The composition of the paint or the paint base, the way to enhance the biocidal efficacy of the composition of the paint or the paint base

 

(57) Abstract:

The composition is used for marine and household paints, practically does not contain tin, lead and vanadium, contains biocide mixture peritioneal zinc salts and copper oxide (I) or copper thiocyanate. 2 S. p. f-crystals, 1 table.

The invention relates to the composition of the paint or paint base and the way to enhance the biocidal efficacy of the composition of the paint or the paint base. The composition or base paints according to the invention are used for marine and household paints.

The prior art paints containing pyrithione. For example, in U.S. patent 4039 312 described marine paint containing N-hydroxypyridinone connection and holodmor or haloalkaline, which are believed to provide a synergistic biocidal efficiency. However, the paint of this patent has not been utilized in industry, to the authors ' knowledge the present invention, it is possible, due to the relatively low number of total biocide specified in this patent is from 0.3 to 15%, preferably from 0.8 to 3.6 per weight of the composition of the paint.

Most industrial marine paint contains metals, such as tin, as biocidal additives. Recently was at the and, in paints and so-called "basic colors" (i.e. components of the paint before adding pigment) for reasons of toxicity. It was disclosed the use of other heavy metals such as vanadium, in paints and inks, as illustrated vanadium-containing composition in example 27 of U.S. patent 4918147 that also creates a problem of toxicity. Because these metals usually provide antimicrobial efficacy, for the production of paints in the industry need to replace antimicrobial additives in paints. In addition, they are highly desirable improved ink composition exhibiting enhanced antimicrobial efficacy. Moreover, the producers and consumers of marine paints conduct an intensive search for advanced marine paints exhibiting high antimicrobial efficacy against the growth of barnacles barnacles and other marine organisms.

The closest analogue of the invention is U.S. patent N 4918147, class C 09 D 5/16, 1990, which describes the composition of the paint, including paint, which contains a polymer resin, rosin, pigment, organic solvent and biocide.

The proposed composition according to the invention differs from the known fact that he's in to the m also described similar way to enhance the biocidal efficacy of the paint or the paint base, namely, that in the paint or paint base, introduce a biocide.

The difference of the proposed method is used as a biocide mixture peritioneal zinc salts and copper oxide (I) or copper thiocyanate in an amount of 10 to 75 wt.% calculated on the total weight of the paint or the paint base.

This invention relates to compositions of paint or the paint base, which practically do not contain tin, lead and vanadium and is characterized by enhanced biocidal efficacy, in which the composition of the paint or the paint base includes peritioneal salt and copper oxide (I) or copper thiocyanate, and specified peritonea salt is present in amount between about 5 and 50%, said copper oxide (I) or copper thiocyanate is present in amount between about 5 and 50%, and the total number peritioneal salt and copper oxide (I) or copper thiocyanate is between about 10 and 75% calculated on the total weight of the paint or composition of the paint base. In addition, the present invention relates to an improved method of increasing the biocidal effectiveness of the composition of the paint or the paint base, which contains almost no tin, lead and vanadium. This improvement includes adding the specified paint or to the salt is added in amount between about 5 and 50%, the specified copper oxide (I) or copper thiocyanate is present in amount between about 5 and 50%, and the total number peritioneal salt and copper oxide (I) or copper thiocyanate is between about 10 and 75% (preferably between about 20 and 75%) calculated on the total weight of the paint or composition of the paint base.

Increased biocidal efficiency achieved according to the invention, provides benefits to a large variety of colors, including household paints for indoors and outdoors. Particularly advantageous results are obtained when the method and composition of the present invention are used in combination with marine paints, for example for use when painting the hull. In addition, the composition and method of the present invention provide excellent results with paints like latex and alkyd types outside of the premises.

Typical paint composition may contain a resin, a pigment and various optional additives, such as thickening agents, moisturizing agents, and the like, as is well known in the prior art. The resin preferably is selected from the group consisting of vinyl, alkyl, epoxy, acrylic, polyurethane which may contain optional additives, which have a beneficial effect on viscosity, onlinemost and dispersion, and stability to freezing and to the action of electrolytes and the ability to foaming. If you are a marine paint, it preferably contains a swelling agent in order to give the ability to paint a gradual "peeling" in the marine environment, thereby resumes the biocidal effectiveness of newly exposed biocide (ie, pyritinol salt plus copper oxide (I) or copper thiocyanate) on the surface of the paint in contact with the aqueous environment of the sea. Preferred swelling agents are natural or synthetic clays, such as kaolin, montmorillonite (bentonite) clay mica (Muscovite and chlorite (geektonic) and the like. It was found that in addition to the clays other swelling agents, including natural or synthetic polymers, such as industrial available polymeren, are useful in the compositions of the invention in order to provide the desired effect of exfoliation. Swelling agents can be used as such or in combination. The preferred swelling agent is bentonite. The total amount of optional additives are preferred is the composition of the paint. Typical thickening agents include cellulose derivatives, such as methyl, hydroxyethyl, hydroxypropyl and carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, salts of polyacrylic acids and salts of copolymers of acrylic acid with acrylamide.

Suitable hydrating and dispersing agents include sodium polyphosphate, salt of low molecular weight polyacrylic acids, salts polyethersulfone acids, salts polyvinylformal acids, salts polimolekuly acid and salts of copolymers of maleic acid with ethylene, alpha-olefins having from 3 to 18 carbon atoms and/or styrene.

In order to increase the stability of the paint composition to the action of frost and electrolytes it can be added various Monomeric 1,2-diols such as glycols, propylene glycol-1,2 and butyleneglycol-1,2, or polymers, or ethoxylated compounds, for example the interaction products of ethylene oxide with long chain-alkanols, amines, carboxylic acids, inorganic salts of carboxylic acids, polypropylenglycol or poliatilenglikol.

The minimum film forming temperature (point clenched) of the paint composition may be polygenetic, butyldiglycol, benzene or alkylated aromatic hydrocarbons. As protivovspenivayushchie agents are suitable, for example, polypropylenglycol and polysiloxane.

The paint composition of the invention can be used as a paint for natural or synthetic materials, such as wood, paper, metals, textiles and plastics. It is particularly suitable as paint outdoors and is excellent for use as a marine paint.

This invention is additionally illustrated by the following examples. Unless otherwise specified, "parts" and"%" are "mass parts" and "mass%", respectively.

Example 1. The definition of a biocidal effectiveness of paints containing salt of pyrithione plus copper oxide (I) or copper thiocyanate.

A. Method of preparation of samples for testing. Inks were prepared in accordance with the following method. For dispersion of 42 g of resin ROSJNWW, natural wood resin (a product of the company Hercules Inc.) in 330 g of solvent was used ball mixer. The solvent consisted of 1 wt.h. xylene, 2 wt.h. of isobutyl ketone and 1 wt.h. carbitol. To the resulting company Pfizer Inc.) and a leveling agent (BEECH 307, silicone product company BIC Chemie) together with pyrithione zinc (zinc amadin, the product of the company Olin Corp.) and copper oxide (I) or copper thiocyanate. The amount of each component of the formulation given in the table.

The resulting mixture was kneaded for 3 hours until it is completely homogeneous and then added 62 g of ternary polymer vinyl chloride-vinylacetylene alcohol (vinyl UAGH, the product of the company Union carbide Corp.), and the resulting mixture is milled in a ball mill for 72 hours to obtain a paint composition.

The paint composition was applied to a fiberglass panel with the formation of the paint film, having a thickness of from 5 to 8 mils (1 mil=0.025 mm). The paint film was dried for about one and a half hours.

These film of paint on the fiberglass were tested in the marine environment in accordance with the following test mode.

B. test Mode.

The number of test samples prepared by the above method was tested in the ocean on marine research equipment away from Miami, pc. Florida. The panels were mounted on a raft under ASTM D 3623 test dive in order to simulate the hull of the ship at anchor. It was also the CSOs by spraying water on the ship at anchor. Previously it was found that during this test the waterline produces large quantities of marine organisms growing on the control panel. The test and the control panel was tested and photographed every 2 weeks for 5 months in order to document fouling. The test results are shown in table. As a comparison were prepared and tested test panel in a similar manner using industrial marine paint. One commercially available paint contained biocidal packaging polymer Mattinata presence of TBT and copper thiocyanate (industrial available as Interlux), and other industrial paint contained a greater concentration of oxide of copper as a biocide.

The results shown in the table, indicate that with the use of biocidal compositions of the present invention provides enhanced biocidal efficacy against a wide range of marine organisms, including barnacles barnacles, and microorganisms. More specifically, these results suggest that salt copper minimizes the number of barnacles growing crustaceans and microorganisms on painted surfaces fiberglass panel. This biocidal e is its toxic biocides for barnacles barnacles, such as ORGANOTIN compounds. Of course, when compared with the recipe interluxe containing ORGANOTIN compound, and which provides full fouling 10% (blue paint) and 60% (black paint) from the surface of panel during test dives to the waterline, the biocidal composition of the present invention provided in General increased biocidal activity, as can be understood from the data given in the table.

1. The composition of the paint or paint comprising a paint or paint base and a biocide, wherein it as a biocide contains a mixture pyritinol zinc salts and copper oxide (I) or thiocyanate copper 10 - 75% calculated on the total weight of the paint or the paint base, the mixture contains 5 to 50 wt.% peritioneal zinc salts and 5 to 50 wt.% copper oxide (I) or copper thiocyanate.

2. The way to enhance the biocidal efficacy of the composition of the paint or the paint base by introducing into the paint or paint base of biocide, characterized in that as a biocide use a mixture peritioneal zinc salts and copper oxide (I) or copper thiocyanate in an amount of 10 to 75%, based on the total weight of the paint or paint base, the mixture contains 5 to 50% peritioneal zinc salts and 5 to 50 wt.% the oxide is

 

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