formed by the reaction between the rosin or rosin equivalent contained in the composition and the other components of the paint composition, for example copper, which is the reaction product between cuprous oxide and rosin It is also intended to include resinates.

The advantage of using a metal resinate in place of rosin or rosin equivalent is that the strength of the paint is increased and the drying speed is faster compared to the same paint using unreacted rosin. Thus, in a preferred embodiment of the present invention, the rosin portion of the antifouling paint according to the present invention contains one or more of the following rosin metal salts: zinc resinate, copper resinate, aluminum resinate, calcium resinate and magnesium resinate , Preferably at least zinc resins, copper resins and calcium resins or mixtures of said metal salts. Such salts may be formed by mixing the rosin with other paint ingredients or by using the rosin itself.

Moreover, other resinates such as ammonium resinate have properties that can be an advantage of the antifouling paints of the present invention. An example of an amine that can react with a rosin or rosin equivalent to the corresponding ammonium resinate is the biologically active agent 2-methylthio-4-tert-butyl-amino-6-cyclopropylamine-s-triazine. It should be understood that mixing of metal salts with ammonium salts is possible within the scope of the present invention. In a further embodiment of the invention, the rosin portion of the paint comprises one or more ammonium salts.

As used herein, the term "rosin or rosin equivalent" is intended to mean any of the components within the meaning of "rose rosin", "rose rosin equivalent (s)" and mixtures thereof.

Some other properties of rosin can be used commercially for other purposes. See the list above. In order to obtain a paint composition that is sufficiently stable to weathering such as oxidation by oxygen dissolved in air or seawater and exposure to light, it is desirable to have a low content of rosin or rosin equivalent having a carbon-carbon double bond which is easy to oxidize. Do. Looking at the backbone of abienic acid, the tendency to react with oxygen is related to the presence of conjugated carbon-carbon double bonds; That is, abienic acid has two double bonds that are easy to oxidize.

One method of measuring the content of non-aromatic double bonds (actually the degree of unsaturation) in rosin samples (eg 100 mg / ml dissolved in CDCl ₃ ) is by using 1 H-NMR techniques. Resonance intensities from hydrogen atoms bonded to unsaturated carbon atoms (tetramethylsilane (TMS)) to the intensity of resonances from hydrogen atoms bonded to saturated carbon atoms (δ0.5-2.5 range; 100% compared to TMS) For δ4.8-5.3) is a suitable and reliable method for measuring the content of non-saturated carbon-carbon bonds (non-aromatic double bonds). Thus, it is also a suitable and reliable method of measuring the degree of oxidation of rosin samples. As can be practiced by one skilled in the art, the strength can be easily measured by using an NMR operating at least 200 MHz in combination with signal integration software.

Regarding the degree of unsaturation (as mentioned above), it is believed that the unsaturation value for rosin's natural raw material is about 6%. The beneficial properties of rosin are those having an unsaturation of less than 6%, preferably less than 4%, in particular less than 3.5%, in particular less than 3%.

Moreover, in one preferred embodiment of the invention, the rosin or rosin equivalent (s) is less than 40%, preferably less than 30%, more preferably less than 20%, 10% by weight of the abienic acid. Less than 15% by weight is particularly preferred. Since abietinic acid is not the only compound with two conjugated double bonds (neobiethic acid, palutrinic acid, and levoparic acid are other examples), the rosin or rosin equivalent used in the paint of the present invention An abietinic acid-type compound having two conjugated double bonds (ie, a compound having an abiotic acid backbone) is less than 50%, preferably less than 40%, such as 30%, particularly preferably less than 15% It contains less than 20%.

Ultraviolet spectroscopy (UV) technology or infrared spectroscopy (IR) (preferably Fourier transformation IR) technology can be implemented by one skilled in the art, for example, Naval Stores (Stump, JH ed.), Chapter 25: Quality Control (Tall oil, rosin and fatty acids), page 860 and as described in ASTM Designation D 1358-86 can be used to determine the content of abietinic acid and abietinic acid-type compounds.

In definition terms, the entire binder system contains at least 30% by volume of solids of the rosin or rosin equivalent. The amount of rosin or rosin equivalent is greater than 30%, such as greater than 40% of the solids volume of the binder system, in particular greater than 50%, or greater than 70%, of the solids volume of the binder system, such as greater than 60%. do. In an interesting embodiment of the invention, the content of rosin or rosin equivalent in the binder system ranges from 85-100%.

It is clear that the remainder of the rosin-based binder system consists of additional binder components such as oil and polymer binders. Thus, the content of the additional binder component is (by definition) less than 70% of the solids volume of the binder system. Preferably, the content is less than 60%, such as less than 50%, less than 40%, or less than 30%. In a specific embodiment, the content is 0-15% by solids volume of the binder system.

In a further preferred embodiment of the marine antifouling paint of the present invention, the content of rosin or herpes equivalent (s) is in the range of 15-80% by solids volume of the paint, preferably 20-70%, such as 20-60%. And particularly preferably 25-60%, such as 25-50%.

Moreover, the additional binder component is preferably 0-15%, in particular 0-20%, such as 1-10%, in the solids volume of the paint.

The total amount of binder component, ie rosin or rosin equivalent, oil and polymer binder components (both of which are called binder systems) is 20-70, such as 15-80%, preferably 25-60%, by the solids volume of the paint. %, Even more preferably 35-60%, such as 35-50%.

It has proven useful to use rosin or rosin equivalents in the form of metal salts, for example zinc salts, copper salts or calcium salts. Thus, in a preferred embodiment of the present invention, at least the rosin or rosin equivalent is in the form of a metal resinate, and the content of the metal resinate is preferably greater than 20% by volume of solids in the rosin-based binder system, more preferably greater than 40%. More than 30, most preferably more than 50%, such as 60%.

In a preferred embodiment of the marine antifouling paint of the present invention, the entire rosin-based binder system, i.e. rosin and rosin equivalent (s) and additional binder components, is hydrophilic, or when mixed with paint or in contact with the marine environment (hydrolysis) , Ion exchange, or mechanical wear) to become hydrophilic by chemical or physical processes (hydrolysis or complexation). Whether intrinsically or by one or more of these processes, the antifouling paint as a whole is automatically worn out.

As used herein, the term "hydrophilic binder system" ranges from 30-80 mN / m, such as 30-70 mN / m, preferably 40-80 mN / m, particularly preferably 50-80 mN / m, such as 60-80 mN / m. It is intended to mean a component characterized by having a surface tension in the m range.

An important and interesting feature of the antifouling paints of the present invention is the presence of a polymer softener, which is used to control the mechanical properties of the rosin-based binder system as well as the wear properties of the paint. As used herein, the term "polymer softener" should be understood to relate to one or several polymer softeners as defined below.

In order to distinguish between the polymer softener and the polymer binder system, the glass transition temperature of the polymer softener component is defined at up to 25 ° C.

Polymeric softener component (s) is a class of polymers that can be prepared with the selection of the appropriate monomers, which have glass transition temperatures up to 25 ° C; However, polymers derived from monomers selected from the following monomer classes are of particular interest:

Alkenes such as ethene, propene and butene;

Perhaloalkenes such as tetrafluoroethylene;

Dienes such as halo-1,3-butadiene, alkyl-1,3-butadiene such as isoprene, and alkoxy-1,3-butadiene;

Acrylates such as C _1-18 alkyl (meth) acrylates and methacrylates (known as (meth) acrylates), for example methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl ( Meth) acrylate, 2-profil (meth) acrylate, 1-butyl (meth) acrylate, 2-butyl (meth) acrylate, iso-butyl (meth) acrylate, and tert-butyl (meth) acrylic Rate; Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; Haloalkyl (meth) acrylates such as 2-chloroethyl (meth) acrylate; Hydroxy-C _1-10 -alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 1-hydroxy-2-propyl (meth) acrylate, and 2-hydroxy- 1-propylethyl (meth) acrylate; One, two or three in the benzene ring with benzyl (meth) acrylates and substituted homologues thereof, such as C _1-7 alkyl, C _1-7 alkoxy, hydroxy, thio, cyano, nitro or halogen Homologues having substituents; And polyoxy-Ci_ ₅ -alkylene (meth) acrylates such as polyoxyethylene (meth) acrylate and polyoxypropylene (meth) acrylate;

Styrene and alpha-methyl styrene with C _1-7 alkyl, C _1-7 alkenyloxy, C _1-7 alkoxy, hydroxy, thio, cyano, or halogen optionally substituted in the 2-, 3- or 4-position; Same styrene;

Acrylamide, NC _1-7 alkyl acrylamide (eg N-methylacrylamide and N-propylacrylamide), NC _1-7 dialkylacrylamide (eg N, N-diethylacrylamide), N-hydride Roxy-C _1-7 -acylacrylamide (eg N-methylloylacrylamide), and NC _1-7 -alkoxy-C _1-7 -alkylacrylamide (eg N-tert-butoxymethyl-acrylic) Acrylamides such as amides) (acrylamide as well as methacrylamide);

Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl ethyl butyl ether, vinyl hexyl ether, vinyl-2-ethylhexyl ether, and vinyl cyclohexyl ether;

Polyoxyalkylene allyl ethers such as allyl methyl ether, allyl ether ether, allyl propyl ether, allyl hexyl ether, allyl-2-ethylhexyl ether, allylcyclohexyl ether, and polyoxyethylene allyl ether;

Maleic acid, fumaric acid and maleic anhydride, as well as derivatives thereof; And

Vinyl esters such as straight or branched chain alkanoic acids of C _2-20 and vinyl esters of alkenoic acids.

It should be borne in mind that the aforementioned monomers are included in the homopolymer as well as the copolymer. It will be apparent to those skilled in the art that monomers of the same class as well as monomers of other classes form such copolymers.

The following homopolymers and copolymers are particularly suitable as examples of components of the polymer softener within the scope of the present invention.

Polyalkenes such as polyethylene, polypropylene and polybutene;

Polyalkenes such as poly (halo-1-butenylene), poly (alkyl-1-butenylene), and poly (alkoxy-1-butenylene);

Poly (meth) acrylates (polyacrylate-type polymers) such as polymers of the aforementioned acrylate and methacrylate monomers; In addition, acrylate, methacrylate, and acrylate / methacrylate copolymers, preferably any copolymers;

Copolymers of the aforementioned styrene monomers as well as polystyrenes such as polymers, and other copolymers of the above-mentioned styrene monomers with the above-mentioned (meth) acrylate monomers;

Polyacrylamides such as polymers and copolymers of the aforementioned acrylamide monomers;

Copolymers and terpolymers of the above-mentioned acrylamide and methacrylate monomers and the above-mentioned (meth) acrylates and styrene monomers, for example poly (styrene-co-acrylate ester-co-acrylamide) and poly ( Acrylate ester-co-ethylacrylate-co-acryl acrylamide resins such as ethyl acrylate-co-styrene-co-acrylamide;

("Polyacrylamide-type" polymer refers to polymers defined as polyacrylamide and "copolymers and terpolymers.")

Fluoro polymers;

Polyvinyl ethers of the aforementioned vinyl ethers (polyvinylether-type polymers) and copolymers thereof, particularly preferably any copolymers;

The esterified livers of C _2-20 straight and branched alkanoic acid, alkenoic acid, and alkadienoic acid are polyvinyl esters, and their copolymers, preferably any copolymers (eg, poly (vinyl acetate-co) Vinyl-larurate).

Moreover, the softener component may also be selected from other types of polymers, such as for example condensation of polymers:

Polyoxy-C _1-6 alkylenes and their homologues substituted with C _1-7 alcohols, halogens, cyano groups; C _2-15 -α, ω-dihydroxyalkanes such as cycloaliphatic as well as saturated, monounsaturated or diunsaturated aliphatic and aromatic C _4-30 di, tri or tetracarboxylic acids with propanediol, butanediol and pentanediol, And trihydroxyalkanes such as glycerol, and polyhydroxyalkanes and polyoxyalkylenediols, triols and tetraols, such as polyoxyethylenediols, polyoxyethylenetriols, polyoxyethylenetetraols, polyoxyethylene Polyesters such as polyesters from -co-polyoxyflopylenediol, polyoxyethylene-co-polyoxyflopylenetriol, polyoxyethylene-co-polyoxyflopylenetetraol and polyoxybunylenediol; Saturated polyesters, saturated hydroxy, low branched polyesters, unsaturated polyesters and oil free polyesters; Besides, other polyesters known in the field of the present invention are polyesters described in F. Pilati "Comprehensive Polymer Science". The Synthesis, Characterization, feactions & Application of Polymers ", Sir Geoffrey Allen (ed), Volume 5, 1989, pp 275-329 and A. Fradet, ibid., Pp331-344;

Aromatic and aliphatic reacted and unreacted polyurethanes and their hydroxy derivatives such as elastomeric polyurethanes; Besides, other polyurethanes known to those skilled in the art, such as K.C. frisch and d. Polyurethanes described in Klempner, ibid, Pp413-426;

Polysulfides such as poly (thio-isobutylene), poly (thio-methylene), poly (thio-propylene), poly (oxyethylene, dithioethylene), poly (oxyethylene, thioethylene) and others Vietti, dE well-known polysulfides exemplified by those described in pp533-542;

Polyamides such as R.J. Gaymans and D.J. Polyamides described in Sikkema, ibid., Pp357-373 and L. Wollbracht, ibid., Pp375-386;

Polyimines such as polyethyleneimine and other polyimines that are detrimental to those skilled in the art, such as those described in B. Sillion, ibid., Pp 499-532;

Epoxy esters such as epoxy-modified alkyd resins, such as short oil epoxy esters and epoxy modified conjugated dry fatty acids;

Polysiloxanes such as aliphatic and aromatic substituted polysiloxanes; And

In addition, any of the condensation polymers described in the applicant's publication WO 96/14362.

Particularly interesting polymers of these are: poly (meth) acrylates, polyacrylamides, in addition to their copolymers and terpolymers, acrylamide resins, acrylic acrylamide resins, polyvinyl ethers, polyvinyl esters, polyesters, Polyoxy-Ci_ ₅ -alkylenes, polyurethanes, and epoxy esters.

Particularly interesting polymers are the following types of polymers: polyvinylether-type, polyacrylamide-type, and polyacrylate-type.

It is believed that copolymers of all the aforementioned polymer types can be used; However, any copolymer is particularly advantageous because of the smaller tendency of crystallinity in this class. In addition, only one Tg can be measured for any copolymer.

Interesting examples of commercially available polymer softeners include PLEXISOL B-372 ex ROHM, Germany, PARALOID C-10 LV ex ROHM & HAAS, USA, ALBURESIN HA 14 ex ALBUS, Spain, SYNOCRYL 7013 ASB and SYNOCRYL839S ex CRAY VALLEY, Spain , LTW RESIN ex HULS, Germany, URACRON CS 106 XB, URACRON CS 104 M, URAFLEX EU 66 N, URAFLES EU 110 M1, URAFLEX EU 221 M1 ex DSM, Netherlands, JAGALYD FES 421 and JAGOTEX F 238 ex JAGER, Germany, LUMIFLON 552, NEOREZ U-480, and NEOREZ U-322 ex ZENECA, Spain, LUTONAL M40 ex BASF, Germany, LARODUR 103 RB ex BASF, Germany, WORLEEDUR MF 45 and WORLEEDUR D 46 ex WORLEE, Germany, and VINNAPAS B 100/20 VL and VINNAPAS B 500/20 VL ex WACKER, Germany.

If the homopolymers and copolymers described above are commercially available, these may be prepared by methods known in the polymer art.

In order to represent the full range of rosin-based antifouling paints according to the invention, certain criteria must be met with regard to the glass transition temperature and the average molecular weight of the polymer softener.

Thus, the glass transition temperature (Tg) of the polymer softener component (s) (as mentioned above) is defined below 25 ° C. Preferably the Tg is -45 to 25 ° C, such as -45 to 0 ° C, more preferably -45 to -25 ° C, such as -40 to -30 ° C, or -40, such as -35 to -25 ° C for some polymers. To -20 ° C, or even -20 to 0 ° C, such as -15 to -5 ° C. Tg in the range of -30 to 25 ° C. may also be applied to some polymers.

If at least one component of the polymer softener is preferably polyvinylether-type, most of such glass transition temperature (Tg) is preferably in the range -40 to -20 ° C.

Alternatively, if at least one component of the polymer softener is preferably polyacrylamide type, the glass transition temperature (Tg) of these components ranges from -30 to 25 ° C, for example -30 to -10 Preference is given to 0 ° C or 0-25 ° C.

Furthermore, if at least one component of the polymer softener is preferably polyacrylate-type, most of these glass transition temperatures (Tg) are preferably -30 to 0 ° C.

As a matter of definition, the average molecular weight of the polymer softener is at least 1,000.

In general, the average molecular weight of the polymer softener is preferably at least 2,000, in particular 2,000-25,000, such as 5,000-200,000, and more preferably 7,000-175,000.

Moreover, in order for the polymer softener to function fully, the polymer softener component must be an amorphous compound.

In a preferred embodiment of the invention, the polymer softener is comprised of at least 0.5% by volume of paint solids, preferably 0.5-40%, such as 1-20%, most preferably 2-20%, such as 2-15%.

Preferred polymeric softener components according to the invention are mixed in model paint A and tested in a laboratory cracking test (see Example 1) and have a cracking grade of at least 3, preferably at least 4.

Accordingly, the present invention also relates to a marine antifouling paint, comprising a binder system containing at least 30% by volume of solids of rosin or rosin equivalent, wherein the binder system is present in the paint in the above amounts and (i) Large cracking or small cracking at 4 mm extension indicates that the resulting cracking test has a rating of 5 or less, or (ii) no major component exists that offsets mechanical defects in the steel sheet elongation test herein.

(Iii) additionally contain more than one type of fibers, and when mixed in the volume of 4 parts by volume with model paint A, the cracking grade of model paint A is at least as tested in the laboratory cracking test described herein. 1; And

(Ii) additionally contain at least one polymer softener component, and these polymer softeners are mixed in model paint A and tested in the laboratory cracking test described herein and have a cracking grade of model paint A of at least 3.

A preferred example of marine antifouling paint according to the present invention is a paint in which a rosin-based binder system (a rosin and rosin equivalent (s) and additional binder components) is mixed with a polymer softener component (s) with a wear rate of 1-50 μm. At least 1 μm / 10,000 dissociation, such as the / 10,000 dissociation range, preferably 1-30 μm / 10,000 dissociation range;

In relative amounts, the mixture of rosin-based binder system and polymer softener was 60% by solids volume,

Zinc oxide (see Model Paint A) is 26% solids

Cuprous oxide (see Model Paint A) is 10% by solids volume.

Thixotropic bentonite (see Model Paint A) is 4% solids

And the polishing rate test described in this specification was performed.

Although the principle of using polymer softeners is for fiber containing paints containing high amounts of rosin or rosin equivalent (s), polymer softeners alone, i.e., offset the mechanical deficiencies of paints made of rosin-based binder systems. It can be explained that it can be used for paints that do not contain fibers. Thus, many polymer softeners can change (improve) the mechanical properties of a rosin-based binder system in a manner useful only by the polymer softener itself. Thus, the principles, mixing, and ranges mentioned herein in connection with the blending of fibers and softeners are equally applicable to those used alone as softeners.

With respect to the list of suitable polymer softener components, in addition to polyacrylamide, copolymers and terpolymers of (meth) acrylates, styrene and acrylamide monomers, acrylamide resins, acryl acrylamide resins, polystyrenes, polyvinyl ethers, polyvinyl esters , Polyamide polyimines, polyesters, polyoxyalkylenes, polyurethanes and epoxy esters are particularly suitable when used in rosin-high antifouling paints that do not contain fibers.

Since the paint of the present invention is an antifouling paint, it is advantageous to mix at least one biologically active agent in the paint in order to further improve the antifouling properties.

As used herein, the term "biologically active agent" is intended to mean a chemical compound capable of inhibiting the attachment and / or growth of marine life or a mixture of such compounds, and a substrate containing the biologically active agent. The suppression can be carried out by a lethal mechanism of life, by a mechanism that results in the suppression and / or control of the life without death or death, or by any mechanism that inhibits the attachment of the life without death or death. .

Examples of biologically active agents are as follows:

Organometals such as hydroxytripetylstannan, dibutylbis (1-oxododecyloxy) -stannan, fluorotriphenylstannan, tributylfluorostannan, chlorotriphenylstannan, tributyl Trialkyltins such as fluorostannan and tributyltin maleate; Hexabutyldistannoic acid; Trialkyltin copolymers such as tributyltin acrylate copolymer and tributyltin methacrylate copolymer tributyltin resinate; Bis (dimethyldithiocarbamato) zinc, ethylene-bis (1-hydroxy-2- (1H) -pyridinthionato-O, S- (T-4) zinc, ethylene-bis (1-hydroxy- Metallo-dithiocarbamates, such as 2- (1H) -pyridinethiona-O, S)-(T-4) copper; copper acrylate; bis (1-hydroxy-2- (1H) -pyridine Thionato-O, S)-(T-4) zinc, phenyl (bispyridyl) -bismuthdichloride; tributyltinoxide; tributyltinfluoride; triphenyltinfluoride;

Metal biocides such as copper metal alloys such as copper, copper-nickel alloys; Metal oxides such as cuprous oxide and cupric oxide (although only cuprous oxide and cupric oxide have dye properties, they are only recognized herein as biologically active agents); Metal salts such as copper thiocyanate, barium methaborate and copper sulfide;

Heterocyclo nitrogen compounds, for example 3a, 4,7,7a-tetrahydro-2-((trichloromethyl) -thio) -1H-isoindole-1,3 (2H) -dione, pyridine-tri Phenylmoran, 1- (2,4,6-trichlorophenyl) -1H-pyrrole-2,5-dione, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, 2 -Menylthio-4-tert-butyl-amino-6-ciflopropylamine-s-triazine, and quinoline derivatives;

Heterocyclic sulfur compounds such as 2- (4-thiazolyl) benzimidazole, 4,5-dichloro-2-octyl-3 (2H) -isothiazolone, 4,5-dichloro-2-octyl- 3 (2H) -isothiazoline, 1,2-benzisothiazolin-3-one and 2- (thioxyanatomethylthio) -ventthiazole;

Urea derivatives such as N- (1,3-bis (hydroxymethyl) -2,5-dioxo-4-imidazolidinyl) -N, N'-bis (hydroxymethyl) urea, and 3- (3,4-dichlorophenyl) -1,1-dimethyl urea;

Amides or imides of carboxylic acids; Amides or imides of sulfonic and sulfonic acids, for example 1,1-dichloro-N-((dimethylamino) sulfonyl) -1-fluoro-N- (4-methylphenyl) -methane-sulfenamide, 2 , 2-dibromo-3-nitnilo-propionide, N- (dichlorofluoromethylthio) -phthalimide, N, N-dimethyl-N'-phenyl-N '-(dichlorofluoromenyl Thio) -sulfamide and N-methyloyl formamide;

Salts or esters of carboxylic acids, for example 2-((3-iodo-2-propynyl) oxy) -ethanol phenylcarbamate and N, N'-dideyl-N-methyl-poly (oxyethyl) ammonium Propionate;

Amines such as dehydroabiethylamines and cocodimethylamine;

Substituted methanes such as di (2-hydroxy-ethoxy) methane, 5,5'-dichloro-2,2'-dihydroxydiphenylmethane, and methylene-bisthiocyanate;

Substituted benzenes such as 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile, 1,1-dichloro-N ((dimethylamino) -sulfonyl) -1-fluoro- N-phenylmethanesulfenamide and 1-((diiodomethyl) sulfonyl) -4-methyl-benzene;

Tetraalkyl phosphonium halides such as tri-n-butyltetradecyl phosphonium chloride;

Guanidine derivatives such as n-dodecylguanidine hydrochloride;

Disulfides such as bis- (dimethylthiocarbamoyl) -disulfide, tetramethylthiuram disulfide;

And mixtures thereof.

For antifouling paints, the total amount of biologically active agent (s) is 2-50%, such as 3-50%, preferably 5-50%, such as 5-40% by the solids volume of the paint. Depending on the type and specific activity of the biologically active agent, the total amount of the biologically active agent is, for example, 5-15% or 10-25% by the solids volume of the paint.

Typical antifouling paints according to the invention may consist of a rosin-based binder system, one or more polymer softener component (s), optionally at least one biologically active agent and possibly fibers. Moreover, antifouling paints may contain at least one or more components selected from pigments, fillers, dyes, additives and solvents. It should be understood that no solvent can be included in the content referred to as "% solids". Instead, the content of solvent (s) is expressed as "solid volume ratio" or SVR, which means the volume of the dry matter relative to the total paint volume comprising the solvent.

Examples of pigments include titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, titanium dioxide, black iron oxide, graphite, indanthrone blue, cobalt Aluminum oxide, carbanol dioxazine, chromium oxide, isoindolin orange, bis-acetoacet-o-tolidiol, benzimidazolone, quinalphthalone yellow, isoindolin yellow, tetrachloroisointolinone, kunolphthalone It is yellow grade. The characteristic of these materials is that they make the final paint opaque and non-translucent. Such pigments may further be selected from pigment-like components such as fillers. Examples of fillers are calcium carbonate, dolomite, talcum, mica, barium sulfate, kaolin, silica, pearlite, magnesium oxide, calcit and quartz powder. These materials do not render the paint non-translucent and do not contribute significantly to hiding any material under the paint coating of the present invention.

In a preferred embodiment of the invention, the paint has a total pigment content in the range of 1-60%, preferably 1-50%, particularly preferably 1-25%, of the solids volume of the paint.

Examples of the dyes include 1,4-bis (butylamino) anthraquinone and other anthraquinone derivatives; Toluidine dyes and the like.

Examples of additives are as follows:

Plasticizers such as chlorinated paraffin; Phthalates such as dibutyl phthalate, benzylbutyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate; Phosphate esters such as tricresyl phosphate, nonylphenol phosphate, octyloxypoly (ethyleneoxy) ethyl phosphate, tributoxyethyl potassium phosphate, isooxyl phosphate and 2-ethylhexyl diphenyl phosphate; Sulfonamides such as N-ethyl-p-toluenesulfonamide, alkyl-p-toluene sulfonamide; Phosphonic acid triethyl ester; Butyl stearate; Sorbitan trioleate; And epoxidized soybean oil.

Surfactants such as derivatives of propylene oxide or ethylene oxide such as alkylphenolethylene oxide condensates; Ethoxylated monoethanolamides of unsaturated fatty acids such as monoethanolamide of ethoxylated linolenic acid; Sodium dodecyl sulfate; Alkyl phenol ethoxylates; And soy lecithin;

Wetting agents and dispersing agents, for example, M. Ash and I. Ash, "Handbook of Paint and coating Raw Materials, Vol 1", 1996, Gower Publ. Ltd., Great Britain, pp821-823 and 849-851;

Antifoaming agents such as silicone oils;

Catalysts such as polymerization catalysts and initiators such as azobisisobutylonitrile, ammonium persulfate, dilauryl peroxide, di-tert-butyl peroxide, cupene hydroperoxide, p-toluenesulfonic acid; Desiccants such as metal octaate and metal naphthenate; And active agents such as salicylic acid and benzyl alcohol;

Stabilizers such as stabilizers against light and heat, such as hindered amine light stabilizers (HALS), 2-hydroxy-4-methoxybenzophenone, 2- (5-chloro- (2H) -benzotriazole -2-yl) -4-methyl-6- (tert-butyl) phenol, and 2,4-ditert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol; Stabilizers against moisture, such as molecular sieves or water scavengers; Stabilizers against oxidation such as butylated hydroxyanisole; Butylated hydroxytoluene; Propyl gallate; Tocopherols; 2,5-di-tert-butyl-hydroquinone; L-ascorbyl palmitate; Carotene; Vitamin A;

Polymerization inhibitors such as para-benzoquinone, hydroquinone and methylhydroquinone;

Corrosion inhibitors such as aminocarboxylate, calcium silicophosphate, ammonium benzoate, barium / calcium / zinc / magnesium salt of alkylnaphthalene sulfonic acid, zinc phosphate; Zinc petaborate;

Flocculants such as glycol, 2-butoxy ethanol, and 2,2,4-tribetayl-1.3-pentanediol monoisobutylate; And

Thickeners and anti-precipitants, such as colloidal silica, hydrated aluminum silicate (bentonite), aluminum tristearate, aluminum monostearate, linus oil, xanthan gum, salicylic acid, chrysotil silica, hydrogenated castor oil , And organomodified clays.

The paints according to the invention preferably contain 0-15% accumulation in the volume of dyes and additive solids.

Examples of solvents in which the components of the antifouling paint are dissolved, dispersed or emulsified include water (eg in the form of dispersions or emulsions); Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and benzyl alcohol; Alcohol / water mixtures such as ethanol / water mixtures; Aliphatic, cycloaliphatic and aromatic hydrocarbons such as white oil, cyclohexane, toluene, xylene and naphtha solvents; Ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; Ether alcohols such as 2-butoxyethanol, propylene glycol monofetyl ether and butyldiglycol; Esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; Chlorolated hydrocarbons such as methylene chloride, tetrachloroethane and trichloroethylene; And mixtures thereof.

Preferred examples of marine antifouling paints according to the invention are paints which consist of one or more pigment (s) and one or more solvent (s), as well as other necessary and preferred dyes and additives.

Antifouling paints can be prepared by any suitable technique commonly used in the paint industry. Therefore, various components can be mixed using a high speed disperser, a ball mill, a pearl mill, a triroll mill and the like. The antifouling paints according to the invention may optionally contain fibers, which may include fibers, white filter, petroleum filter, wire gap filter, wedge wire filter, metal edge filter, EGLM turnoclean filter (eg Cuno), DELTA strain Filtration may be carried out using a filter (eg Cuno) and a Jenag Strainer filter (eg Jenag) or vibration filtration.

The antifouling paints according to the invention can be applied to any of the offshore structures which are protected by any of the conventional techniques used in the paint art, for example, knots, rollers, pads, dipping, spraying and the like. The choice of the correct technique depends on the object being protected, the specific composition (such as its viscosity) and the specific situation. A preferred application technique is to spray and use a brush or roller.

Depending on the application, the paint preferably consists of a solvent having an SVR in the range of 30-70%.

The antifouling paints of the present invention may be applied to the protected marine structure in one or several successive layers, generally 1-5 layers, preferably 1-3 layers. The total dry film thickness (DFT) of the coated film applied per layer is generally 10-300 μm, preferably 20-250 μm, such as 40-200 μm. Thus, the thickness of the coating is generally 40-600 μm, such as 10-900 μm, preferably 20-750 μm, more preferably about 80-400 μm.

The marine structures to which the paint of the present invention is applied can be any of a wide range of solid objects in contact with water, for example, boats (boats, yachts, motorboats, motor launches, marine ships, tour boats, tankers, containers). Ships and other cargo ships, submarines (including nuclear and conventional) and all types of marine vessels; pipe; Beach and coastal machinery, structures and all types of objects, such as breakwaters, piles, bridge structures, drift devices, underwater oil well structures, etc .; Network and other aquaculture devices; Cooling plant; And buoys; And especially for bulletin boards and pipes of ships and boats.

Prior to applying the paint of the present invention to an offshore structure, the offshore structure may first be coated with an overcoat material-system, which may be several layers and any of the conventional overcoat materials applied to offshore structures. Thus, the primary material system may comprise a layer of tar or bituminous composition followed by a layer of adhesion-promoting primary material. In a preferred embodiment, the priming system is a composition having a wear rate of less than 1 μm per 10,000 nautical miles, ie the priming material is not an autowear coating.

As mentioned herein, the coating with the paint of the present invention is preferably abrasion resistant. Thus, the antifouling paint (actually a coating) should have a wear rate of at least 1 μm per 10,000 nautical miles (18,520 km). Preferably the wear rate is in the range of 1-50 μm, in particular 1-30 μm / 10,000 nautical miles (18,520 km).

More preferably, the coatings of the paints of the present invention exhibit excellent mechanical properties in various mechanical tests.

Therefore, in a preferred embodiment, the paint of the present invention is subjected to the steel sheet elongation test described herein, which is 5 mm elongated without showing a small or large cranking tendency, preferably 6 mm, more preferably 7 mm, such as 8 mm. .

A more preferred example of the antifouling paint of the present invention is the result of a mandrel test having a mandrel having a diameter of at least 16 mm, preferably at least 12 mm, particularly preferably at least 6 mm, such as at least 6 mm, as described herein. It is a paint that does not indicate any failure.

A more preferred example of the antifouling paint of the present invention is a paint that exhibits no failure, as a result of direct impact testing herein of dropping a standard weight at least 50 cm, preferably at least 60 cm, or at least 90 cm, such as at least 70 cm.

The optimal paint composition described herein will of course depend on the nature and properties of each component of the paint. Among these components, one of the most important and decisive factors for obtaining the desired compromise between mechanical strength and antifouling properties is the polymer softener. Thus, a particularly interesting example of the present invention is a marine antifouling paint of the following compositions:

(A) 1) rosin or rosin equivalent, which constitutes 5-18% by volume of solids in the paint; 2) an additional binder component constituting 0-15% by the solids volume of the paint; 3) fibers comprising 0.1-80% of the solids volume of the paint; 4) one or more amorphous polymer softener component (s) making up 1-20% by solids volume of the paint; 5) one or more biologically active agent (s) making up 2-50% of the solids volume of the paint; 6) one or more pigment components making up 1-15% of the solids volume of the paint; 7) dyes and additives which comprise 0-15% by solids volume of the paint; And 8) optionally one or more solvents.

(B) 1) rosins or rosin equivalents that make up 25-60% of the solids volume of the paint; 2) an additional binder component constituting 0-15% by the solids volume of the paint; 3) fibers comprising 2-10% of the solids volume of the paint; 4) at least one amorphous polymer softener component (s) comprising 1-20% by volume of paint, wherein at least one component is polyvinylether-type and has a glass transition temperature (Tg) of -40 to -20 ° C; 5) one or more biologically active agent (s) making up 2-50% of the solids volume of the paint; 6) one or more pigment components making up 1-15% of the solids volume of the paint; 7) dyes and additives which comprise 0-15% by solids volume of the paint; And 8) optionally one or more solvents.

(C) 1) rosins or rosin equivalents that make up 25-60% of the solids volume of the paint; 2) an additional binder component constituting 0-15% by the solids volume of the paint; 3) fibers comprising 2-10% of the solids volume of the paint; 4) one or more amorphous polymer softener component (s) comprising 1-20% by volume of solids of the paint, at least one component being polyacrylamide-type and having a glass transition temperature (Tg) of -30 to 25 ° C; 5) one or more biologically active agent (s) making up 2-50% of the solids volume of the paint; 6) one or more pigment components making up 1-15% of the solids volume of the paint; 7) dyes and additives which comprise 0-15% by solids volume of the paint; And 8) optionally one or more solvents.

(D) 1) rosins or rosin equivalents that make up 25-60% of the solids volume of the paint; 2) an additional binder component constituting 0-15% by the solids volume of the paint; 3) fibers comprising 2-10% of the solids volume of the paint; 4) at least one amorphous polymer softener component (s) comprising 1-20% by volume of solids of the paint, at least one component being polyacrylate-type and having a glass transition temperature (Tg) of -30 to 0 ° C; 5) one or more biologically active agent (s) making up 2-50% of the solids volume of the paint; 6) one or more pigment components making up 1-15% of the solids volume of the paint; 7) dyes and additives which comprise 0-15% by solids volume of the paint; And 8) optionally one or more solvents.

If necessary or desired, additional components may be included in these paints that are not explicitly mentioned.

Test method

Methyl isobutyl ketone was used to remove commercial oils prior to application of the primer / paint.

Laboratory Cracking Test

A test paint was applied on a steel sheet (10 × 15 cm ² ) to a dry film thickness of about 200 +/− 30 μm with a small hand spatula (doctor blade type). This plate was dried in a 60 ° C. oven for 2 days.

Anti-cracking performance was measured on a 0-10 scale.

10-100% of the area of the 0 steel sheet exhibited large cracking.

1 Large cracking occurred at less than 10% of the steel sheet area and / or small cracking occurred at 50-100% of the steel sheet area.

2 Small cracking was observed at less than 50% of the steel sheet area.

3-4 Both large cracks and small cracks were not observed, but the paint film crumbled badly when cut with a sharp knife.

5-6 cranking was not observed. The dry paint film showed some viscosity when cut with a sharp knife.

7-8 cranking was not observed. The dry paint film showed acceptable viscosity when cut with a sharp knife.

9-10 cracking was not observed. The dry paint film showed good viscosity when cut with a sharp knife. The uncut film 1 × ¹ cm ² showed some flexibility and strength.

Large cracking corresponds to medium and large size cracking sieve size types described in TNO circular 92.

Small cracking corresponds to the cracking sieve size type small size and micro size described in TNO circular 92.

Steel Panel Elongation Test

The cold wound steel sheet (15x3x0.1 cm ³ ) is coated by air spraying with 125 μm (DFT) of a commercial cobalt tar epoxy coating (Hempadur Tar Epoxy 15130 ex hempel's Marine Paints A / S). After drying for 12-36 hours at room temperature in the laboratory, the second coating is air sprayed with 80 μm (DFT) of a commercial vinyl primer (Hempanyl Tar 16280 ex Hempel's Marine paints A / S). After drying for at least 24 hours at room temperature in the laboratory, the coating is commercially coated twice with a known spray at about 100 μm (DFT) per coating (total model paint DFT: 200 μm). The interval between two commercial coatings is 24 hours. The plate is dried in an oven at 60 ° C. for 4 days.

Commercially, the test was performed three times by the following method in the Instron apparatus (Instron 4507) at 20-23 degreeC. This steel sheet was fixed to the sample pedestal. The pedestal of one sample was fixed in position and the other sample pedestal moved at a constant speed of 5 mm / min. The complete paint system and steel sheet were stretched until the paint film cracked. And elongation degree was measured. The more elongated, the better the mechanical properties.

Polishing rate test

A commercially available acrylic (13.5x7 cm ² ) with a curvature corresponding to the curvature of a cylindrical drum 1 m in diameter is 80 μm (DFT) of Komtar Tar Epoxy 15130 ex hemjpel's Marine Paints A / S, which is commercially available by air injection Coated with. After drying for at least 24 hours at room temperature in the laboratory, the coating is commercially coated twice with about 100 μm (DFT) per coat (total model paint DFT: 200 μm) (DFT of total test paint: 200 μm). The interval between two commercial coatings is 24 hours. 48 hours after the last coating, a commercially available, 1 cm wide band of a non-corrosive vinyl antifouling coating (Classic 76550 ex Hempel's Marine Paints A / S) is applied to each vertical edge by dipping. As a result, the central portion 5 cm wide remains uncovered with a non-corrosive coating. The plates were dried at room temperature in the laboratory for at least 1 week before testing.

The commercial market is secured to the convex surface of a cylindrical drum with a diameter of 1 m and is located at the Villanova y La Geltru test site in northeast Spain (North 41.2。N (Morale, e. & Arias, E., Rev. Iber. Corros. Y Port., Vol XIX (2), 1998, pp.91-96), rotated in salt water with an average temperature of 26 ° C. and salinity in the range 37-38 parts / 1000. The rotor was rotated at 15 knots circumference for a relative distance of 33,100 nautical miles I was.

Every 3-5 weeks, commercial pieces of paint (1.0 × 0.5 cm ² ) were collected in such a way that the surface of the market consisted of portions coated with both experimental and non-corrosive coatings as well as those coated with experimental coatings only. The pieces were immersed in paraffin wax and cut into microtomes. The cross section of the experimental coating was examined under a microscope. Exposed to the portion coated with the non-corrosive coating, the portion coated with the experimental coating showed a decrease in DFT corresponding to the wear rate. The wear rate (10,000 nautical miles (18,250 km)) was calculated.

Wear rate tests are generally conducted by Furtado, S.E.J. And Fletcher, RL, "Test Procedures For Marine Antifouling Paints. Food Pharmaceutical and Environmental Industries", pp 145-163 (1987) and Van London, AM, "Evaluation of Testing Mothods for Antifouling Paints", Journal of Paint Technology, 42, pp511 -515 (1970).

Mechanical property test-Acute test

A commercial polyvinyl butyral cleaning primer (Hempadur 15200, from Hempel's Marine Paints A / S) was coated on a steel sheet (15 × ¹⁰ × 0.5 cm ³ ) to 10 μm (DFT) by air spraying. After drying 12-36 hours at room temperature in the laboratory, the experimental model paint was once coated by air spraying to about 100 μm (DFT). Prior to testing, the plates were dried in the laboratory for 1 hour at room temperature and further dried in a 60 ° C. oven for one day.

This commercial was tested using a cylindrical mandrel according to ASTM Designation D522 using a cylindrical mandrel. The steel sheet was bent to a mandrel with a different diameter and examined for cracking. Gradually decreasing the diameter of the mandrel, determining the point of failure. The smaller the diameter, the better the mechanical properties. The mandrels with the following diameters were used (32, 25, 20, 19, 16, 13, 12, 10, 8, 6, 5, 4, and 3 mm).

Mechanical Properties Test-Direct Impact Test

A commercial polyvinyl butyral washing primer (Hempadur 15200, from Hempel's Marine Paints A / S) was coated on a steel sheet (15 × ¹⁰ × 0.8 cm ³ ) to 10 μm (DFT) by air spraying. After drying 12-36 hours at room temperature in the laboratory, the experimental model paint was once coated by air spraying to about 100 μm (DFT). Prior to testing, the plates were dried in the laboratory for 1 hour at room temperature and further dried in a 60 ° C. oven for one day.

Direct impact testing according to ASTM Designation D2794 was performed on this market. A standard weight (100 g; 20 mm indenter diameter) was knocked off the indenter and dropped from the height to deform the coating and substrate. As the weight dropping gradually increased, the failure point was determined. The farther the distance is, the better the mechanical properties. Initial height is 10 cm. The height was increased by 10 cm each time visually until failure was observed.

Determination of Average Molecular Weight (Mw) of Weights for Various Polymers

600E pump from Waters, Shoko Co., Ltd, Shodex KF 803 and KF 804 columns from Japan, 700 Satellite WISP autosampler, 410 Differential refractometer detector, and Millenium Ver. 2.10 Mw was determined using laboratory equipment consisting of HPLC and GPC software (all from Waters, USA).

The mobile phase of the system is tetrahydrofuran flowing at a low rate of 1 ml / min. The column temperature is 40 ° C. and the detector temperature is 35 ° C. Samples generally have 1% (w / w) polymer dissolved in tetrahydrofuran. (Use a high sample concentration if the detector signal is very low.) Use 15-100 μl of sample. Internal standards are as follows: Narrow polystyrene standards (Polymer laboratories, Ltd., UK) and toluene (Mw 92) with mean molecular weights 1,200,000, 128,000, 39,000, 5,700, 950, 280.

Determination of Glass Transition Temperature (Tg)

Tg was determined with a Perkin Elmer DSC-7 instrument at a heating rate of 0 ° C./min.

Table 1 shows an overview of the various polymer softener components tested in Example 1.

Sample Type of common polymer Tg / ℃ One Ethyl acrylate -11 2 Copolymer Based on Methylacrylate -8 3 Copolymer based on acrylamide -16 4 Terpolymers Based on Acrylamides -22 5 - 6 Unsaturated polyester -32 7 Terpolymers Based on Acrylamides 21 8 0 9 Reacted Polyurethane Aromatic - 10 Aliphatic -36 11 Aliphatic OH group -35 12 Epoxy ester -20 13 Hydroxy acyl -16 14 Fluoropolymer -11 15 Reacted Aromatic Polyurethane -29 16 -45 17 Polyvinyl methyl ether -30 18 Intramolecular Crosslinked Polyacrylate --- 9 19 Epoxy ester -One 20 - 21 Vinyl Acetate / Vinyl Laurate Copolymer - 22 - Reference polymer 100 Vinyl resin 49 101 Vinyl resin 42 102 Acrylic resin 52 103 Acrylic resin 58 104 Acrylic resin -55

Sample numbers correspond to the following commercial products:

Sample Name of the product producer One PLEXISOL B-372 ROHM, Germany 2 PARALOID C-10 LV ROHM & HAAS, USA 3 ALBURESIN HA 14 ALBUS, Spain 4 SYNOCRYL 7013 ASB CRAY VALLEY, Spain 5 SYNOCRYL 839 S 6 LTW RESIN HULS, Germany 7 URACRON CS 106 XB DSM, The Netherlands 8 URACRON CS 104 M 9 URAFLEX EU 66N 10 URAFLEX EU 110 M1 11 URAFLEX EU 221 M1 12 JAGALYD FES 421 JAGER, Germany 13 JAGOTEX F 238 14 LUNIFLON 552 ZENECA, Spain 15 NEOREZ U-480 16 NEOREZ U-322 17 LUTONAL M 40 BASF, Germany 18 LARODUR 103 RB BASF, Germany 19 WORLEEDUR MF 45 WORLEE, Germany 20 WORIEEDUR D 46 21 VINNAPAS B 100/20 VL WACKER, Germany 22 VINNAPAS B 500/20 VL Reference polymer 100 LAROFLEX MP 25 BASF, Germany 101 VILIT MC 31 HULS, Germany 102 ACRYLOID B-67 ROHM & HAAS, USA 103 ACRYLOID B-66 ROHM & HAAS, USA 104 ACRONAL 4F BASF, Germany

The invention is illustrated by the following examples.

Rosin is a very fragile substance. Paints made with rosin as the main binder component or sole binder component exhibit a pronounced cranking tendency. Laboratory cracking experiments were conducted on the effects of a number of polymer softener components on their anti-cracking rosin-based model paints and on the improvement of film integrity.

Model paint A was prepared having the following composition:

60 parts of zinc resin volume (Terpenato 620 NN50 ex Resisa, Spain)

10 parts of copper oxide volume with an average particle size of 2-4 μm (Nordox copper tetragraph paint grade, red, micromill ex NORDOX Industrier A / S, Norway)

26 parts of zinc oxide volume with a mean particle size of 0.2 μm (Zn oxide predominant red thread SR3S ex fabrica Expanola de Blanco de Zinc, S.A, Spain)

4 parts by volume of thixotropic bentonite (Bentone 38 ex NL Chemicals)

Optionally 16 parts by volume of the polymer softener (component) (see Table 1)

20-30% of the total wet paint weight of xylene

In general, model paints are prepared as follows:

200 ml of a completely mixed coating composition were introduced into a narrow 0.5L metal container with 100 ml of glass beads 2-8 mm in diameter. The vessel was placed in a mechanical stirrer and shaken for 45 minutes. The coating composition was separated from the glass beads by filtration.

Commercial grades of zinc resinate, copper oxide, zinc oxide and bentonite are also used in the following runs. The names of the products used in the following examples correspond to the softener component, the polymer binder component and the fibers listed above. See the fiber in Table 1.

Each step of the test series included no polymer softener as the reference paint. Table 2 shows the test results.

Polymer Softener Sample Number Laboratory cracking test Model Paint A One 9 2 5 3 4 4 4 5 4 6 6 7 4 8 4 9 10 10 7 11 6 12 6 13 5 14 4 15 6 16 6 17 6 18 6 19 4 20 4 21 7 22 7

Polymer Softener Sample Number Laboratory cracking test Model Paint A Reference Material 100 0 Reference Material 101 0 Reference Material 102 2 Reference Material 103 2 Reference Material 104 0 No softener 0

Alternatively, four parts were mixed with model paint A (without the polymer softener) in fiber volume to determine the appearance of the fiber alone. Fibers having a result of at least 1 are recognized to be particularly suitable for use in combination with emulsifiers. Model paint A was prepared as described above. The test results are shown in Table 3 and the fiber sample number corresponds to the list of commercially available fibers given in the specification.

Textile sample number Laboratory cracking test Model Paint A One 8 4 9 5 9 6 9 7 9 8 8 9 7 10 8 12 8 13 8 14 8 15 8 16 8 17 7 18 8 19 5 20 5 21 One 22 5 23 5 24 8 25 6 26 6 27 One 28 8 29 7 30 3 31 5 32 3 33 3 34 7

Textile sample number Laboratory cracking test Model Paint A 35 5 36 8 37 8 38 7 39 5 40 2 41 9 42 6 43 One 44 3 45 3 46 7 47 6 48 6 49 6 50 6 51 4 52 3 No fiber 0

Example 2

Various model paints B were tested to account for the beneficial effects of the polymer softener component (s), fibers as well as the combined effects of the polymer softener (s) and the fibers (see Table 4).

Model paints B1-B10 were prepared in the same manner as model paint A.

Paint number B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 Cuprous oxide 10 10 10 10 10 10 10 10 10 10 Zinc oxide 26 26 26 26 26 26 26 26 26 26 Benton 38 4 4 4 4 4 4 4 4 4 4 Zinc resinate 60 60 60 60 60 60 60 60 60 60 Lapinus RF5104 4 4 Nyad G 4 4 Inorphil 061-10 4 4 Lanco MIKAL 00180 4 4 Lutonal M 40 16 Synocryl ASB 7013 16 Plexisol B 372 16 Laroflex MP 25 16 16

Xylene was used as solvent to bring the solids by volume ratio to 50% in each of paints B1-B10. All ratios are% solids volume. Lanco MIKAL 00180 ex G.M. Langer, Germany, was used as a stable filler component in this and the following examples.

The increased mechanical strength of model paints B2-B7 for reference compositions B1 and B8-B10 is illustrated as steel sheet elongation test, direct impact test, mandrel test and laboratory cracking test, and is schematically shown in Table 5.

Model Paint Number Steel sheet elongation test Direct impact test Severe test Laboratory Cracking Test DFT (μm) Elongation at which film starts to break (nm) Height at which failure occurs (cm) Diameter of first mandrel where cracking occurs (mm) Worst 0Best 10 B1 250 1.3 10 32 2 B2 208 5.7 60 19 7 B3 176 12.2 80 3 9 B4 223 5.0 50 19 6 B5 169 7.3 60 19 7 B6 227 6.3 60 19 8 B7 216 15.1 80 3 9 B8 192 1.3 10 32 2 B9 244 1.4 10 32 2 B10 212 1.4 10 32 2

Example 3

The beneficial effect of the fibers with the polymer softener component (s) is further illustrated by the model paints C1-C12 and D1-D4 (test results see Tables 6, 7, and 8). Model paints C2-C7 and D2 are compositions according to the invention and model paints C1, C8-C12, D1 and D3-D4 are reference paints. Model paints C1-C12 and D1-D4 were prepared in the same manner as model paint A.

Paint number C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 Cuprous oxide 35.1 3.2 30.5 33.2 30.5 33.2 30.5 33 32.1 30.5 30.5 30.5 Zinc oxide 9.5 9 8.3 9 8.3 9 8.3 9 8.8 8.3 8.3 8.3 Kemira RD 2 4.7 4.5 4.1 4.5 4.1 4.5 4.1 4.5 4.3 4.1. 4.1 4.1 NUSA 5000007 2.1 2 1.8 2 1.8 2 1.8 2 1.9 1.8 1.8 1.8 Bentone 38 4.9 4.7 4.3 4.7 4.3 4.7 4.3 4 4.5 4.3 4.3 4.3 Zinc Resinate 43.7 41.3 38 41.3 38 41.3 38 41 40 38 38 38 Lapinus FR5104 5.3 5 5 Nyad G 5.3 5 Inorphil 061-10 5.3 5 Lanco MIKAL00180 5 5 5 Lutonal M 40 8 8 Synocryl ASB7013 8 Plexisol B372 8 Laroflex MP 25 8.4 8 8

In each of the paints C ₁ -C ₁₂ , xylene was used as the solvent to bring the solids volume ratio to 45%.

All ratios are expressed in% solids volume.

Kemira RD 2 ex kimira, Finland and NUSA 57 ex Nusa, Spain were used as titanium dioxide and additives in this and other examples.

Paint number D1 D2 D3 D4 Cuprous oxide 32.6 30 32.6 30 Zinc oxide 9.7 8.9 9.7 8.9 Kemira RD 2 4.3 4 4.3 4 NUSA 57 2 1.8 2 1.8 Benton 38 4.7 4.3 4.7 4.3 Zinc resinate 35.9 33 35.9 33 Laroflex MP 25 5.4 5 5.4 13 Inorphil 061-10 5.4 5 Lanco MIKAL00180 5.4 5 Lutonal M 40 8

In each of the paints D1-D4, xylene was used as the solvent to bring the solids volume ratio to 45%.

All ratios are expressed in% solids volume.

Model Paint Number Steel Panel Extension Test Direct impact test Severe test Laboratory crack test (DFT) (μm) Elongation at which cracking starts (mm) Failed Height (cm) Indicates the first mandrel diameter (mm) split 0 Worst 10 Best C1 230 1.5 10 25 3 C2 220 6.0 70 16 7 C3 208 9.2 80 5 8 C4 221 5.2 50 16 6 C5 225 6.0 60 16 6 C6 227 6.8 70 16 8 C7 217 7.3 80 5 8 C8 225 1.6 10 25 3 C9 210 2.0 10 25 3 C10 213 2.0 10 25 4 C11 233 5.2 60 12 7 C12 208 4.2 50 19 6 D1 230 4.5 50 19 6 D2 217 6.2 70 10 8 D3 226 2.0 10 25 4 D4 228 1.5 10 25 4

Claims (27)

1) rosin or rosin equivalent (s); 2) fibers; And 3) Marine antifouling paint consisting of one or more polymer softener component (s). The paint contains rosin or rosin equivalent at least 30% in solids volume, and (i) the paint is rated 5 or less as a result of the laboratory cracking test herein or (ii) any mechanical defect is offset. A binder system containing at least 30% of a rosin or rosin equivalent in a solids volume, wherein large cracks or small cracks appear when 4 mm elongated in the steel sheet elongation test of the present disclosure when no major component is present; (a) a mixture of 4 parts of Model Paint A and tested in the laboratory cracking test described herein further contains at least one type of fibers having a cracking grade of Model Paint A of at least 1; And (b) Marine antifouling paint, which further comprises one or more of a polymer softener component having a cracking grade of at least 3 as a result of mixing in model paint A and testing in the laboratory cracking test described herein. The marine antifouling paint according to any one of the preceding claims, wherein said paint further comprises at least one biologically active agent. The marine antifouling paint according to any of claims 1 to 3, wherein the paint is an autowear antifouling paint. The marine antifouling paint according to any of the preceding claims wherein the content of the rosin or rosin equivalent (s) is at least 30%, such as at least 50% by solids volume of the binder system. The marine antifouling paint according to any one of the preceding claims wherein the content of rosin or rosin equivalent (s) is in the range of 15-80% by solids volume of the paint. The marine antifouling paint according to any one of the preceding claims, comprising an additional binder component in an amount of 0-15% by volume of solids of the paint. The marine antifouling paint according to any one of the preceding claims, wherein the rosin or rosin equivalent (s) contains less than 30% of abiotic acid-type compounds having two conjugated double bonds. The marine antifouling paint according to any one of the preceding claims, characterized in that, when determined by the NMR method described herein, the degree of unsaturation of the rosin or rosin equivalent (s) is less than 3%. The marine antifouling paint according to claim 1, wherein at least a portion of the rosin is in the form of a metal resinate. The marine antifouling paint according to claim 10, wherein said metal resinate is selected from zinc resinate, copper resinate and calcium resinate. The marine antifouling paint according to claim 1, wherein at least a portion of the rosin is in the form of ammonium resinate. The marine antifouling paint according to any one of the preceding claims wherein the glass transition temperature (Tg) of each polymer softener component (s) is in the range of -45 to 25 ° C. The polymer softener component (s) according to any one of the preceding claims is a poly (meth) acrylate, a polyacrylamide, as well as copolymers and terpolymers thereof, acrylamide resins, acrylic acrylamide resins, poly A marine antifouling paint characterized by being selected from vinyl ethers, polyvinyl esters, polyesters, polyoxy-C _1-5 -alkylenes, polyurethanes, and epoxy esters. The marine antifouling paint according to any one of the preceding claims wherein the polymer softener component (s) comprises 1-20% by solids volume of the paint. The method according to any one of the preceding claims, 60% of the solids volume of the mixture of binder system and polymer softener in relative amounts Zinc oxide is 26% by volume of solids 10% by volume of copper oxide solids The binder system (the rosin or rosin equivalent (s) and optionally additional binder components) and the polymer softener when thixotropic bentonite was mixed in the model paint at 4% by solids volume and tested in the wear rate test described herein. (S) the marine antifouling paint, characterized in that it has a wear rate of at least 1 μm per 10,000 nautical miles. The marine antifouling paint according to any one of the preceding claims wherein the fibers are natural or synthetic inorganic fibers, natural or synthetic organic fibers, or mixtures thereof. 18. The marine antifouling paint according to claim 17, wherein the fibers are inorganic fibers, preferably mineral fibers. The marine antifouling paint according to any one of the preceding claims wherein the fiber has a ratio between average length and average thickness of at least 5. The marine antifouling paint according to any one of the preceding claims wherein the fiber concentration is in the range of 0.5-10% by solids volume of the paint. The marine antifouling paint of claim 1, further comprising one or more pigment (s), one or more dye (s) and additive (s), and one or more solvent (s). 1) rosins or rosin equivalents that make up 15-80% of the solids volume of the paint; 2) additional binder components making up 0-15% of the solids volume of the paint; 3) fibers comprising 0.1-30% of the solids volume of the paint; 4) one or more non-crystalline polymer softener component (s) constituting 1-20% by solids volume of the paint; 5) one or more biologically active agent (s) making up 2-50% of the solids volume of the paint; 6) one or more pigment (s) comprising 1-15% by solid volume of the paint; 7) dyes and additives which comprise 0-15% by solids volume of the paint; And 8) optionally one or more solvents Marine antifouling paint. 1) rosins or rosin equivalents that make up 25-60% of the solids volume of the paint; 2) additional binder components making up 0-15% of the solids volume of the paint; 3) fibers comprising 2-10% of the solids volume of the paint; 4) at least one non-crystalline polymer softener component which constitutes 1-20% by volume of paint and has at least one component polyvinylether-type and a glass transition temperature (Tg) in the range of -40 to -20 ° C. field); 5) one or more biologically active agent (s) comprising 2-50% by volume of solids in the paint composition; 6) one or more pigment (s) comprising 1-15% by solids volume of the paint composition; 7) dyes and additives which comprise 0-15% by solids volume of the paint; And 8) optionally one or more solvents Marine antifouling paint. 1) rosins or rosin equivalents that make up 25-60% of the solids volume of the paint; 2) additional binder components making up 0-15% of the solids volume of the paint; 3) fibers comprising 2-10% of the solids volume of the paint; 4) one or more non-crystalline polymer softener component (s) comprising 1-20% of the solids volume of the paint, at least one component being polyacrylamide-type and having a glass transition temperature (Tg) in the range of -30 to 25 ° C. ); 5) one or more biologically active agent (s) making up 2-50% of the solids volume of the paint; 6) one or more pigment (s) comprising 1-15% by solid volume of the paint; 7) dyes and additives which comprise 0-15% by solids volume of the paint; And 8) optionally one or more solvents Marine antifouling paint. 1) rosins or rosin equivalents that make up 25-60% of the solids volume of the paint; 2) additional binder components making up 0-15% of the solids volume of the paint; 3) fibers comprising 2-10% of the solids volume of the paint; 4) at least one non-crystalline polymer softener component (s) comprising 1-20% of the solids volume of the paint, at least one component being polyacrylate-type and having a glass transition temperature (Tg) in the range of -30 to 0 ° C. ); 5) one or more biologically active agent (s) making up 2-50% of the solids volume of the paint; 6) one or more pigment (s) comprising 1-15% by solid volume of the paint; 7) dyes and additives which comprise 0-15% by solids volume of the paint; And 8) optionally one or more solvents Marine antifouling paint. Marine antifouling paint consisting of rosin or rosin equivalent (s) and one or more polymer softener component (s). 27. The marine antifouling paint of claim 26, further defined by the characteristics defined in any of claims 3-16 and 21.