DE1919324C2 - Anti-rust agents - Google Patents

Description

When coatings are used for metals, this is one of them Tackiness is undesirable for both aesthetic and safety reasons. Another Problem that has occurred with rust preventives of the type described,! Lays in the propensity of FH-men or coatings deposited with the agents on metal surfaces. have been chalky and to become brittle and eventually peel off and expose the metal backing if the plating is used for extended periods of time Periods of time is exposed to changing weather conditions.

The object of the present invention is to create new anti-rust agents with low tack (based on on the film deposited on surfaces with the solvent-based rust preventive is) and improved weather resistance than previously known rust inhibitors, which are less with water Are subject to emulsification as known, strongly basic, Metal-containing anti-rust agents !, which, particularly on metals, have a relatively thick film or coating result, with this film under changing weather conditions, such as intense sunlight, high relative Humidity and periodic rain, not being destroyed or flaking.

According to the invention, this object is achieved by a rust preventive agent of the type mentioned at the outset in that that there is 20 to 70% by weight of a volatile hydrocarbon solvent with an initial boiling point below 230 ° C and

a viscous high melting point dissolved in the solvent Composition containing from 5 to 80 wt .-% of the metal salt of an oil-soluble sulfonic acid as an oil-soluble dispersant, 5 to 45% by weight of the alkaline earth carbonate, the Weight percentage of the carbonate based on the non-volatile part of the viscous composition is, which has a boiling point above 230 ° C, and an effective amount of an organic, the weathering and the anti-rust agent stickiness-reducing agent of a natural or synthetic one Wax, a carboxylic acid with a molecular weight of at least 165 containing at least 10 carbon atoms contains and is solid at 38 ° C, a metal salt of this carboxylic acid or a mixture of waxes, Acids and / or salts, the waxes being organic, thermoplastic substances with a melting point between 38 and 149 ° C.

It has now been found that certain important properties of the rust preventive compositions of the type described can be improved if the chemical make-up of these known compositions is modified, either by the fact that the usually introduced non-volatile diluent! or carrier material is substantially eliminated, or more importantly and preferably in that the Composition of certain organic, weathering and tackiness reducing materials added will. The latter materials can be used in the rust preventive compositions in lieu of the total amount or a portion of the non-volatile diluent oil or carrier material ordinarily incorporated or the materials that reduce weathering and stickiness in addition to such a non-volatile diluent oil or carrier material can be added. The effect of the incorporation of the described wax and / or acid and acid salt additives in the compositions consists in reducing the tackiness of the rust preventive agents and, what is of more significant and practical advantage, the films that are discounted on Surfaces are applied. The incorporation of the additives described also improves the weather resistance the anti-rust film.

The amount of additives that are incorporated into the compositions can range from 0.5 to about 60% by weight based on the total weight of the composition is and depends on the particular one used Addition, it should be noted that mixtures or combinations of the various Additives can be used effectively in some cases. In all cases it will be effective Amount of additive incorporated to reduce the stickiness of the composition and its weather resistance to improve. This amount can be determined by routine tests within the specified limits to be determined. In either case, the additive used in the compositions is the To reduce stickiness and improve weather resistance, with the oil-soluble sulfonate dispersant used, and also with any non-volatile diluent oil that is In the composition can be used, compatible and preferably miscible. It is further desired that the additive used is resistant to the formation of emulsions with water and that it is at Temperatures below 38 ° C is a solid.

As already mentioned above, the compositions according to the invention are derived from a modification from the grease and rust preventive compositions that (a) by two-stage workwelsen from in the U.S. Patent No. 3,242,079, or (b) by a one-step process of the general type be produced as it is described in the above-mentioned German patent application, with qualitative similar reactants or starting materials as used together in the two Stages of the two-step process can be used. For a more complete explanation of the species and catfish in the compositions according to the invention are prepared, the one- and two-stage below Arbeltswelsen for the production of the already known strongly basic, metal-containing fat and rust preventive compositions Described in general terms.

According to the two-stage process described in US Pat. No. 3,242,079, a mineral oil solution is first used of a carbonized, basic alkaline earth metal salt. The salt is made by making a mixture an alkaline earth metal salt of a sulfonic acid and an alkaline earth metal base is carbonized. Theoretically it will assumed that a carbonate complex of the alkaline earth metal and the acid salt develops. the Carbonated mixture is characterized by having a "metal ratio" of at least 4.5. The metal ratio is given as the ratio of the total chemical equivalents of the metal In the Metal salt defined as the chemical equivalents of the metal that is in the form of a normal or neutral Salt of the sulfonic acid used is present. The complex is or can be soluble in mineral oil solvents be dispersed therein. When he disperses on these catfish there is an oil-soluble sulfonate dispersant, a non-volatile diluent oil and an alkaline earth metal carbonate complex.

For making the grease or rust preventive compositions from the mineral oil solution or dispersion

of the complex, the solution or the dispersion is treated with a compound having active hydrogen, for example alcohol or water or a mixture of alcohol and water. When carrying out this stage of fat production, the mineral oil solution should contain at least about 10% by weight of the carbonized basic salt and preferably at least 30% by weight of the mineral oil. The source of the mineral oil is not critical, but the oil preferably has a viscosity in the range of 50 Saybolt Unlversal-seconds at 38 ⁰ C up to 500 Saybolt Unlversal-seconds at 99 ° C. The amount of the active hydrogen compound or mixture of active hydrogen compounds used in the treatment of the mineral oil solution is 1 to about 80% by weight based on the weight of the metal salt present (both in the neutral metal salt dispersant and the metal salt present in the complex) . The reaction between the compound having active hydrogen and the carbonated, basic alkaline earth metal salt is preferably carried out. By refluxing the reaction mixture to drive off the volatile solvents and convert the mixture to the desired fat product. The fat products can be dissolved in a suitable light hydrocarbon solution! can be dissolved to form a rust preventive agent that can be applied as a film or coating to metal surfaces.

In another known two-step process, a colloidal dispersion is first prepared, which is a non-volatile diluent, an oil soluble Contains dispersant and an alkaline earth metal carbonate compound. The carbonate compound is preferred In the colloidal dispersion In the form of particles Formed in situ with an average diameter of 0.25μ or less. Method of manufacture of these colloidal dispersions are in U.S. Patents 3,150,089, 3,150,088, 29 56 018, 29 37 991 and 28 95 913 described, to which reference is made for the purposes of the description of the present invention.

In the second stage of this two-step process, the colloidal dispersion is made with a small amount (at least 3 wt .-%) water in the presence of a small Amount (about 0.5 to about 10% by weight) of an alcohol treated, which is typically a C, - bis Cic-alkanol, a monoether alcohol of ethylene glycol with up to 8 carbon atoms, a monoether alcohol of ethylene glycol or mixtures thereof. The mixture of colloidal dispersion, water and alcohol is heated until a modulation response tion takes place in which the liquid mixture is subject to a pronounced change in viscosity and in fat is converted. Either by carrying out the reaction in the presence of a volatile solvent or by adding such a solvent to the fat product, an easily applied rust preventive can be made getting produced.

In the already known one-step process for the production of strongly basic, metal-containing greases and rust prevention compositions, small amounts of water and alcohol are incorporated into a mixture of a non-volatile diluent oil, an alkaline earth metal carbonate complex and an oil-soluble dispersant, which is preferably an alkaline earth metal salt of a sulfonic acid . In this mixture, the amount of dispersant used is generally from about 2 to about 65 weight percent and the amount of non-volatile diluent oil is from about 5 to about 80 weight percent. The alkaline earth metal carbonate complex is generally present in the mixture in an amount from about 1 to about 25 percent by weight, and the water and alcohol are in amounts from about 1 to about 6 percent by weight and from about 1 to about, respectively 40 wt -.% present. The mixture can also contain up to about 60% by weight of a volatile processing solvent.

The mixture described is then heated under controlled conditions to turn the mixture into a Grease or rust preventive composition (after blending with a light hydrocarbon solvent) to convert. In order for the desired products to be obtained, the mixture must be at a temperature heated above 50 ° C, and it is still necessary to heat the mixture above 100 ° C, around the water, alcohol and light processing solvents within an acceptable range of time to remove from it. It is necessary, however, that when traversing the temperature zone from about 50 to about 100 ° C the rate of temperature increase does not exceed a certain maximum value if the amount of water present in the mixture is less than about 2.5 moles of water per mole of alkaline earth metal that is present as a carbonate complex.

Fat compositions resulting from the one- and two-step processes described generally contain at least 20% by weight of a non-volatile mineral oil diluent or carrier material, about 10 to about 80% by weight of the dispersant (alkaline earth metal salt) and about 5 to about 45% by weight .- ° _{0 of} the basic metal carbonate compound or the basic metal carbonate complex. When the fat compositions are dissolved in a light hydrocarbon solvent such as Stoddard solvent, they can be spray or brush applied to metal surfaces to provide relatively thick protective coatings with good rust preventive properties. Salt spray corrosion testing of metal surfaces coated on these catfish shows that the films or coatings thoroughly protect the metal against corrosion by the fog over long periods of time.

It has now been found, however, that the corrosion-promoting conditions which exist in the salt spray test, Widely used to determine the susceptibility of metals to corrosion, does not provide a useful indication of the ability of films or coatings of the type described to be long To withstand exposure to the open air or long periods of exposure to the elements. So is when mild steel materials coated with the strongly basic, metal-containing rust inhibitors described and in Oklahoma had been kept outdoors for six months, facing south, whitening or exuding of the rust preventive film occurred, accompanied by the onset of corrosion as it was quite brittle Coating flakes off and gets lost. There. "The same exudation and peeling of the coating occurs in one Period of about 2 to 4 months in the humid, rainy climate of southern Louisiana.

It has now been found that the cause of this exudation and peeling of the rust preventive film or coating in the loss of the non-volatile used Diluent oil or carrier material and also in loss of dispersant. this leads to for the deposition of potassium carbonate (lime) on the metal surface. The mechanism for this limescale formation or exudation and for the loss of

Thinner oil and sulfonate dispersant seem to act on the evaporation and oxidation of the oil and emulsifying the oil-soluble sulfonate salt with Attributed to rainwater. The conditions that cause the lime formation described and the loss of coating cause are the alternating periods of high temperature and intense sunlight and with heavy periodic rain that occurs when long-lasting, south-facing effects in the Free present.

It has now been found that by the invention Addition of an organic anti-rust agent that reduces weathering and stickiness Means in the strongly basic described. Metal containing greases and rust preventive compositions succeeds in reducing the formation of limescale and flaking of the rust inhibitor described.

The organic agents added according to the invention are to be described qualitatively in detail below will. Waxes that are useful in such adjuncts include synthetic and natural occurring waxes of animal, vegetable or mineral origin, whereby in the description of the present Invention "waxes" generally as cloudy or translucent organic thermoplastic substances a melting point between about 38 and 149 ° C are defined, such thermoplastics with organic, non-polar solvents form pastes or gels, are water-resistant, whitening properties possess, melt to liquids with relatively low viscosity and show no thread spinning phenomena. All Waxy substances which are suitable for the present invention have the common property of one long saturated carbon chain and most of them are fatty acid esters of alcohols other than Glycerins. However, in addition to the latter type of waxy materials, there are certain exceptions compared to the latter definition, which are still generally regarded as waxes, in the present one Invention in general also applicable. These include, for example, the Japan waxes, the Baywachsc (Mvrica waxes) and certain synthetic waxes.

The waxes that are preferably used in the compositions of the invention are Waxes derived from petroleum, such as microcrystalline, semi-microcrystalline and crystalline Waxes. Since the crystalline paraffir waxes are derived from the fractionated cuts that are produced during the distillation of crude petroleum are available, they are often referred to as petroleum distillate waxes to distinguish them from the so-called to distinguish microcrystalline waxes. that differ from certain tarry or more viscous residues derived from certain fractionations left in the petroleum refining process. The latter Waxes consist of mixtures of isoparaffins, naphthenes and small amounts of aromatic and straight chain hydrocarbons. They can be further distinguished from paraffin waxes in that than they are characterized by higher molecular weights and higher boiling points than paraffin wax. the microcrystalline waxes are also generally dukiil ^ r and show higher viscosities and higher refractive indices than the paraffin waxes. You make preferred Materials for use as tackiness reducing and weather resistance improving Agent in the anti-rust agents according to the invention. The amount of wax used in the anti-rust agents according to the invention used can range from about 0.5 to about 60 weight percent. Preferably the Wax content about 20 to about 50% by weight, based on the high melting point composition. Because the rust preventive is blended with a light solvent or are dissolved in a light solvent, which is about 20 to about 70 wt .-%, is the The wax content of these rust inhibitors ranges from about 0.10 to about 42 weight percent, and is preferably about 6 to about 35 weight percent.

The ones used in the rust inhibitors of the invention Carboxylic acids are preferably straight-chain aliphatic carboxylic acids of at least 12 and less than 24 carbon atoms. The acids used are of course intended to be compatible with the ones used in the rust inhibitors Dispersant and also with the non-volatile thinner! tolerable and preferably be soluble in it. Typical carboxylic acids useful in the present invention include Stearic acid, palmitic acid, tallic acid, tetradecanoic acid and oleic acid.

Although practically every metal salt of one of the carboxylic acids described shows some improvement in the stickiness and weather resistance of the rust inhibitors according to the invention, they are salts of the metals of groups IIA, HB and IHA preferred, while salts of metals from Group IHB, IVB, VB, VIB, VIIB and VIII are less preferred but better than Salts of metals of Group IA are. Aluminum, zinc, calcium and / or barium salts of stearic acid, Palmitic acid, tallic acid, tetradecanoic acid and / or oleic acid are particularly preferred.

The high melting point composition generally contains between about 0.5 wt% and less than 10% by weight of a carboxylic acid and / or a carboxylic acid salt. The high-melting composition preferably contains 1 to 4% by weight of at least one carboxylic acid and / or one carboxylic acid salt.

It has been found that a particularly effective Rust preventive agents with a view to applying rust preventive films or coatings to metal surfaces the high melting point composition about 40% by weight of a microcrystalline wax and Contains about 4% by weight aluminum stearate. The special ones Amounts of waxes, carboxylic acids or carboxylate salts or mixtures of these materials which are included in A specific rust inhibitor used is subject to considerable variation, such as from width of the specified ranges, and the optimum amount will vary depending on the other components the composition and the particular end-use application envisaged.

For a more complete description of the rust inhibitors according to the invention, the following are the oil-soluble ones Dispersants, which make up a major part of the high melting point composition, in more detail and described more fully. The term "metal" in "metal sulfonates" denotes the metals that are conventionally used can be used for the production of the metal sulphates available on the market. This includes Metal sulfates, which contain the metals sodium, potassium, magnesium, calcium and barium. at of the more suitable sulfonates, the metal of the metal sulfonate is the same as the alkaline earth metal found in the Rust preventive is present as a carbonate or as a carbonate complex.

The terms "oil-soluble sulfonates" used herein and "oil-soluble dispersants" refer to compounds with a hydrocarbon part with a

Molecular weight In the range of about 300 to about 1000. This molecular weight is preferably in the range from about 370 to about 700. The oil-soluble sulfonates can either be synthetic sulfonates or the so-called mahogany sulfonates or natural sulfonates be. The term "mahogany sulfonate" is considered understandable because it has been used extensively in the literature described 1st. The term "synthetic sulfonates" denotes sulfonates that are different from sulfonation starting materials that are synthetically produced. Synthetic sulfonates include alkyl sulfonates and alkarylsulfonates. This also includes substances with cycloalkyl groups (i.e. with naphthenic groups) In the rare chains associated with the benzene ring. The alkyl groups can be straight-chain or branched be. The alkaryl radical can be derived from benzene, toluene, ethylbenzene, xylene isomers or naphthalene.

An example of an oil-soluble alkaryl sulfonate (a synthetic sulfonate), which is particularly useful in the rust inhibitors according to the invention, is that as Postdodecylbenzenesulfonate known material. Postdodecylbenzene is a residue product from manufacturing of dodecylbenzene. The alkyl groups of postdodecylbenzene are branched. Postdodecylbenzene consists of monoalkylbenzenes and dialkylbenzenes in the approximate molar ratio 2: 3 and has the following typical properties:

specific weight at 38 ° C
average molecular weight
% sulfonable O O 0 O O 341.5
361.2
379.5
404
413.4 0.8649
385
88 ASTM-D-158 Engler: ⁰ C 415 initial boiling point,
5
50
90
95 Final boiling point Refractive index at 23 ° C 1.4900 Viscosity at: -23.3 ° C, cp
- 6.67 ° C, cps
4.44 ° C, cps
26.7 ° C, cp - 31.7 2800
280
78
18th Aniline point, ⁰ C 69 Pour point, ° C

An example of another oil soluble synthetic Alkaryl sulfonate, which is particularly useful in the rust inhibitors of the invention, is the sulfonate, which is derived from a sulphonation starting material, known as "dimeric alkylate". Like postdodecylbenzene, "dimeric alkylate" has branched branches Alkyl groups. Briefly summarized, dimeric alkylate is produced by the following steps:

(1) Dimerization of a suitable starting material, for example cat-poly gasoline and

(2) Alkylation of an aromatic hydrocarbon with the polymer formed in step (1).

A Friedel-Crafts alkylation sludge is preferably used as the catalyst in the polymerization step. This Arbeltswelse and the resulting product are in the German patent application P 15 18 650.2 described.

An example of another oil-soluble synthetic Alkaryl sulfonate useful in the present invention, especially in admixture with at least 60% by weight of one of the sulfonates mentioned above, is that Sulphonate, derived from a sulphonation material known as "NAB residue". NAB residue or stripped »N-alkylene« residue consist mainly of Dl-n-alkaryl compounds, wherein the alkyl groups contain 8 to 18 carbon atoms. They differ from the above-mentioned foundation materials mainly in that they are straight-chain and contain a large amount of oil-substituted Material included. A method of making these materials and the resulting product are Described in the German patent application P 15 68 268.5. Another method of making a DI-n-alkaryl product is in the German patent application P 15 68 271 described.

To complete the description of the present invention, reference is made to the German patent applications P 15 18 650.2, P 15 68 271.0 and P 15 68 268.5 are referred to.

Other sulfonates that can be used include, for example, mono- and polywax-substituted naphthalene sulfonates, Nonylnaphthalene sulfonates, diphenyl ether sulfonates, naphthalene sulfonates, diphenylamine sulfonates, Dicetylthianthrenulfonate, Dllauryl- / J-naphtholsulfonate, Dicaprylnitronaphthalene sulfonates, unsaturated paraffin wax sulfonates, hydroxyl-substituted paraffin wax sulfonates, Tetraamylenesulfonates, mono- and polychlorosubstituted paraffin wax sulfonates, Nltrosoparaffin wax sulfonates, cycloaliphatic sulfonates, such as laurylcyclohexylsulfonate, mono- and polywax-substituted Cyclohexyl sulfonates and the like.

Below are some of the non-volatile diluent oils and carrier materials

4u described the other than the organic ones described Agents can be introduced into the rust inhibitor. These materials are generally characterized by that they have a boiling point above about 230 ° C and in the Disperslonsmittel used are soluble. Examples of non-volatile diluent oils or carrier materials that can be used Lubricating oils obtained by any conventional refining process include synthetic Lubricating oil, for example polymers of propylene, polyoxyalkylenes, polyoxypropylene, dicarboxylic acid esters and esters of phosphoric acids, vegetable oils such as corn oil, cottonseed oil and castor oil, and animal oils Oils, such as bacon oil and spermacet oil. The rust inhibitors according to the invention preferably contain at least 20% by weight of a non-volatile diluent oil. The ones used in the rust inhibitors of the invention Alkaline earth metal carbonates are preferably calcium, magnesium, barium and strontium carbonates, with the calcium salt being most preferred.

As for the method of incorporation of the described, tack-reducing and weather resistance Improving Organic Agents In the rust preventive agents of the present invention, it has been found that familiarization can be achieved. By adding the waxes, acids or metal salts into the mixture or Solution introduced or dispersed, which in the case of the two-stage process with a compound with active hydrogen is implemented, or in the case

of the one-step process is heated to convert the mixture into the desired products.

The following examples illustrate the invention. In the examples, the percentages given relate to on components or reactants in each case to percentages by weight of the total compositions.

Comparative example 1

The present example and example 2 illustrate the weather resistance, the rust preventive films typically show that are made from rust preventive agents by a typical one described above Two step processes have been established.

A colloidal dispersion of potassium carbonate, prepared by the process described in US Pat. No. 3,150,088, containing about 30% by weight of calcium sulfonate and about 43% by weight of light oil diluent and having an acetic acid base number of 300 is used converted into a fat by reacting it in an operational fat kettle at 94 ° C for about 1 hour with 10% by weight of water and 0.5% by weight of ethylene glycol monomethyl ether (methylcellosolve). The volatiles of the composition are then removed by heating at 182 ° C _{for about 1/2 hour.} The ASTM Elndringung of the resulting fat is at 77 ⁰ C for about 171st

The fat product described is In Stoddard solvents, a mixture of hydrocarbons with a boiling range of about 155 to about 218 ° C and a flash point in the open container of about 41 ° C. The amount of used in the solution Stoddard solvent is 70 -96 by weight. A steel plate is immersed in the rust preventive agent to apply a film to the steel plate, which after evaporation of the solvent has a thickness of about 22.6 μ.

In order to simulate long-term exposure of the coated steel plate to southerly outdoor weather conditions, the plate is placed in a conventional weatherometer, in which artificial, accelerated weathering is carried out. Be! According to this text, the coated metal is subjected to a 102 minute "dry cycle" in which bright, artificial sunlight is shone on the metal, the temperature is about 74 ° C and the relative humidity is between 60 and 7096. This dry cycle is followed by an artificial "rain cycle" in the weatherometer, which lasts 18 minutes, during which the steel plate is sprayed with water while artificial sunlight is directed against the plate. The temperature during spraying is salaries at about 6O ⁰ C and the relative humidity is between 80 and 100%. The weatherometer is operated continuously (24 hours a day), with the above cycles being repeated alternately. The 22.6μ film deposited with the rust preventive prepared in the manner described in the present example begins to show lime formation and whitening after 1 day in the weatherometer, and rusting of the steel plate begins after 5 days in the weatherometer.

Comparative _{Example 2 fi5}

According to that described in U.S. Patent 3,150,088 In the process, a strongly basic calcium sulfonate dispersion is made in the following manner:

A mixture of an oil-soluble sulfonic acid (the Acid contains about 10% by weight of hydrocarbon oil (apart from sulfonic acid), Stoddard solvent, η-hexane and a small amount of a mixture of 70% by weight of water and 30% by weight of ethylene glycol monomethyl ether is produced. This mixture is added at a temperature of 30 to 38 ° C in a range of 15 Minutes of sufficiently carbonated calcareous alcoholate complex of the type described in US Pat. No. 3,150,088 given to neutralize the sulfonic acid. The mixture is then made overbased, by simultaneously at a temperature of 38 to 40 ° C a lot of carbonized calcareous alcoholate complex and a mixture of water and methyl cellosolve in one Weight ratio of 70:30 can be added. The water / methyl cellosolve blend is spread in a tent 48 minutes and the complex is added over a period of 60 minutes.

After the simultaneous addition of the water / methyl cellosolve mixture and the alcoholate complex, the solvents boiling below 150 ° C. are removed by distillation, followed by stripping with carbon dioxide gas at a temperature of 150 ° C. for about 15 minutes. The resulting dispersion contains about 30 wt -.% Calcium sulfonate, 5 parts by weight 96 non-volatile hydrocarbon oil, and 38.296 Stoddard solvent and shows a Elssigsäure base number of 308.

According to the two-stage Arbeltswelse for producing a rust-proofing agent, the dispersion described in the preceding paragraph is reacted 96 parts by weight of methyl cellosolve in a Laboratoriumsfettmlscher for a tent range of 1 hour at a Rücknußtemperatur of about 94 ⁰ C with 10 wt .-% of water and the first The water and alcohol are then removed from the mixture by distillation. The resulting fat is diluted with additional Stoddard solvent until a flowable, thixotropic product is obtained containing about 70% by weight of the Stoddard solvent. A steel plate is immersed in this rust preventive and the solvent is allowed to evaporate, leaving a residue layer or film coating on the plate which is 25.4 microns thick. The 25.4 micron film on the steel plate is then tested in the weatherometer in the manner described above. After 1 day of tenting, the film begins to show limescale build-up and whitening, and the steel plate also begins to rust.

Comparative example 3

An attempt was made to determine the tendency towards calcification of those produced by the typical two-step process Reduce rust inhibitors and improve your weather resistance by adding such Compositions have incorporated materials that would normally be expected to be improve the stability and weatherability of such films. So were a lot of the example above 1 prepared fat product 0.5 wt. 9b of a commercially available ultraviolet rays absorbent Material and also 0.5 wt .-% of a commercially available antioxidant added (the percentages by weight are on the non-volatile part of the In Comp. example 1 produced fat composition based). This material is then immersed in a 70 wt. SUge Stoddard solvent solution incorporated and applied to a steel plate by dip coating. On the steel plate a film with a thickness of 23.1 μ is deposited

gert. When this coated plate under the In Verglelchsbelsplel 1 is weathered in the weatherometer, the film begins cancel after a tent span of 1 day and cool down and whitening to show. After about 5 days the steel plate will begin to rust.

Comparative example 4

It is believed that a silicone oil repellant material incorporated into rust preventive compositions improves the weathering property of the jarau-derived films. To test this possibility, 0.5 wt .-%, based on the non-volatile substances of a commercial silicone oil having a viscosity of 100 cP at 25 ⁰ C incorporated into the prepared in Comparative Belsplel 1 fat and the resulting mixture is then dissolved in 70% by weight Stoddard solvent. A film with a thickness of 26.5 μm deposited from this solution on a steel section is then tested in the weatherometer. After 1 day in the weatherometer, the film was observed to build up and the steel began to rust after 5 days.

Comparative example 5

Using the one-step manufacturing process described above, which was already described in the introduction mentioned German patent application 1. Described in detail, a product is produced that has a yellow, represents thlxotropes, flowable material, the 12Gew.-96Galzlumsulfonat, 17.3 wt .- * light oil diluent and contains 60% by weight of Stoddard solvents and has an acetic acid base number of about 120.

This product is then diluted to a solvent concentration of about 7796 with Stoddard solvent. A steel plate is coated with the rust preventive agent thus prepared by immersion, a film about 25.4 microns thick is deposited on the plate. The film is in the weatherometer weathered and developed after 1 day limescale and whitening and the panel begins to rust around the fifth day.

example 1

The rust preventive agent described in Comparative Example 5 is heated to about 94 ° C. About this product In a high-shear mixer, add 4 96% by weight of aluminum distearate based on the non-volatile Part of the composition, given. After stirring at high speed for about 15 minutes the product is cooled to 24 ° C (room temperature) and there is sufficient Stoddard solvent to the Composition given to approximate the total volatile solvent content of the mixture 80 wt .- * set. Then a steel plate is through Immersion coated with the resulting rust preventive and after the volatile one has evaporated Solvent is a film with a thickness of 22.9μ deposited.

The coated panel is then placed in the weatherometer and the weathering cycles described exposed. Whitening and calcification of the film begins after a period of 2 days and The plate begins to rust after about the 6th day. It follows that the addition of aluminum distearate to the rust preventive agent produced by the one-step process described in Comparative Example 5 the weather resistance of the films deposited on the plate is improved. The film also has better weather resistance properties than films derived from previously known rust inhibitors, such as those by two-step process can be produced.

Example 2

A strongly basic rust preventive from the example 5 is made by the one-step process and diluted to a 75 wt. * To give a Stoddard solvent solution. The resulting composition is placed in a 1 liter swivel flask brought with stirrer, thermometer, reflux condenser and azeotrope is equipped. Then 5% by weight of stearic acid, based on the non-volatile Part of the composition, added to the solution. The solution will be for a tent span of about Heated to reflux for 4 hours and the water generated in the resulting reaction is by means of the Azeotrope removed. The product is then cooled and Stoddard solvent is added to remove the Adjust the solution composition to a Stoddard solvent content of about 73.8% by weight. One Steel plate, which by immersion with the resulting Rust preventive coating has a solvent-free film on it with a thickness of about 71.1 μ deposited. If the coated panel is exposed to weathering in the weatherometer, it will find for a tent span of 4 days no quay and no whitening of the film takes place.

Example 3

A rust preventive is made through a one step process made to produce a product of the type and composition as described in Comparative Example 5, except that the 17.3 wt .- * light oil diluent by 17.3 wt .- 96% of a crude milk wax with a dropping point of 82 ° C, an oil content of about 2 wt .- *, and an ASTM needle penetration of 49 at 25 ° C will.

The resulting composition is a yellow, thixotropic, flowable material that contains about 12 wt .- * calcium sulfonate, 3.3 wt .- 96% light oil diluent, Contains 14% by weight of raw milk wax and 60% by weight of Stoddard solvent. The composition has an acetic acid base number of about 120. This product is dissolved in Stoddard solvent to make a composition to create a solvent content of 72% by weight. The one deposited with this composition on a dip-coated steel plate Film is about 20.3μ thick. When the panel is subjected to the accelerated weathering in the weatherometer, calking starts or The film becomes white between the 3rd and 4th day and rusting of the plate is observed for the first time. after being exposed to the weather cycle for 12 days.

The present example clearly illustrates that the replacement of a substantial portion of the non-volatile Diluent oil that is conventionally used in a rust preventive agent that is used according to The one-step process is made by waxing the weather resistance properties of films that Abeelaeert on steel laths with such a medium

are markedly improved and the onset of roasting is also greatly delayed in such plates.

Example 4

A rust preventive prepared in the manner described in Example 3 is used before the dilution step with Stoddard solvent to make the final composition with 4 wt% aluminum inlum stearate mixed, based on the non-volatile content of the composition. The mixing is done in one Mixer carried out with high gravity. The resulting product is then in Stoddard solvent dissolved to create a composition containing 76% of the solvent. One with this Composition Film deposited on a steel plate has a thickness of about 30.5 µm. After the accelerated When exposed to the weathering device, the film shows no occurrence of lime formation or whitening after 7 days, and rusting of the plate does not begin before the plate for a period of 10 days of the exposed to accelerated weathering.

This example illustrates that incorporating a relatively large amount of microwax (which is convenient replaces all of the non-volatile diluent oil normally used) and a small amount of carbonic acid salt in the rust preventive agent, the resistance of the rust preventive films derived from the agent against limescale formation and whitening markedly improved and that also the rust-resistant wedge of metal plates coated with the agent.

Example 5

and Comparative Example 6

20th

25th

30th

35

A rust preventive agent is used by means of a working method produced in which the starting material is subjected to the reaction with water and methyl cellosolve is a calcium carbonate dispersion that contains 30% calcium sulfonate (dispersant) and about 43% by weight Contains light-colored oil thinner. This dispersion has an acetic acid base number of 300. The fat-like one The product of the reaction of the dispersion with water and alcohol is dissolved in Stoddard solvent to produce a To form a composition containing 90% by weight of the solvent. To the resulting rust preventive becomes 10% by weight (based on the non-volatile part of the composition) of one synthetic wax, which consists of a nitrogen-containing fatty acid derivative (Octadecenamld). A steel plate is immersed in the product, which results according to the procedure described before the final amount of Stoddard solvent and the 10% synthetic wax are added to the product. One identical steel plate is immersed in the product, which contains the synthetic wax. After the volatiles have evaporated, there is a thin film on each plate deposited, both of which are tested for tackiness by touch. Who differs from the means The dissipative film containing the synthetic wax is significantly less tacky than the film that is away from the Derives means that does not contain wax.

Example 6
and Comparative Example 7

A Stoddard solvent solution is prepared containing about 0.8% by weight aluminum stearate and about 4% by weight

Contains 65 % magnesium stearate. The solution is made. By heating the solvent to a temperature between 80 and 100 ° C and stirring the metal elf into the solvent with vigorous stirring. The metal stearate solution is then added to a rust preventive agent which is prepared generally as described in Example 5, resulting in products which contain 80% by weight of volatile solvent (Stoddard solvent) and 0.6% by weight of aluminum stearate and 3, 1 wt .- * magnesium stearate, both based on the total weight of the non-volatile part of the product. The contact comparison of a film deposited on a steel plate with this agent, which is identical in all respects except that the Stoddard solvent solution of the dlstearates has been incorporated, shows that the addition of the metal stearates to the rust inhibitor has the noticeable tack of films deposited with such an agent.

Example 7
and Comparative Example 8

According to the process described in US Pat. No. 3,150,088, a potassium carbonate dispersion is produced, which is identical to that described in Comparative Example 1, except that virtually all of it non-volatile diluent oil conventionally used in the process by a raw microcrystalline wax with the properties described in Example 3 is replaced. The strongly basic one Dispersion has an acetic acid base number of 300 and contains 30 wt .- * calcium sulfonate, about 8 wt .-% light oil diluent and about 35 weight percent microcrystalline wax.

The dispersion is reacted in an operational boiler fat for about 1 hour at 93 ⁰ C with 10 wt .-% water and 0.5 wt .-% methyl cellosolve. The volatile components are then removed by heating the mixture at 182 ° C _{for a period of about 1V 2 hours.} The resulting grease is dissolved in about 60% by weight Stoddard solvent to form a rust preventive.

Identical steel plates are then used in the present Example prepared rust preventive composition and In a rust preventive composition immersed, which is made by the In Comparative Example 1 Prepared Fat Dissolves in about 60% by weight Stoddard solvent. Which emerges from the Composition different from the wax-containing fat the resulting film is very noticeably less tacky to the touch than the film that emerges from the none Wax-containing composition results, which are made from the fat contained in Verglelchsbelsplel 1 will.

Example 8
and Verglelchsbelsplel 9

The work described in Example 7 is repeated, with the exception that a finished paraffin wax with a melting point between 50 ° C and 52 ° C and an oil content below 0.25 wt .- * used instead of the microcrystalline wax described will. The protective film derived from the anti-rust agent is considerably less tacky than that Protective film made from an equivalent Stoddard solvent solution of In Verglelchsbelsplel 1 Derived from fat product.

From the above description of the invention and from the exemplary embodiments it can be seen that a significant reduction in tack and an improvement in weather resistance are obtained, if according to the invention the additives described in the strongly basic. Anti-rust agents containing metal

funds are brought in. The result of familiarization Benefits resulting from these additives are found in rust preventive compositions obtained by a variety of processes and widely Range may contain varying components.

Claims (8)

Patent claims: 1. Anti-rust agents containing 1) a volatile hydrocarbon solvent, 2) a metal salt as an oil-soluble sulfonic acid oil-soluble dispersant as well 3) an alkaline earth carbonate, characterized in that it contains 20 to 70% by weight of a volatile hydrocarbon solvent with an initial boiling point below 230 ° C and a viscous, high melting point composition dissolved in the solvent contains that from 5 to 80% by weight of the metal salt of an oil-soluble sulfonic acid as an oil-soluble dispersant, 5 to 45% by weight of the alkaline earth carbonate, the percentage by weight of the carbonate being based on the non-volatile part of the viscous composition which has a boiling point above 230 ^° C has, and an effective amount of an organic, the weathering and the stickiness of the rust preventive reducing agent from a natural or synthetic wax, a carboxylic acid with a molecular weight of at least 165, which contains at least 10 carbon atoms and is solid at 38 ° C, a metal salt of this carboxylic acid or a Mixture of waxes, acids and / or salts, the waxes being organic, thermoplastic substances with a melting point between 38 and 149 ^° C. 2. rust preventive according to claim 1, characterized in that it is at least 20 wt .-% of one contains non-volatile diluent oil. 3. Rust preventive according to claims 1 and 2, characterized in that it is used as in the dispersant soluble carboxylic acids straight-chain allphatlsche carboxylic acids with at least 12 and less than contains 24 carbon atoms. 4. Rust preventive according to one of claims 1 to 3, characterized in that the high-melting point Composition 40% by weight of a microcrystalline wax and 4% by weight of aluminum stearate contains. 5. Rust preventive according to one of claims 1 to 4, characterized in that the high-melting point Composition contains 20 to 50% by weight wax. 6. rust preventive according to any one of claims 1 to 5, characterized in that it is the metal salts Contains carboxylic acids with metals from groups HA, HB and HIA of the perlode system. 7. rust preventive according to any one of claims 1 to 6, characterized in that the high-melting point Composition 1 to 4% by weight at least contains a carboxylic acid and / or a carboxylic acid salt. 8. rust preventive according to any one of claims 1 to 7, characterized in that it is a metal salt of the carboxylic acids an aluminum, zinc, calcium and / or Barlum's salt of stearic acid, palmic acid, tallic acid, tetradecanoic acid and / or oleic acid. The present invention relates to rust inhibitors containing Ί) a volatile hydrocarbon solvent, 2) a metal salt of an oil-soluble sulfonic acid as an oil-soluble dispersant as well 3) an alkaline earth carbonate. From FR-PS 12 95 087 is a lubricating oil for diesel engines known. This contains carboxylic acids with one to three carbon atoms as well as calcium carbonate and calcium acetate. The US-PS 3149 074 describes a lubrication for Bearings, electric motors, etc., with properties similar to lithium-based lubricants. It contains one oleaginous carrier, a magnesium or aluminum alkoxide that disperses in magnesium or aluminum sulfonate is, but both magnesium and aluminum cations must always be present. Further it contains sulfonic acids; as an oily carrier, for. B. mineral lubricating oil is used. Possibly a solvent is present. The US-PS 28 31 821 describes a water-resistant Alkaline and alkaline earth containing lubricating grease. This necessarily contains sodium stearate, lubricating oil and magnesium hydroxide and / or magnesium carbonate. From US-PS 26 14 986 lubricating greases are also known. In the introduction to the description the technology one by fatty acid salts, ζ. B. calcium stearate, thickened mineral oil described. It is suggested, instead to use magnesium oxide or carbonate as a thickener. These are magnesium salts not chemically converted, but serve as a lubricant themselves. The US-PS 26 07 735 describes lubricating greases, which essentially a lubricating oil and as a thickener Alkaline earth soaps included. Grease and rust preventive compositions containing strongly basic metal salts are already made been. In most cases, these compositions are mineral oil solutions of an oil-soluble dispersion medium salt, which contain a basic alkaline earth metal salt or a complex thereof dissolved or dispersed. Such compositions can be made in a number of ways, some of which comprise two basic process stages, in which initially a mineral oil solution of a carbonated, basic alkaline earth metal salt is formed, which then In the second stage is treated with an active hydrogen compound to produce the fat compositions to surrender. A typical two step process for making such grease and rust preventive compositions Is described in US-PS 32 42 079 and 33 72 115. Other types of work include a single stage in which a mixture of an oil-soluble dispersant, non-volatile carrier, Water, alcohol and alkaline earth metal carbonate complex is heated under controlled conditions to produce the Effect conversion to fat. A typical Arbeltswelse of this type is described in the German patent application P 19 19 317.0, which describes a process for the preparation of strongly basic fat and rust preventive compositions regards. Greases and rust inhibitors of the type just described usually contain a large amount of a non-volatile one Thinner oil that acts as a plasticizer and emollient. The resulting fats and rust inhibitors are therefore relatively loose and sticky. When these compositions are used as surface