MXPA00005102A - Method for treatment of metal substrates using mannich-derived polyethers - Google Patents

Abstract

Methods for treating metal substrates are disclosed. These methods, which comprise contacting the surface to be treated with a composition comprising a Mannich-derivatized polyether, improve the corrosion resistance and/or adhesion properties of the treated surface. Similar methods for treating polymeric substrates are disclosed.

Description

METHOD FOR THE TREATMENT OF A METAL SUBSTRATE USING POLYETER DERIVATIVES FROM MANNICH Field of Invention The present invention relates to methods for the treatment of metal substrates. particularly, the present invention relates to methods for the treatment of metal substrates with compositions comprising Mannich derivatized polyethers. These methods provide improved corrosion resistance and / or adhesion properties of the paint to the metal substrate being treated. BACKGROUND OF THE INVENTION The present invention is directed to methods that are generally useful in the metal substrate treatment technique, particularly the treatment of phosphate metal substrates, and particularly the post-treatment of phosphate metal substrates. Such treatments impart improved corrosion resistance to the substrate, and improve the adhesion of the final coating layers such as paints, inks, lacquers and plastics. The need for Ref: 120271 applying protective coatings to improve corrosion resistance and / or adhesion characteristics of paint are well known in the finished metal technique, as well as other metal techniques. The usual technique for the application of such protective coatings to metal substrates involves contacting a clean metal substrate with a solution containing phosphate and possibly other metal ions to form a non-reactive, phosphate-resistant complex coating. corrosion in the metal substrate. "Because such coatings convert the metal substrate from a chemically active surface readily susceptible to oxidation to one that has improved corrosion resistance and / or paint adhesion properties, these are known in the technique as "conver s ion coatings' The corrosion resistance and the adhesion to the paint of the conversion coatings can also be increased by the treatment of the metal substrate with a post-treatment solution. Typically such solutions are solutions of aqueous acid containing a hexavalent chromium compound. Due to the toxic nature of the hexavalent chromium compounds, however, expensive treatment must be used to remove the chromates from the wastewater to prevent contamination of rivers, streams, drinking water sources, etc. Therefore, notwithstanding the known post-treatment solutions and chrome processes to be effective, they have recently developed efforts aimed at discovering alternatives to chromium containing compounds for post-conversion coating conversion.

U.S. Patent No. 4,376.00 discloses processes for the post-treatment of a coated metal surface of a phosphate-type conversion comprising contacting the surface with polyvinyl-1-phenol or its derivatives. U.S. Patent Nos. 4,433,015 and 4,517,028 disclose aqueous compositions comprising polyvinylphenol and polyalkane 1-phenol derivatives and acid salts thereof, respectively; the processes for the treatment of a metallic surface comprises contacting said surface with these aqueous compositions also described. U.S. Patent No. 4,457,790 claims an aqueous solution comprising a metal ion and a polyvinylphenol derivative or acid salt thereof. A process for the treatment of a metal surface comprising contacting said surface with the aqueous solution is also described.

U.S. Patent No. 5,523,363 relates to a resin obtained by the reaction of an epoxy resin, an amino compound and a phenol compound and an epoxidized novolac substituted phenolic resin. The resin is useful as an aqueous coating, particularly for cationic cross-recrystallizations. This does not teach to polymerize the components, or to use the resin to treat metallic or polymeric surfaces.

U.S. Patent No. 5,298,289 discloses processes for the treatment of certain plastics or painted surfaces with a liquid surface treatment comprising water and a dispersible or water soluble polyphenol polymer containing substituted aminomethyl groups in some of the phenyl rings of polyphenol . Other polyphenol compounds useful in the treatment of metals are described in U.S. Patent Nos. 5,116,912, 5,039,770 and 5, 266, 10 and EPO 319 016.

U.S. Patent No. 5,324,347 refers to a composition comprising a liquid solvent or dispersant or surface coating composition and a 2,6-bi s (aminomet i 1 substi tuido) phenol. This does not teach that phenol can be impregnated with an epoxy.

U.S. Patent Nos. 5,389,405, 5,412,011 and 5,451,431 disclose aqueous solutions for coating a metal surface comprising a polymer, a silicate and an organofunctional silane. Methods of coating a metal surface comprise contacting said surface with the aqueous solutions described.

WO 93/09265 describes a treatment for the formation of a corrosion resistant film on metal surfaces. This treatment includes the use of a phosphate surface treatment bath containing a cationic organic polymer compound having at least one cationic nitrogen atom. Described as one of the polymeric compounds, it is the adduct of HN (CH3) 2 with an epoxy resin.

European Patent Application 639,627 discloses aqueous solutions for pre-treating a metal surface, particularly aluminum, consisting essentially of an anionic polyactyl lick copolymer. A method of coating a metal surface comprising contacting said surface with any of the aqueous solutions is also described. The uses of other acrylate-containing compositions in the treatment of aluminum are also described in U.S. Patent Nos. 4,191,596 and 5,122,202.

U.S. Patent No. 3,994,989 discloses a paint binder comprising the reaction product of a Mannich base and an epoxide resin containing at least one 1,2-epoxide group. U.S. Patent No. 4,001,155 similarly describes a paint binder for the electrochemical cathodic coating of electrically conductive metal surfaces comprising the reaction product of a Mannich base and an epoxide resin containing 1,2-epoxide groups. U.S. Patent No. 4,396,732 describes the Mannich base of an amine resin prepared by reacting a dihydric phenolic compound with a diepoxide. None of these references, however, disclose the use of such resins as a sealant rinse in the treatment of metal or polymeric surfaces.

The Mannich condensates of a substituted phenol and an alkylamino containing internal alkoxy groups are described in European Patent Application 469,203.

This results in a real and substantial need for chromium-free methods for the treatment of various metal substrates, particularly phosphated metal surfaces. The present invention addresses this need.

Brief description of the invention.

The present invention is directed to a method for the treatment of various surfaces comprising contacting said surfaces with an effective amount of a composition comprising one or more Mannich-derived polyethers in a suitable solvent. These methods are particularly applicable to the post-treatment of a coated metal surface by phosphate conversion. These methods use compositions comprising the product of the condensation polymerization of a Mannich derivatized bisphenol resin and a bifunctional monomer.

It is therefore an object to provide a method for treating a metal surface using a non-chromed formulation.

It is a further object of the invention to provide such a method using the product of the condensation polymerization of a bisphenol and a bifunctional monomer.

Still another object of the invention is to provide such a method that improves the characteristics of corrosion resistance and / or adhesion of the paint to the metal surface being treated.

A further object of this invention is to provide a method for the treatment of polymeric substrates using non-chromated formulations.

Brief Description of the Drawings Figure 1 shows a schematic diagram of the method for preparing a preferred compound used in the methods of the present invention.

Detailed description of the invention The present invention is directed to a method for treating a metal surface comprising contacting said substrate with an effective amount of a composition comprising: a) a polyether, or an acid salt thereof, having the following formula (1): where R is selected from the group consisting of Y wherein R to R are independently selected from the group consisting of H, CqH2q +? and CqH2q-OH; R5 is selected from the group consisting of H, CqH2q + _, -CqH2q-OH, and CqH2q-COOH; q is between about 1 and 18; the sum of m and m 'is between about .5 and 4.0; n is between about 0 and 3; Z is selected from a straight chain or branched chain divalent aliphatic radical having between about 1 and 3 carbon atoms, S02, SO or O; And it is and X is between about 1 and 60; and b) an appropriate solvent or mixtures thereof. Preferably, the composition comprises between about 0.01 to about 60% active, based on the total weight of the composition, of component a), more preferably between about 0.01 to about 5% active, based on the total weight of the composition, and more preferably from 0.05 to about 1.0% active, based on the total weight of the composition. The present invention is further directed to a method for the treatment of a polymeric substrate with the composition comprising the polyether of formula (1) described above.

One skilled in the art will appreciate that the polyether of formula (1) is the product of the condensation polymerization of a Mannich derivatized bisphenol resin and a difunctional epoxy. The polyether can be nonionic, but preferably is cationic. The polyether is comprised of alternative hydrophilic and hydrophobic resin components. The water solubility of the compound can therefore be altered by increasing or reducing the amount of each component. The hydrophilic portion, referred to herein as "Resin AA- is generally represented by formula (2): where "R", "m", "m" and "Z" are as described above.

The hydrophobic portion, referred to herein as "Resin B", is generally represented by the formula (3): where \\ ? II and they are as described above Resin A is the Mannich derivative of a known class of compounds broadly referred to as bisphenols. The bisphenols that may be used in accordance with this invention are generally represented by the formula (4): wherein Z is selected from a straight-chain or branched-chain divalent aliphatic radical with from 1 to 3 carbon atoms, SO 2 and 0. The preferred bisphenol is bisphenol A (BPA) in which Z is 2,2-propylidene and the two OH groups are in the para position. Other bisphenols that may be used include, but are not limited to, 4,4'-thiodiphenol and 4,4'-sulphonyl diphenol. Bisphenol resins are widely commercially available.

Resin B is a resin having two epoxide groups and is therefore a difunctional epoxy. More specifically, Resin B is a diglycidyl coated prepolymer of bisphenol and epichlorohydrin. As illustrated in formula 3 above,. Resin B contains an internal repeat unit that can occur in the resin between 0 and 3 times. The variable "n", therefore, it can be between 0 and 3, and preferably it is between 0 and 1. The most preferred of these resins is. the difunctional bisphenol base epoxy resin, where Z is 2, 2 -propi 1 ideno and the two OH groups are in the para position. A preferred diepoxy resin, therefore, is the diglycidyl ether of BPA (DGEBPA), which is commercially available from Shell Chemicals, Houston, CT in this EPON line of liquid epoxy resins and resin blends. Particularly preferred is EPON® 828, which have a molecular weight of between about 370 and 384. Other EPON products having molecular weights in the range of 350 to 1.450 may also be used.

The polyether used in the present invention can be generally represented by the formula [A-B] x, where X refers to the number of repeating units in the polymer and A and B refers to Resin A and Resin B, respectively. X may typically be in the range between about 1 and 50, more preferably between about 1 and 12 and more preferably between about 1 and 4. This generally corresponds to the molecular weight ranges of 1,000 to 50,000; 1,000 to 12,000; and 1,000 and 4,000, which are the preferred, more preferred and much preferred molecular weights, respectively, for use in the present invention. A polyether having a molecular weight within a wide range can be used in all as the excess polyether dispersible or soluble in the desired solvent. Suitable polyethers for use in the present invention are also represented by the general formulas [A-B-A] x and [B-A-B] x, where X is such as the molecular weight of the resin described above. More complex link structures due to the nature of the condensation reaction and the characteristics of the reagents are also within the scope of the present invention.

It will be appreciated that the resin [A-B] x generally described above, represents a repeating unit that is characterized by the compound used in the methods of the present invention; Unfinished final units are described. The final group of the polymers of the present invention not described may be selected by the skillful artisan related in the techniques described in the art. For example, the final groups of the polyether can either be those resulting from the specific polymerization process employed, or those intentionally added to alter the characteristics of the polymer. For example, the final groups may be hydrogen, hydroxyl, initiation fragments, chain transfer agents, disproportionate groups, or other similar methods of chain termination of polymer grown.

The preparation of the polyethers used herein is described in the art in, for example, U.S. Patent No. 4,001,155. Preferably, the first step is to prepare the Mannich derivative of the bisphenol compounds described above as the formula 4. The terms "Mannich derivative" and "Mannich derivative" refer to the product resulting from the reaction of a phenolic group, such as a bisphenol, with an aldehyde and an amine. Reactions between a resin, an aldehyde and an amine are referred to as Mannich Reactions, and methods for executing such reactions are well known to those skilled in the art.

Formaldehyde is the typically preferred aldehyde for use in the Mannich reaction, although any suitable aldehyde can be used.

Similarly, any suitable amine known to those skilled in the art to effect Mannich derivatization of a resin can be used, including, but not limited to, primary amines, secondary amines, alkanol amines, dialkanol amines, and mixtures thereof. As an example of an appropriate primary amine is monoethanolamine. Suitable secondary alkyl amines that can be used are those of the general formula (5): wherein R1 and R2 are the same or different and are selected from the group consisting of H, CqH2q +? CqH2q-OH, where q is between about 1 and 18.

Methanolamine (MEA) and diethanolamine (DEA) are preferred, with DEA being the most preferred.

It will be appreciated by those skilled in the art that bisphenols and numerous other resins are generally insoluble in water. The Mannich derivation of the resin serves to improve its solubility in aqueous systems.

The percentage of bisphenol units in the resin that may undergo derivation during the Mannich reaction, expressed as the "percentage of derivation", may vary. That is, the number of "R" groups linked to each bisphenol molecule can vary from molecule to molecule. Typically, the derivation percentage of the Mannich derivative used in the methods of the present invention, represented in formula 1 by the value of m and m 'together, can be in the range from about 0.5 to 4.0, with the range from 2.0 to 3.5 being the preferred one. It will be understood that the value for both m or m 'can be equal to zero, although the sum of the two can be greater than zero. The solubility and / or the water dispersibility of the Mannich derivatized resin can generally be increased with a percentage of derivation. Consequently, as with molecular weight, the percentage of derivation of the units needs only be sufficiently high to realize the desired level of dispersibility or solubility.

As described above, the R groups that bind to the bisphenol resin by means of the Mannich reaction are generally described by the formula (6): R1 through R4 can be either the same or different and vary depending on the amine used in the Mannich reaction. For example, when the amine used in the Mannich reaction is the DEA, both R1 and R2 are equal to Cq-H2q-OH, where q equals 2 and R3 and R4 are both hydrogen. Preferably, R3 and R4 are both hydrogen and R1 and R2 are both C2H.OH. Typically, R1 through R4 are independently selected from the group consisting of hydrogen, CqH2q + _ and CqH2q-OH, where q is between about 1 and 18. Preferably, q is between about 1 and 4.

Formula 6 can also be protonated or quaternized to obtain formula (7): where R is selected from hydrogen, CqH2q + ?, CqH2q-OH or CqH2q-COOH, wherein q is between about 1 and 18. Preferably, q is between 1 and 4. Preferably, R5 is selected from hydrogen, CqH2q + ?, CqH2q -OH or CqH2q-COOH, wherein q is between about 1 and 18. Preferably, q is between 1 and 4. Preferably, R5 is selected from the group consisting of -H, -CH3, and -CH2CH2OH. R1 to R4 are as described above.

The Mannich derivatized bisphenol (MBP) is then polymerized with difunctional epoxy "Resin B" to form a polyether. This polymerization is a condensation polymerization, which is described in the Examples and which will be well understood by one skilled in the art.

The polyether is preferably prepared in an appropriate solvent. As used herein, the term "appropriate solvent" refers to any organic or inorganic solvent, or mixtures thereof, which are capable of dissolving or solubilizing the polyether derivative. Examples may include, but are not limited to, alcohols, ketones, glycol ether-based solvents and mixtures of these solvents. Particularly preferred are ethanol, propylene glycol n-propyl ether, and dipropylene glycol methyl ether.

In a preferred embodiment of the present invention, presented in Figure 1, BPA is reacted with formaldehyde and DEA to form MBPA. The MBPA is then reacted with DGEBPA to form a polyether generally represented by formula 1.

The Mannich derivatized resins used in the methods of the present invention may preferably have a molar ratio of BPA: to the aldehyde: amine in the range of from about 1: 1: 1 to 1: 4: 4. A relationship that gives good results in the present method is 1: 3.4: 3.6.

Mannich bisphenol derivatives having a ratio of components within an extended range are typically soluble in water, either alone or in their protonated or quaternized form, as described more fully below. The molar ratio of MBP to difunctional epoxide is typically in the range of about 1: 2 and 2: 1, with a ratio of 1.5-2.0: 1 being preferred.

Although the polyethers used in the methods of this invention are soluble in organic solvents and can be used when dissolved in an organic solvent such as, for example, ethanol, as a practical way that is desired to apply the treatment compound of a aqueous solution. To provide the desired water solubility or water dispersibility of the polyether, an organic or inorganic acid can be used for the protonisation or saturation of the amine portion thereof. Acids useful for this purpose include, but are not limited to, acetic, citric, oxalic, ascorbic, phenolic, phosphonic, chloromethyl phosphonic, mono, di and trichloroacetic, trifluoroacetic, nitric, phosphoric, hydrofluoric, sulfuric, boric acids. , hydrochloric, hexafluorosilic, hexafluorot, hexane, hexafluorozirconic or tet rafluoroboric, alone or in combination with each other. Phosphoric acid and acetic acid are preferred. The agents cuat erni zant is include, but are not limited to, methyl chloride, dimethyl sulfate, iodomethane and chloroacetic acid. The addition of water to the above-mentioned protonated or quaternized treatment compounds results in a water-soluble or water-dispersible solution of the polyether derivative useful for the treatment of the metal or polymer substrate in accordance with the present invention. The use of one or more of the acids listed above yield the corresponding acid salt of the starting resin. The use of quaternizing agents yields the corresponding quaternized species of the starting resin. Generally, only enough of the protonated or quaternized compound is added to solubilize the polyester resin.

The pH of the polyether composition can vary from about 4 to 9. The preferred pH range in terms of both the results achieved and the stability of the product is from 5 to 7.

It is contemplated that the treatment compositions of the present invention are used in a working solution at a dilute concentration. Under some circumstances, however, for example by transporting or storing the solution, a concentrate of the solution may be preferred. A solution comprising up to 65% by weight based on the active ingredient of the treatment composition can be provided. From a commercial point of view, an appropriate concentrate of this invention comprises from about 5% by weight to about 65% by weight of the treatment compound.

The present invention concerns the application of a treatment solution to a substrate, thereby improving the characteristics of corrosion resistance and / or adhesion of the substrate paint. The present invention particularly concerns the post-treatment of a metal substrate. As used herein, the term "post-treatment" refers to the treatment of a metal substrate that is not a bare metal, for example a metal substrate undergoing the conversion coating. The treatment of metal substrates having an uncovered metallic surface is also within the scope of the present invention. The term "metal substrate", therefore, is used herein to refer to any metal surface, regardless of whether it undergoes a conversion coating. Typical metal substrates include, but are not limited to, zinc and its alloys, aluminum and its alloys, iron, steel, galvanized steel and cold rolled, milled, deoxidized and hot rolled steel.

Although the inventors believe that the methods of the present invention can be effectively employed in any metal substrate. The best results are typically obtained if the metal substrate has been coated by conversion. The processes and solutions for forming conversion coatings on metal surfaces are well known. The processes for applying a phosphate coating are described, for example, in Metals Handbook, Volume II; 8th edition, pages 531-547 of the American Society for Metals. Different types of conversion coatings are available, depending on factors such as the level of quality required, the type of paint or coating to be applied, method of application and the processed substrate. Examples of conversion coating solutions include, for example, solutions comprising iron phosphate, magnesium phosphate, manganese phosphate, zinc phosphate, calcium-modified zinc phosphate, nickel or magnesium ions, mixtures of oxides and coatings. organometallic titanium or zirconium. It is within the ordinary skill of someone practicing in the art to determine the best conversion coating or the most appropriate one for use in a given application. It is also within the present invention to incorporate the compositions described herein into the conversion coating formulation. In this way, both the conversion coating and the sealant rinse are applied to the substrate simultaneously.

In addition to the treatment of metal substrates, the methods of the present invention can also be used to treat substrates such as polymeric materials, including, but not limited to, rubbers and plastics, for example, thermoplastics and thermosets. The treatment of such substrates in accordance with the methods of the present invention is believed to increase the adhesion of the paint or other decorative coatings to the substrate, to prevent the surface release of mold release agents and to improve the conductivity for electrostatic paints. .

As used herein, the terms "contact" and "contact" refer to applying the composition used in the methods of the present invention by any conventional method known in the art. For example, the composition can be applied to a surface or substrate by atomized coating, roller coating, soaking or immersion. Spray coating is widely used in the metal working industry. The temperature of the composition when applied to the substrate can vary over a wide range, but is preferably from 70 ° F (21.1 ° C) to 160 ° F (71 ° C).

It will be understood by one skilled in the art that an effective amount of the polyether composition may be applied to the treated substrate. As used herein, the term "effective amount" refers to the amount of the present composition necessary to impart the desired level of corrosion resistance and / or adhesion properties of the paint to the treated substrate, or to adequately coat the substrate. treaty. For example, contacting each square foot (m2) of the treated substrate with a composition comprising at least 0.01% of the active ingredient typically can represent the minimum effective amount for most uses. The preferred effective amounts of the composition have a range of active ingredient percent by weight from about 0.01 to 5.

After application of the treatment solution to the substrate, the substrate can optionally be rinsed. Although the good results obtained are rinsed, it is believed that the best results are achieved by rinsing the excess solution completely. Typically, the end use is determined if the rinse is applied at this stage. If the rinse is given, a typical contact time for the composition and the substrate before the rinsing step is in the range from about 5 seconds to 5 minutes, depending on the substrate treated and the level of protection desired.

Next, the treated substrate is dried. The drying can be carried out by, for example, air circulation or oven drying. Drying at room temperature is typically not as fast as oven drying. It is also believed that oven drying yields better results than air drying, however the inventors do not wish to stick to this. Oven drying can be carried out at a temperature between about 300 and 400 ° F (149 and 204 ° C) for a period of between about 1 and 15 minutes. Again, the needs of use can determine what drying technique is used.

After drying, the substrate is ready for treatment such as painting, applying adhesive or the like. The substrate is suitable for standard painting or other coating application techniques such as brush painting, spray painting, electrostatic coating, roller coating, as well as elementary coating. As a result of the methods of the present invention, the substrate, for example the metal surface, which is treated has improved paint adhesion and corrosion resistance properties.

As an example of a modality representative of the best mode, a Mannich derivation is prepared by means of a Mannich reaction using BPA, formaldehyde and diethanolamine. The MBPA is then polymerized with DGEBPA to form a polyether, which is then treated with phosphoric acid. The composition is then applied to a phosphated iron surface, rinsed after a contact time of about 2 minutes and dried in an oven at about 300 ° F (149 ° C) for about 2-3 minutes before of the painted.

Examples The following examples are intended to illustrate the invention and are not constructed to limit the invention in any way.

Example 1 - Preparation of the Mannich Bisphenol A derivative ("MBPA") / condensed EPON (the "Polyether") To prepare the MBPA, about 289.5 g of Bisphenol A (97%, 1.23 moles) is dissolved in 216.0 g of dipropylene glycol methyl ether, obtained from Arco Chemicals as Arcosolv® DPM, and heated to 80 ° C. To this solution is added 391.5 g of diethanolamine (99%, 3.73 moles) while the solution is covered with a stream of nitrogen. While maintaining the nitrogen cover, 298.5 g of formalin is fed (37% aqueous formaldehyde solution, 3.70 moles) in the solution over a period of 30 minutes. The solution is maintained at 80 ° C with stirring for about 5 hours. The BPA: formaldehyde: diethanolamine ratio was 1: 3.0: 3.0. To this solution was added 231.8 g of EPON® 828 (0.62 mol). The reaction mixture was stirred to about 80 ° C for about hours. The resulting product was diluted in an aqueous solution by adding 198.4 g of 80% phosphoric acid and 3093 g of deionized water and stirred until uniform. The product was an aqueous solution having 20% by weight of the active ingredient and a pH of about 6.5. The polyether had an average molecular weight of about 3,000 and an EPON: MBPA ratio of 1: 2. The polyether is referred to as "Sample 1" below.

Example 2 The above procedures were repeated to make polymer of different compositions varying the ratios of phenol: formaldehyde: amine, and EPON®: MBPA. In addition, different EPON® resins were used, as well as different neutralizing acids, quaternary agents and amines. The variations for each of Samples 2-25 are shown in the Table. 1 below Molecular weight was not determined for each sample MAE = 2- (methylamino) ethanol APL = 3-amino-1-propanol Example 3 The diluted solutions of the polyether prepared according to Examples 1 and 2 were applied to an iron phosphate metal at room temperature by either atomization or immersion as indicated in Table 2. The cold roll steel panels were cleaned with a alkaline cleaner, rinsed, treated with an iron phosphate (AC-8225, available from Calgon Corporation, Pittsburg, PA), rinsed, treated with one of the above polyether samples, rinsed and dried. Drying was either at room temperature or by rapid drying, as indicated in Table 2. The alkaline cleaner is a standard Calgon Corporation product containing a caustic inhibitor, water and an amphoteric type wetting surfactant. The product AC-8225 is an iron phosphate that contains phosphoric acid with inorganic accelerators. The treatment with the polyether samples was either by atomization for about 10-30 seconds or by immersion for 2 minutes at room temperature. Quick drying was done by placing the panels in an oven at 300 ° F (149 ° C) for 2 minutes.

After the treatment, the panels were painted with Duracron 200 (PPG Industries, Pittsburg, PA) without any primer. The thickness of the paint was measured in millimeters. The adhesion of the paint was determined in accordance with the "Standard Test Methods for Measuring Adhesion by Tape Test" ASTM D3559 using method B. The combs were drawn from the center down for the spent metal, and subsequently subjected to to the neutral salt spray test to place it in a salt spray cabinet containing a 5% aerated sodium chloride solution at 95 ° F (35.0 ° C). The salt solution was nebulized continuously in the chamber. The panels were removed from the chamber for around 250 hours, and the air used to remove the lost paint was blown. The ASTM and mm read ranges reflect the distance from the center of the plot determined in accordance with the "Standard Test Method for the Evaluation of Painted or Coated Specimens Subjected to Corrosive Environments". The results are given in Table 2.

TABLE 2 Performance Test Results the panels treated with these samples dried quickly.

The ASTM values presented in Table 2 above correspond to the measures presented in Table 3.

TABLE 3 ASTM Values Example 4 The methods of Example 3 are repeated using various polymer application conditions. A range of concentrations, drying temperatures and neutralization acids are used. The treatment and panels are described in Example 3 and are illustrated in Table 4 below.

TABLE 4 As can be seen in Table 4, the ASTM value uses various drying temperatures, pH, and acids where all are higher with the polymers of the present invention than with the control panel.

E j us 5.

The above methods are repeated to compare the panels rinsed after phosphating and those not rinsed after phosphating. Two types of panels, Bonderite® 1000 panels and AC-8225 panels were used. The AC-8225 panels are those described in Example 3. Bonderite® 1000 prepared panels are commercially available phosphate panels from ACT Laboratories, Hillside, MI.

TABLE 5 As can be seen in Table 5, the rinsed panels gave better results than the unrinsed panels, although the unrinsed panels still perform better than the control panels. The performance of the BlOO and AC-8225 panels was around the same While the particular embodiments of this invention have been described above for purposes of illustration, it will be apparent to those skilled in the art that numerous variations of the details of the present invention can be made without departing from the invention as defined in the appended claims. .

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (22)

Claims

1. A method for the treatment of a substrate, characterized in that the substrate is contacted with a composition comprising: a) a polyether derivative, or an acid salt thereof, having the following formula (1): where R is selected from the group consisting Y wherein R1 to R4 are independently selected from the group consisting of H, CqH2q +? and CqH2q-OH; R5 is selected from the group consisting of H, CqH2q + 1, -CqH2q-OH, and CqH2q-COOH; q is between about 1 and 18; the sum of m and m 'is between about .5 and 4.0; n is between about 0 and 3; And it is Z is selected from a group consisting of a straight chain or branched chain divalent aliphatic radical having between about 1 and 3 carbon atoms, S02, SO or O; and X is between about 1 and 50; and b) an appropriate solvent or mixtures thereof.

2. The method according to claim 1, characterized in that the substrate is a metal.

3. The method according to claim 2, characterized in that the metal substrate is a metal surface coated by a phosphate-type conversion.

4. The method according to claim 1, characterized in that the substrate is a polymeric material.

The method according to claim 4, characterized in that the polymeric material is selected from the group consisting of rubber, thermoplastics and thermosets.

6. The method according to claim 1, characterized in that the contact time is between 5 seconds and 5 minutes.

7. The method according to claim 1, characterized in that m and m 'together are equal to between 3.3 and 3.5.

8. The method according to claim 7, characterized in that R3 and R4 are both hydrogen; and R1 and R2 are both C2H40H.

9. The method according to claim 8, characterized in that n is between 0 and 1.

10. The method according to claim 9, characterized in that Z is 2,2-propi leader.

11. The method according to claim 1, characterized in that the molecular weight of the composition is between 1,000 and 50,000.

12. The method according to claim 11, characterized in that the molecular weight of the composition is between 1,000 and 4,000.

13. The method according to claim 1, characterized in that R5 is selected from the group consisting of -H, -CH3, CH2CH20H, and CH2C00H.

The method according to claim 1, characterized in that the phenol: to ldehyde: amine ratio is between 1: 1: 1 and 1: 4: 4 and the diepoxy resin to the phenol derivative ratio Mannich is 1: 2 and 2: 1.

15. The method according to claim 14, characterized in that the ratio of phenol: amine aldehyde is 1: 3.4: 3.6 and the ratio of diepoxy resin to Mannich derivative phenol is between 1: 1.5 and 1: 2.0.

16. The method according to claim 1, characterized in that the contact between the substrate 'and the composition is carried out by atomization, and the contact time is between 30 seconds and 90 seconds.

17. The method according to claim 1, characterized in that the contact between the substrate and the composition is carried out by immersion, and the contact time is between one minute and two minutes.

18. A method for the treatment of a substrate, characterized in that it comprises: a) coating the substrate with a phosphatizer; b) contacting the substrate of step a with a polyether derivative, or acid salt thereof, having the following general formula (1): where R is selected from the group consisting of and wherein R1 to R are independently selected from the group consisting of H, CqH2q +? and CqH2q-0H; R5 is selected from the group consisting of H, CqH2q +? -CqH2q-0H, and CqH2q-C00H; q is between about 1 and 18; the sum of m and m 'is between about .5 and 4.0; n is between about 0 and 3; And it is Z is selected from a straight chain or branched chain divalent aliphatic radical having between about 1 and 3 carbon atoms, S02, SO or 0; and X is between about 1 and 50 in an appropriate solvent or solvent mixtures; c) dry the substrate from step b] and d: paint the substrate of step c)

The method according to claim 19, characterized in that it comprises the step of rinsing the substrate between steps a) and b).

20. The method according to claim 19, characterized in that it additionally comprises the step of rinsing the substrate between steps b) and e).

21. The method according to claim 20, characterized in that it additionally comprises the step of rinsing the substrate ent re b) and e).

22. The method according to claim 1, characterized in that the composition is added to the conversion cover formulation before being contacted with the substrate. METAL USING MANNICH DERIVED POLYETERS Summary of the Invention Methods for the treatment of metal substrates are described. These methods, which comprise contacting the surface to be treated with a composition comprising a Mannich derivatized polyether, improve the corrosion resistance and / or adhesion properties of the treated surface. Similar methods are described for the treatment of polyamine substrates.