Patent Publication Number: US-3876574-A

Title: Rust preventing paint consisting essentially of high molecular metal-combining reaction product

Description:
United States Patent 1191 Nagahisa et al.  
 1111 3,876,574 14 1 Apr. 8, 1975 [73] Assignee: Kansai Paint Co Ltd., Hyogo,  
  Japan 221 Filedz Sept.2l, 1972 [211 Appl. No.: 291,042  
 Related US. Application Data [63] Continuation-impart of Ser. No. 793,595, Jan. 23. 1969. abandoned, and a continuation-in-part of Ser. No. 178.784, Sept. 8, 1971, abandoned.  
 [30] Foreign Application Priority Data Jan. 23. I968 Japan 43-3496 52 us. 260/22 1); l06/l4; 260/22 R; 260/40 R 51 im. (21..., C08g 17/16 [58] FieldofSfearch ..106/l4;252l387;252/388; I 117/132; 260/429,435,437,414,22 D,  
 22CA, 22 CB, 22 A [56] References Cited UNITED STATES PATENTS 2.715,]11 8/1955 Wiinberg 260/22 CA 3.2l9,604 11/1965 Fischer 260/22 CB 3,258,475 6/l966 Faulkne et al. 260/22 CA Primary Exan1iner&#39;Lewis T. Jacobs Attorney, Agent, or Firn1Wenderoth, Lind &amp; Ponack [57] ABSTRACT A rust preventing paint for steel which contains high molecular weight metal-combining reaction product as a film-forming material.  
 8 Claims, No Drawings RUST PREVENTING PAINT CONSISTING ESSENTIALLY OF HIGH MOLECULAR METAL-COMBINING REACTION PRODUCT The present application is a continuation-in-part of our corresponding application Ser. No. 793,595, filed Jan. 23, 1969 and application Ser. No. 178,784, filed Sept. 8, 1971, both abandoned.  
  This invention relates to a rust-preventing paint for steel containing a high molecular weight metalcombined reaction product as a film forming-material.  
  The object of this invention is to provide a novel rust preventing paint which can be easily applied to the surface of steel. In the case of rust remaining on the surface of the steel to be painted said paint permeates into the layer of rust; and in the cases where no rust exists on the surface of the steel, said paint adheres well thereon. As a result, in either of the above cases, the paint of this application can prevent corrosion of steel in the atmosphere.  
  For the rusty surface of steel, heretofore, an oleoresinous paint consisting of linseed oil and red lead has been used, but such a paint has been insufficient in its rust preventing effect in polluted air and in its quickness in drying. The rust preventing effect of an anticorrosive paint consisting of synthetic resins (for example, red paint of long oil alkyd resins) is also insufficient because said paint is insufficient in its ability to permeate into underlying rust and as a result, the paint is insufficient for preventing the growth of rust.  
  As described above, heretofore it has been very difficult to prepare a paint effective against the rusty surface of steel and having the following properties.  
  1. Good wetting, permeating, and adhering properties.  
  2. Good weather property and rust preventive effect in polluted air.  
  3. Good workability and rapid drying property in practice.  
  It has been discovered that these difficulties are solved by using high molecular weight metal-combined reaction products as film forming materials for rust preventing paints. Said reaction products are produced from reactions between (1) aliphatic polycarboxylic acids, (2) monocarboxylic acids, (3) reactive compounds of metals selected from the group consisting of lead, calcium, cobalt, zinc, iron, manganese, nickel, magnesium, barium, cadmium, strontium and chromium, and (4) polyhydric alcohols.  
  Heretofore, a polyester resin composition modified with an aliphatic monocarboxylic acid through the agency of metal linkage was well known and is characterized by a remarkable increased viscosity in uncured condition.  
  On the other hand, the high molecular weight metalcombining reaction products of the present invention has respective metals in their polymer structure and differ from above-mentioned polyester resin in their of red lead, lead powder, lead suboxide, zinc dust, basic lead chromate and zinc yellow, and a basic pigment such as zinc oxide and iron oxide powder as an auxiliary pigment. When said paint is applied on the surface of steel, a water impermeable dryed film can be easily formed, and, as a result, the pigment in said film converts anticorrosive substances produced by electrochemical reaction, or the oxidation and aging of film into a passive state, thereby preventing the formation of rust.  
  While, in the rust preventing paint consisting essentially of high molecular weight metal-combining reaction product of the present invention, the said high molecular weight metal-combining reaction product itself employed as a film forming material has rust preventing action and accordingly, the addition of an anticorrosive pigment is not particularly required. However, a coloring pigment and extender for general use may be added to said film forming material to afford a suitable viscosity and fluidity, whereby the paint can be uniformly and thickly applied on a steel material. The film so applied is reinforced and made to afford favorable durability, and further a desirable coloring can thereby be attained.  
  The process for the production of the rust preventing paint of this invention comprises the following steps.  
  1. Into an aliphatic polycarboxylic acid having two carboxyl groups in its molecule, as a single component, or a mixture obtained by adding an equimolar or less of a monocarboxylic acid to the said aliphatic polycarboxylic acid, a 0.2 to 0.7 equivalent based on the total amount of carboxylic .groups present in aliphatic polycarboxylic acid or mixture thereof with monocarboxylic aid of a reactive metal compound is added and the mixture is heated to obtain a-reactio&#39;n product having a high acid value. A 0.1 to 0.7 equivalent based on the carboxylic groups present in the reaction product of a polyhydric alcohol is caused to react with the carboxyl groups of said reaction product to increase its molecular weight. Thereby a high molecular weight metalcombining reaction product having carboxyl groups at the terminals of its structure is produced. The thus obtained metal-combined reaction product is dissolved or dispersed and suspended into an organic solvent to produce the dispersion of a high molecular weight metalcombining reaction product.  
  In the preparing process for the high molecular weight metal-combining product, increased amount of the reactive metal over 0.7 equivalent may be used if desired, but the excess amount usually simply acts as a filler. If the amount of the reactive metal of less than 0.2 equivalent is used, the resultant product has no desirable rust preventive property and acidity. Also, if the amount of the polyhydric alcohol over 0.7 equivalent or less than 0.1 equivalent is used, the reaction product having desirable molecular weight and carboxyl groups at the terminal parts of its structure is unobtainable.  
  In general, it may be stated that the amount of reactive metal and polyhydric alcohol used usually falls within the previously mentioned range depending upon variables as amount of added aliphatic polycarboxylic acid, acidity desired and molecular weight of the reaction product desired.  
  2. Next, the above-mentioned dispersion of high molecular weight metal-combined reaction product is independently employed as a vehicle, and a dryer for paint, etc. are added thereto to produce the rust preventing paint of the invention without any pigment.  
  3. On the other hand, the dispersion of the high molecular weight metal-combined reaction product is separately used or mixed with other paint vehicle; further, a coloring pigment, extender, and additives for paint (that is, auxiliary agents such as dispersing agent, dryer, and anti-skinning agent, hereinafter these agents are refered to simply as additives) are further added thereto to obtain a mixture, and said mixture is sufficiently kneaded by a dispersing device such as ball mill, and roll mill thereby to produce the rust preventing paint containing the dispersion of this invention. In this case, an anticorrosive pigment may be mixed with said dispersion.  
  The following components are used for producing the dispersion of the high molecular weight metalcombining reaction product compound of this invention:  
  1. Aliphatic polycarboxylic acids having two carboxyl groups in its molecule, which may be used, include dimer acids such as tall oil dimer acid, linseed oil dimer acid; maleic acid.  
  Tall oil dimer acid is obtained from tall oil. Dimer content is from 70 to 95 wt.%, the rest is the mixture of trimer and monomer.  
  Linseed oil dimer acid is obtained from linseed oil. Dimer content is from 60 to 95 wt.%, the rest is the mixture of trimer and monomer.  
  2. Monocarboxylic acids which may be used, include C C aliphatic monocarboxylic acids, consisting of a single carboxyl group attached to the end of a straight hydrocarbon chain such as linseed oil fatty acid, soybean oil fatty acid, tall oil fatty acid; rosin acid existing into wood rosin, gum rosin and tall rosin, aromatic monocarboxylic acid such as benzoic acid.  
  Linseed oil fatty acid is obtained by the saponification of linseed oil. Said fatty acid has the iodine value from 160 to 210. Soybean oil fatty acid is obtained by the saponification of soybean oil. Said fatty acid has the iodine value from 100 to 155. Tall oil fatty acid is obtained by the cracking of tall oil, comprising a fatty acids content in the range of 90 to 98 wt.%. Rosin acid which may be used, is contained into wood rosin, gum rosin and tall rosin, comprising abietic acid as chief component.  
  3. Reactive metal compounds which may be used, include oxides or hydroxides of metals such as lead, calcium, cobalt, zinc, iron manganese, nickel, magnesium, barium, cadmium, strontium and chromium.  
  4. Polyhydric alcohols which may be used, include trihydric alcohols having three of average number of functional groups such as glycerine, trimethylolethane and trimethylolpropane; trihydric alcohol containing amino nitrogen in its molecule such as trishydroxymethylaminomethane.  
  Heretofore, it has been commonly known that a rust preventing paint in which an anticorrosive pigment selected from the group consisting of lead pigments such as lead oxide, tri-lead tetroxide, basic lead chromate, and a metal powder (for example, zinc dust) is used, having been principally used for the preventing the formation of rust on the surface of steel and preventing the influence of polluted air, and considerable effects could have been obtained by the use of said paint.  
  On the other hand, a paint prepared by physically suspending hydroxides or oxides of a reactive metal compound selected from the group consisting of lead, calcium, cobalt, zinc, iron, manganese, nickel, magnesium, barium, cadmium, strontium, chromium, etc., as a single or admixture component, into a processed drying oil or the other film forming material has little rust preventing effect. Even if there are some effects, the efficiency of those is far inferior to the anticorrosive paints produced from said lead pigments, and accordingly, heretofore, these metal oxides have been merely used for an extender or coloring pigment.  
  On the other hand, the rust preventing paint of this invention and the dispersion of those including various metal compounds other than the above-mentioned lead pigments as a constituent has the following excellent characteristic features.  
  1. Favorably dilutable with organic solvents or capable of preparing a stable dispersed suspension therewith.  
  2. Capable of affording a flexible film due to its amorphousness, little change in the physical properties of said film by the lapse of time, and highly weather resistant.  
  3. Due to the existence of a carboxyl group at the terminal portion of its high molecular weight structure, favorable wettabilit y, permeability, and adhesiveness to the surface of a steel material and the rust remaining thereon, and accordingly, particularly suitable for the rust preventing coating for a rusty surface of steel.  
  4. Excellent durability because of the coated films being hardly subjected to hydrolysis.  
  5. Rapid drying. Accordingly, in short period after applying the rust preventing paint of this invention, a synthetic resin type paint can be over-coated, and it shows excellent adhesiveness to the over-coated film.  
 6. Favorable storage stability.  
  As a result, if the rust preventing paint of this invention is employed for rust preventive painting of steel materials for construction, the working property of coating becomes easy. Furthermore, in both cases when rust is present or absent on the surface of a steel, and further even if uneven rust is present on said surface, the paint favorably adheres, wets, permeates thereinto, and rapidly dries, whereby the durability of the steel material can be remarkably increased. Moreover, the finishing of coating can be completed in an early stage and this is useful in practice.  
 In the following disclosure, examples of the rust preventing paint of the present invention consisting essen-- tially of the high molecular weight metal-combined reaction product as a film forming material will be shown.-  
 7 The examples are for the purpose of illustration only and this invention shall not be limited to the examples.  
 Example 1 1680 parts by weight (3 moles) of linseed oil dimer (dimer content about wt.%, iodine value 180, neutralization value 200: hereinafter the same) acid and 560 parts by weight (2 moles) &#39;of soybean oil fatty acid (iodine value 135, neutralization value 200: hereinafter the same) were placed in a three-necked flask with a stirrer, thermometer, and condenser provided with branched tube and heated for 30 minutes while stirring. When the temperature of the contents in said flask reached C, 74.1 parts (1 mole) by weight of calcium hydroxide was added thereto little by little, and the obtained mixture was made to react for 1 hour while keeping the temperaturewithin the range of 160 180C. Further, 46 parts by weight (0.5 mole) of glycerine was added to the reacted substance, the temperature of which was elevated to 200C to react them for 3 hours. When the total amount of the distillate water reached 63 parts by weight (theoretical value), the heating was stopped and the reaction product cooled. When the temperature of said product reached about 80C, xylene was added thereto to produce a high molecular weight metal-combined reaction product I having a concentration of 60% by weight.  
  In accordance with the formula of the following Table 1, into this high molecular metal-combined reaction product I, a coloring pigment and extender were added and kneaded well with a roll or ball mill. A dryer and solvent were added thereto to produce so called rust preventing paint containing pigment of the invention which contains iron oxide pigment.  
 TABLE I (parts by weight) Red Iron Oxide 8.0 Heavy Calcium Carbonate 48.0 Weight metal-combining reaction product 1 (solid matter 60%) 39.0 Lead Naphthenate (Pb: 0.8 Cobalt Naphthenate (Co: 5%) 0.2 Mineral Spirit 4.0  
 Total: 100.0  
 Example 2 Example 1 l TABLE 2 Exam- Reactive Blending Total High Molecular ple Metal Amount Amount Metal-combined Compound (parts by of Reaction weight) Distil- Product late Water (parts) y weight) 2 Cobalt 92.9 63 High Molecular Hydroxide Cobalt-combined Reaction Product II 3 Zinc 99.4 63 High Molecular Hydroxide Zinc-combined Reaction Product III 4 Iron 106.9 81 High Molecular Hydroxide Iron-combined Reaction Product IV 5 Manganese 88.9 63 High Molecular Hydroxide Nickel-combined Reaction Product V 6 Nickel 92.7 63 High Molecular Hydroxide Nickel-combined Reaction Product VI 7 Magnesium 58.3 63 High Molecular Hydroxide Nickel-combined Reaction Product VII 8 Barium 171.3 63 High Molecular Hydroxide Barium-combined Reaction Product VIII TABLE 2-Continued 630 parts by weight (1.12 moles) of tall oil dimer acid (dimer content about wt.%, acid value 190, saponification value 195: hereinafter the same) was put in a three-necked flask with a stirrer, thermometer and condenser provided with branched tubes, heated for 30 minutes while stirring, and at the time when the temperature of the contents had become to C, 25.2 parts by weight (0.34 mole) of calcium hydroxide was added little by little and allowed to react for 1 hour keeping the temperature at 160 C. 40 parts by weight (0.33 mole) of trihydroxymethylaminomethane was added keeping the temperature at 180C, and the mixture allowed to further react for 1 hour. At the time when the total amount of the distillate water has accounted to 27 parts by weight (90% of the theoretical value), heating was stopped and the product allowed to cool. At the time when a temperature of the product had fallen to about 80 C, xylene was added, and dispersion of nitrogen-containing high molecular weight calcium-combined reaction product XII of 60% concentration by weight was obtained.  
  Into this dispersion of nitrogen-containing high molecular weight calcium-combined reaction product XII, a dryer and solvent were added in accordance with the following formula of Table 3, and the rust preventing paint without pigment of the invention was obtained. 8n  
 TABLE 3 (parts by weight) Dispersion of Nitrogen-containing Example 13 Example 22 The same procedure as described in Example 12 is followed, substituting the calcium hydroxide by one equivalent&#39;mole of respective hydroxide of various metals shown in Table 4. The thus obtained respective nitrogen-containing high molecular weight metalthe invention was obtained.  
 TABLE 4 Reactive Blending Total Nitrogen-containing Metal Amount Amount High Molecular Exam- Compound (parts of Metal-combined ple by Distil- Reaction weight l/ate Product ater (parts y weight) l3 Cobalt 3 l .6 27.0 Nitrogen-containing Hydroxide High Molecular Cobalt-combined Reaction Product XIII 14 Zinc 33.8 33.0 Nitrogen-containing Hydroxide High Molecular Zinc-combined Reaction Product XIV Iron 36.4 33.0 Nitrogen-containing Hydroxide High Molecular Iron-combined Reaction Product XV l6 Manganese 30.2 27.0 Nitrogen-containing Hydroxide High Molecular Manganese-combined Reaction Product XVI I7 Nickel 31.5 27.0 Nitrogen-containing Hydroxide High Molecular Nickel-combined Reaction Product XVII l8 Manganesium 19.8 27.0 Nitrogen-containing Hydroxide High Molecular Mangnesiumcombined Reaction Product XVIII l9 Barium 58.2 27.0 Nitrogen-containing Hydroxide High Molecular Barium-combined Reaction Product XIX Cadmium 49.8 27.0 Nitrogen-containing Hydroxide High Molecular Cadmium-combined Reaction Product XX 2l Strontium 41.2 27.0 Nitrogen-containing Hydroxide High Molecular Strontium-combined Reaction Product XXI 22 Chromium 35.0 33.0 Nitrogen-containing Hydroxide High Molecular Chromium-combined Reaction Product XXII 22b Lead Oxide 76.0 2l.0 Nitrogen-containing High Molecular Lead-combined Reaction Product Xllb Example 23 The dispersion of nitrogen-containing high molecular weight calcium-combining reaction product XII of Example 12, was mixed with long oil alkyd resin varnish (oil length 60% by weight, long oil alkyd resin was produced by the modification of polyester, comprising the reaction product of phthalic anhydride and pentaerythritol, with soybean fatty acid; hereinafter the same). There was then added coloring pigment and extender as shown in the formula of the following Table 5. The mixture was kneaded well by roll or ball mill. To the mixture was added a dryer and solvent. The rust preventing paint containing pigment of the invention, which is a mixture of 80% long oil alkyl resin and 20% dispersion of nitrogen-containing high molecular weight calcium-combined reaction product XII, containing iron oxide pigment, was obtained.  
 TABLE 5 Red Iron Oxide Calcium Carbonate 4 Aluminum Stearate Dispersion of Nitrogen-containing High Molecular Calcium-combined Reaction Product XII (solid Matter 60%) Long Oil Alkyd resin Varnish (Solid Matter 60%) 28.0 Lead Naphthenate (Pb: 15%) 0.8 Cobalt Naphthenate (Co: 5%) 0.2 Mineral Spirit 10.5  
 Total: 100.0  
 Example 24 Example 33 Following Example 23, substituting the nitrogencontaining high molecular weight metal-combined reaction product as shown in the following Table 6 for the nitrogen-containing high molecular weight metalcombined reaction product XII in the formula (parts by weight) of Table 5, the rust preventing paint containing pigment of the invention was obtained.  
 TABLE 6 Reactive Metal Compound Nitrogen-containing High Molecular Metal-combined Reaction Product Example 25 Zinc Hydroxide 26 Iron Hydroxide 27 Manganese Hydroxide 28 Nickel Hydroxide 29 Magnesium Hydroxide 30 Barium Hydroxide 3 l Cadmium Hydroxide 32 Strontium Hydroxide 33 Chromium Hydroxide 33b Lead Oxide Example 34 336 parts by weight (0.6 mole) of tall oil dimer acid and 112 parts by weight (0.4 mole) of linseed oil fatty acid (iodine value 180, neutralization value 200: hereinafter the same) are put in a three-necked flask with a stirrer thermometer and condenser with branched tube and heated for 30 minutes while stirring. At the time when the temperature of the contents reaches C, 37.1 parts by weight (0.5 mole) of calcium hydroxide is added little by little and the mixture allowed to react for 1 hour keeping the temperature at 160 180C. There is added 16.2 parts by weight (0.12 mole) of trimethylolpropane, the temperature is raised to 200C and the mixture allowed to react for 3 hours. At the same time when the total amount of the distillate water has accounted to 24.5 parts by weight (theoretical value), heating is topped and the mixture allowed to cool and at the time when the temperature of the reacted product has fallen to about 80C, xylene is added so that the concentration of the product is diluted to 60% by weight. Thus high molecular weight calciumcombined reation product XXIII was obtained.  
  Using this high molecular weight calcium-combined reaction product XXIII and following Example 1 according to the formula (parts by weight) as shown in the following Table 7, the rust preventing paint containing pigment of the invention was obtained.  
 TABLE 7 (parts by weight) Red Iron Oxide 8.0 Heavy Calcium Carbonate 48.0 High Molecular Calcium-combined 39.0 Reaction Product XXlll 39.0 (Solid Matter 60%) Lead Naphthenate (Pb: 08 Cobalt Naphthenate (Co: 5%) 0.2  
 Mineral Spirit 4.0 Total: 1000 Example 35 Example 44 Following Example 34, substituting the calcium hydroxide by respective hydroxide of various metals as shown in the following Table 8 and allowing the mixture to react, there is produced respective high molecular weight metal-combined reaction product. These are substituted for the high molecular weight calciumcombined reaction product XXIII in the formula of the rust preventing paint shown in Table 7, and thus the rust preventing paint containing pigment of the invention was obtained.  
 Reaction Product XXVllI TABLE 8-Continued Exam- Reactive Blending Total High Molecular ple Metal Amount Amount Metal-combined Compound (parts of Reaction by Distil- Product weight) late Water (parts y weight) 40 Magnesium 29.2 24.5 High Molecular Hydroxide Magnesium-combined Reaction Product XXIX 41 Barium 85.7 24.5 High Molecular Hydroxide Barium-combined Reaction Product XXX 42 Cadmium 73.2 24.5 High Molecular Hydroxide Cadmium-combined Reaction Product XXXl 43 Strontium 60.8 24.5 High Molecular Hydroxide strontium-combined Reaction Product XXX&#34; 44 Chromium 51.5 33.5 High Molecular Hydroxide Chromium-combined Reaction Product XXXlll 44b Lead Oxide l 1 1.6 l5.5 High Molecular Lead-combined Reaction Product XXXlllb Example 45 98 parts by weight (1 mole) of maleic acid anhydride and 280 parts by weight (1 mole) of linseed oil fatty acid were put in a three-necked flask with a stirrer, thermometer and condenser provided with branched tube and the mixture heated to raise the temperature up to 200C in about 30 minutes. The mixture is allowed to react for about 5 hours. After the temperature of the contents has fallen to C there are added 37.1 parts by weight (0.5 mole) of calcium hydroxide little by little and the mixture allowed to react for about 1 hour at the temperature 160 180C, while stirring. There is then added 32 parts by weight (0.27 mole) of trimethylolethane little by little, keeping the temperature of the content at 180C and the mixture is allowed to react 1 hour. At the time when the total amount of the distillate water has accounted to 32.5 parts by weight, heating&#39;is stopped and the mixture allowed to cool. At the time when the temperature of the contents has fallento 80C, xylene is added and thus high molecular weight calcium-combined reaction product XXXIV of 60% concentration by weight was obtained.  
  Using this high molecular weight calcium-combined reaction product XXXIV, according to Example 1, after the formula (parts by weight) shown in the following Table 9, the rust preventing paint containing pigment of the invention, which contains iron oxide pigment, was obtained.  
 Example 46 Example 55 TABLE Exam- Reactive Blending Total High Molecular ple Metal Amount Amount Metal-combined Compound (parts of Reaction by Distil- Product weight) late Water (parts y weight) 46 Cobalt 46.5 32.5 High Molecular Hydroxide Cobalt-combined Reaction Product XXXV 47 Zinc 49.7 32.5 High Molecular Hydroxide Zinc-combined Reaction Product XXXVI 48 Iron 53.4 41.5 High Molecular Hydroxide Iron-combined Reaction Product XXXVIl 49 Manganese 44.5 32.5 High Molecular Hydroxide. Manganese combined Reaction Product XXXVIII 50 Nickel 46.4 32.5 High Molecular Hydroxide Nickel-combined Reaction Product XXXIX 51 Ma nesium 29.2 32.5 High Molecular Hy roxide Magnesium-combined Reaction Product XL 53 Cadmium 73.2 32.5 High Molecular Hydroxide Cadmium-combined Reaction Product XL&#34; 54 Strontium 60.8 32.5 High Molecular Hydroxide Strontium-combined Reaction Product 55 Chromium 51.5 41.5 High Molecular Hydroxide Chromium-combined Reaction Product XLlV 55b Lead Oxide l 1 1.6 13.0 High Molecular Lead-combined Reaction Product XLIVb Example 56 560 parts by weight (1 mole) of tall oil dimer acid and 302 parts by weight (1 mole) of&#39; gum rosin acid (Softening point 78C, acid value 180, hereinafter the same) were put in a three-necked flask with a stirrer, thermometer and condenser provided with branched tube and heated for about 30 minutes. At the time when the temperature of the contents becomes 160C 34.1 parts by weight (0.46 mole) of calcium hydroxide were added little by little while stirring and the mixture allowed to react for about 1 hour keeping the temperature at 160 180C There was added 53 parts by weight (0.44 mole) of trishydroxymethylaminomethane and keeping the temperature at 180C,  
 themixture allowed to react for 1 hour. At the time when the total amount of the distillate water has accounted to 36 parts by weight (90% of the theoretical value), heating was stopped and the mixture allowed to cool. At the time when the temperature of the product has. fallen to C, xylene was added, and thus nitrogen-containing high molecular weight calciumcombined reaction product XLV of 60% concentration by weight was obtained.  
  This nitrogen-containing high molecular weight calcium-combined reaction product XLV was added with a drier and solvent as in the formula of the following Table 11, and thus the rust preventing paint without pigment of the invention was obtained.  
 TABLE 11 (parts by weight) Oily Dispersoid Nitrogen-containing High Molecular Calcium-combined 90.0 Reaction Product XLV (Solic Matter 60%) Lead Naphthenate (Pb: 15%) 0.8 Cobalt Naphthenate (CO: 5%) 0.2 Xylene 9.0  
 Total: 100.0  
 Example 57 Example 66 Following Example 56, substituting calcium hydroxide by 0.46 mole of respective hydroxide of various metals shown in the following Table 12, there was produced respective nitrogen-containing high molecular weight metal-combined reaction product. These were substituted for nitrogen-containing high molecular weight calcium-combined reaction product XLV in the formula (parts by weight) of the rust preventing paint without pigment shown in Table 1 l of Example 5 6, and thus the rust preventing paint without pigment of the invention was obtained. 8n  
 Reaction Product L TABLE l2-Continued TABLE l3-Continued 630 parts by weight (1.12 moles) of tall oil dimer acid were placed in a three-necked flask with a stirrer, thermometer and condenser provided with branched tube and heated for 30 minutes while stirring. At the time when the temperature of the contents become 160C, 19.1 parts-by weight (0.34 mole) of calcium oxide was added little by little and the mixture allowed to react for 1 hour while keeping the temperature at 160 180C. There were then added 40 parts by weight (0.33 mole) of aminomethane, the temperature kept at 180C, and the mixture allowed to further react for 1 hour. At the time when the total amount of the distillate water has accounted to 21.5 parts by weight (90% of the theoretical value), heating was stopped and the product allowed to cool. At the time when the temperature of the reaction product had fallen to about 80C, xylene was added, and thus the nitrogen-containing high molecular weight calcium-combined reaction product LVI of 60% concentration by weight was obtained.  
  This nitrogen-containing high molecular weight calcium-combined reaction product LVI was mixed with long oil alkyd resin varnish (oil length 60%, modified with soybean oil), and added with coloring pigment and extender shown in the formula (parts byweight) of the following Table 13 and kneadedwell by roll or ball mill. There were added a dryer and solvent, and thus the rust preventing paint containing pigment of the invention which was a mixture of 80% by weight long oil alkyd resin varnish and 20% by weight nitrogencontaining high molecular weight calcium-combined reaction product LVI containing iron oxide pigment, was obtained.  
 trishydroxymethyl- Nitrogen-containing High Molecular (parts by weight) calcium-combined Reaction Product 7.0  
 (Solid Matter 60%) Long Oil Alkyd Resin Varnish (SOlld Matter 60%) 28.0  
 (oil length 60%, modified with soybean oil) Lead Naphthenate (Pb: 15%) 0.8  
 Cobalt Naphthenate (Co: 5%) 0.2  
 Mineral Spirit 10.5 Total: 100.0  
 Example 68 Example 73 Following Example 67, substituting calcium oxide by respective oxide of various metals shown in the following Table 14, there were produced respective nitrogencontaining high molecular weight metal-combined reaction product. These were substituted at the same ratio for the nitrogen-containing high molecular weight calcium-combined reaction product LVI in the formula of the rust preventing paint shown in Table 13 of Example 67, and thus the rust preventing paint containing pigment of the invention were obtained.  
 TABLE 14 Reactive Metal Total Compound Example Nitrogencontaining High Molecular Metal-combined Reaction Product 69 Zinc Oxide 27.6 21.5  
  70 Manganese Oxide 53.8 26.5  
 71 Magnesium Oxide 21.5  
 Barium Oxide 52.0 21.5 Nitrogencontaining High Molecular barium-combined Reaction Product LXI Nitrogencontaining High Molecular Strontiumcombined Reaction Product 73 Strontium Oxide 31.4 21.5  
  The following test examples are set forth in order to provide a comparison between the compositions of the present invention and certain reference formulations. In the following Reference formulas, those which are 3,876,574 15 v 16 prescribed in Japanese Industrial Standard (JlS) are in- TABLE l7-C0ntinued dicated. REFERENCE 1 Oily Red Lead Rust Preventing Paint (parts by weight) b It N h h c 0.2 (JlS K 5622-1 Red Lead Rust Preventing Paint) 5 S i g, fi 0 0) 85 TABLE 15 I Total: 100.0  
  (pm by weigh) REFERENCE 4 Red Lead (Pb O, 93%) 79 0 Long Oil Alkyd Resin Clear Paint Zinc OxideS 1.0 Aluminum tearate 0.5 Processed Drying Oil 18.0 TABLE 18 Manganese Naphtenate (Mn: 5%) 0.2 Mineral Spirit 1.3  
 Total: 100.0 (pans by Long Oil Alkyd Resin Varnish (solid matter 60%) 90.0 2 (oilblength 60%, modified with so ean oil Olly Iron Oxide Rust Preventing Paint Le ad Na ht henate (Pb: 15%) 0.8 (.118 K 5621-1 Rust Preventing Paint for General Q aRhihenate (Cm 5%) 02 Use) Mineral Spirit 9.0 Total: 100.0  
 TABLE 16 rts b ht (pa y Some test results of the Examples in comparison with 2 d l rpn oxide 3.8 the References are shown as follows:  
  111C X1 6 Calcium Carbonme 470 Test plate 1 1s a steel plate upon which rust rema ns [Aluminuantearatgl 8-3 Test plate 2 is a steel plate from which the rust has rocesse rymg r Lead Naphthenate (Pb: 15% Q8 been completely removed by sufficient sandblasting. Manganese lflaphthenate (Mn: 5%) 0.2 Test plate 3 1s a non-rusted polished mild steel plate SPrlt 3O sufficiently cleaned by polishing.  
 Total: 100.0  
  The plates were coated twice at an interval of 24 hours so as to be of uniform thickness by brushing with the above mentioned rust preventing paints. The coated plates were thereafter allowed to stand in a room for 7 days, exposed at atmospheric exposure, for  
 REFERENCE 3 Long Oil Alkyd Resin Red Lead Rust Preventing Paint (S K 5622 2 Red Lead Rust Preventing Paint) 6 months as to the rust preventing paint without p gment, and for 8 months as to the rust preventing paml TABLE 17 containing pigment, and then investigated.  
  The test results of the investigation were shown in the (P y welghtl following Test Example 1 3.  
 Red Lead (Pb O. 98%) 64.0 Zinc Oxide 2- TEST EXAMPLE I Aluminum Stearate I y 0.5 Lsonlgdohiil Alkydolesin Varnish h 0i ler o) 24.0 Rust preventing paint wit out pigment nitrogengg uz&#39;z g mdlfied containing high molecular weight metal-combined re- Lead Naphthenate (Pb: 15%) 08 action product, used alone.  
 TABLE 19-].  
  No. of Test Piece Example Test item 12. 13 1t 15 1e 17 18 19 2o 21 22 56 22b Atmospheric- Rust preventi 9) exposure, Test plate effect conned twice 3 Square cut (0 months) Cello-tape test TABLE 19-2 No. of Te t Pi Example R f, Test Item 57 58 59 b0 b1 b2 63 6 65 66 66b A mospheric Rust preventing exposure, Test plate effect A 82 fif 3 Square cut 0 t. s Cellompe test Rust preventing Paint containing pigment, high molecular weight metal-combining reaction product alone TEsT EXAM PLE 2 TEST EXAMPLE 3 Rust preventing paint containg pigment in which a vehicle prepared by admixing long oil alkyd resin var- &#34;Cello-tape&#34; is a trade mark of pressure sensitive adhesive tape.  
 as vehicle. nish with nitrogen-containing weight metal-combined reaction product is used. TABLE -1 No. of Test piece Example Testite 123t-5o7e91011 3411b Atmospheric Test plate Appearance exposvre, l (rust, scab) coate twice a Test plate Appearance (bnonths) 2 (rust, scab) S uare cut Cello tapetest TABLE 20-2 v No. of Test piece Example Test Item 36 37 3s 39 to 41 n2 as an 1+5 #6 ab Atmospheric Test plate Appearance exposure, 1 (rust, scab) c ated t i Test plate Appearance (6 months) 2 (rust, Scab) 3 cut cgiigf o o o o o o o o o o o TABLE 20-3 No. of Test piece Example Reference s m +7 +8 #9 5 5 53 5h 55b 1 2 3 Atmospheric Test plate Appearance exposure, 1 (rust, scab) A A X (cgated twice months Test plate Appearance g 2 (rustscaM OOQ Square cut ello-tapetest AAA TABLE 21-1 No. of Test piece Example? Test item 23 2b, 25 26 27 28 29 3O 31 32 33 67 33 Atmospheric Test plate Rust preventing exposure ff t coated twice S re cut (Fm-mks) gfi test o o o o o o o o o o o TABLE 21-2 No. of Test piece Example Reference Test item 68 69 70 71 72 73 -3 Atmospheric Test plate Rust preventing exposure 1 effect coated twice Square cut months, Cello-tape test A (Note) Notations in the above Tables have the following meanings excellent 0 2 good fair A somewhat bad x bad It is clear from the results of Test Examples 1 3, that the rust resisting paint of the invention which is composed of the film forming material containing high molecular weight metal-combining reaction product that has a carboxyl group at the terminal part of its struc ture, has good wetting properties and permeates to the rusty surface of a steel. Furthermore, the rust preventing paint of this invention has good adhesion to the surface of a steel, the rust on which was previously removed sufficiently and a film of which, after coating, has excellent characteristic features such that so coated steel surface can be maintained in a state free from corrosive substances in polluted air.  
  The foregoing description contains a limited number of embodiments of the present invention. It will be understood, however, that such embodiments are only illustrative and that numerous variations are possible without departing from the purview of this invention as defined in the following claims.  
  In the foregoing description and in the following claims, the terms high molecular metal-combining and high molecular weight metal-combining and like terms are used interchangeably.  
 What is claimed is:  
 1. A rust preventive paint comprising as a film forming material the reaction product of:  
 a. the reaction product of:  
 1. an aliphatic polycarboxylic acid having two carboxyl groups in its molecule selected from the group consisting of tall oil dimer acid, linseed oil dimer acid and maleic acid or mixture thereof with a monocarboxylic acid selected from the group consisting of linseed oil fatty acid, soybean oil fatty acid, tall oil fatty acid, rosin acid and benzoic acid, and  
 2. a 0.2 to 0.7 equivalent based on the total amount of carboxylic groups present in 1) of an oxide or hydroxide of a metal selected from the group consisting of lead, calcium, cobalt, zinc, iron, manganese, nickel, magnesium, barium, cadmium, strontium and chromium and b. a 0.1 to 0.7 equivalent based on the carboxylic groups present in reaction product a) of a trihydric aliphatic alcohol or trihydric aliphatic alcohol containing an amino nitrogen selected from the group consisting of glycerine, trimethylolethane, trimethylolpropane and trimethylolaminoethane.  
  2. The rust preventive paint of claim 1 wherein the monocarboxylic acid is employed in an equimolar or less amount against the aliphatic polycarboxylic acid.  
  3. The rust preventive paint of claim 2 wherein 3 moles of linseed oil dimer acid as the aliphatic polycarboxylic acid 2 moles of soybean oil fatty acid as the monocarboxylic acid, 1 mole of metal oxide or hydroxide and 0.5 moles of glycerine as the trihydric alcohol are employed.  
  4. The rust preventive paint of claim 2 wherein 1.12 moles of tall oil dimer acid as the aliphatic polycarboxylic acid, 0.34 moles of metal oxide or hydroxide and 0.33 moles of trimethylolaminomethane are employed.  
  5. The rust preventive paint according to claim 2 wherein 0.6 moles of tall oil dimer acid as the aliphatic polycarboxylic acid, 0.4 moles of linseed oil fatty acid as the monocarboxylic acid, 0.5 moles of metal oxide or hydroxide and 0.12 moles of trimethylolpropane as the trihydric alcohol are employed.  
  6. The rust preventive paint according to claim 2 wherein 1 mole of maleic acid anhydride as the aliphatic polycarboxylic acid, 1 mole of linseed oil fatty acid as the monocarboxylic acid, 0.5 moles of metal oxide or oxide or hydroxide and 0.27 moles trihydric alcohol are employed.  
 7. The rust preventive paint according to claim 2&#39; wherein 1 mole of tall oil dimer as the aliphatic polycarboxylic acid, 1 mole of rosin acid as the monocarboxylic acid, 0.46 moles of metal oxide or hydroxide acid, 0.44 moles of trihydroxymethylaminomethane are employed.  
  8. The rust preventive paint according to claim 2 wherein 1.12 moles of tall oil dimer acid as the aliphatic polycarboxylic acid, 0.34 moles metal oxide or hydroxide and 0.33 moles trihydroxymethylaminomethane are employed.