JP6282700B2 - Method for processing ferrous metal substrates - Google Patents

Description

This application is a continuation-in-part of US patent application Ser. No. 12 / 237,770, filed Dec. 7, 2011, and is filed on Sep. 25, 2008. This is a continuation-in-part of U.S. Patent No. 13 / 313,473, which is currently acquired as 8,097,093. This application claims the benefit of US Provisional Patent Application No. 60 / 975,957, filed Sep. 28, 2007, which is hereby incorporated by reference.

The present invention relates to a method for treating ferrous metal substrates, such as cold rolled steel, hot rolled steel, and electrogalvanized steel. The invention also relates to a coated ferrous metal substrate. The present invention provides for the removal of iron from the pretreatment bath when the pretreatment bath is on the processing line, both in the presence of an article coated with the pretreatment composition and when the pretreatment bath is off-shift. It also relates to a method for removal.

Background Information The use of protective coatings on metal substrates for the purpose of improved corrosion resistance and paint adhesion is common. Conventional techniques for coating such substrates include techniques including pretreatment of metal substrates with a phosphate coating treatment and a chromium-containing rinse. A typical phosphate film treatment operates where the phosphate is at least in the range of about 1,000 parts per million ("ppm"), which results in waste disposal problems. Thus, the use of such phosphate and / or chromium containing compositions raises environmental and health concerns.

  As a result, chromate-free and / or phosphate-free pretreatment compositions have been developed. Such compositions are generally based on chemical mixtures that react with the substrate surface in some way and bond to the surface to form a protective layer. For example, pretreatment compositions based on IIIB or IVB metal compounds have recently become more widely used.

However, when processing a ferrous metal substrate using a pretreatment composition based on a IIIB or IVB metal compound, the concentration of secondary (Fe ⁺³ ) iron in the pretreatment composition bath increases the amount of iron. As the metal based on is processed, it increases with time. In particular, soluble (Fe ⁺² ) iron from the substrate becomes insoluble (Fe ⁺³ ) through enhancement of Fe ⁺² concentration, oxidation, and subsequent reaction with oxygen and water. The obtained insoluble rust, that is, hydrated iron (III) oxide (Fe ₂ O ₃ .nH ₂ O) and / or iron oxide hydroxide (III) (FeO (OH)) formed agglomerates and insoluble rust. The particles are less likely to settle during gentle agitation while the part is being processed. As a result, insoluble rust particles can adhere or deposit on the substrate and can be transferred to subsequent processing steps such as downstream electrocoating baths used to deposit organic coatings (particularly, If filtration equipment is not available). Such cross-contamination can have a detrimental effect on the performance of such subsequent electrodeposition coatings.

  As a result, as a precaution, periodically diluting the pretreatment bath to reduce soluble iron concentration, and adding replenisher to the pretreatment bath to replenish the bath components and regain coating capacity, It has been practiced in this industry. In some cases, the pretreatment bath must be removed from the processing line and a process must be performed to remove rust from the bath. Alternatively, the pretreatment bath must be drained every 1 to 2 weeks to form a new bath. Each of these practices is costly due to significant product loss, waste disposal, and inconvenience.

  As a result, it would be desirable to provide an improved method for treating ferrous metal substrates and for removing soluble iron that addresses at least some of the foregoing.

SUMMARY OF THE INVENTION In one aspect, the present invention is directed to a method for coating a ferrous metal substrate.

In one aspect, a method for coating an iron metal substrate comprises: (a) an iron metal substrate; the pH is from 4 to 5.5 and (a) a IIIB and / or IVB group metal compound; (b) phosphoric acid Contacting an aqueous pretreatment composition comprising ions and (c) water, wherein the IIIB and / or group IVB metal compound is present in the pretreatment composition in a metal amount of 10 to 500 ppm, The weight ratio of Group IIIB and / or Group IVB metal to phosphate ions in the composition is at least 0.8: 1, wherein the phosphate ions are in the bath of the pretreatment composition, (i) in the bath In an amount sufficient to essentially prevent the formation of insoluble rust, and (ii) not sufficient to prevent the deposition of IIIB or IVB metal coatings having a coverage of at least 10 mg / m ² on ferrous metal substrates. In a sufficient amount, and (i ii) maintaining the weight ratio of phosphate ions to ferric ions in an amount that provides 1 to 1.8: 1; then (b) contacting the substrate with a coating composition comprising a film-forming resin And forming a coated metal substrate exhibiting corrosion resistance characteristics.

In certain other aspects, a method for coating an iron metal substrate comprises: (a) an iron metal substrate; the pH is 4 to 5.5; and (a) a group IIIB and / or group IVB metal compound, (b) Contacting an aqueous pretreatment composition comprising phosphate ions and (c) water, wherein the IIIB and / or Group IVB metal compound is present in the pretreatment composition in a metal amount of 10 to 500 ppm; The weight ratio of Group IIIB and / or Group IVB metal to phosphate ions in the pretreatment composition is at least 0.8: 1, wherein the phosphate ions are in the bath of the pretreatment composition, (i) in the bath In an amount sufficient to essentially prevent the formation of insoluble rust on the substrate, and (ii) prevent deposition of IIIB or IVB metal coatings having a coverage of at least 10 mg / m ² on the iron metal substrate. Insufficient amount And (iii) maintaining the weight ratio of phosphate to additional soluble iron in the ferrous state in an amount ranging from 1.8 to 10: 1; then (b) the substrate; Contacting a coating composition comprising a film-forming resin to form a coated metal substrate exhibiting corrosion resistance properties.

  In certain other aspects, the present invention is directed to a method for removing iron from a pretreatment bath comprising the steps performed when the pretreatment bath is in an offshift.

  In one aspect, an off-shift method for removing iron from a pretreatment bath containing a pretreatment composition comprising a Group IIIB and / or Group IV metal (a) reduces the pH of the pretreatment bath by at least 0.2. (B) adding phosphate ions to the pretreatment bath in (a); and (c) increasing the pH of the pretreatment bath by at least 0.2 in (b).

  In certain other aspects, an offshift method for removing iron from a pretreatment bath containing a pretreatment composition comprising a Group IIIB and / or Group IVB metal comprises: (a) adding an acid to the pretreatment bath; (B) a step of adding phosphate ions to the pretreatment bath in (a); (c) a pH of the pretreatment bath in (b); To 4.0 and 5.5.

The present invention is also directed to a substrate processed and coated thereby.
In the embodiment of the present invention, for example, the following items are provided.
(Item 1)
A method for removing iron from a pretreatment bath containing a pretreatment composition comprising a Group IIIB and / or Group IV metal comprising:
(A) reducing the pH of the pretreatment bath by at least 0.2;
(B) adding a phosphate ion to the pretreatment bath in (a);
(C) increasing the pH of the pretreatment bath by at least 0.2 in (b).
(Item 2)
Item 2. The method according to Item 1, wherein the pH of the pretreatment bath is reduced by at least 1.0.
(Item 3)
The method according to item 1, wherein the reducing step includes a step of adding an acid to the pretreatment bath.
(Item 4)
4. The method of item 3, wherein the acid comprises a Group IVB fluorometal acid, phosphoric acid, sulfuric acid, sulfamic acid, nitric acid, and mixtures thereof.
(Item 5)
4. The method of item 3, wherein the acid comprises hexafluorozirconic acid.
(Item 6)
The method of item 1, wherein the source of phosphate ions comprises alkali metal orthophosphate, ammonium orthophosphate, and mixtures thereof.
(Item 7)
The method of item 1, wherein the source of phosphate ions comprises monosodium phosphate.
(Item 8)
The method according to Item 1, wherein the pretreatment bath in (c) is substantially free of iron.
(Item 9)
The method according to Item 1, further comprising a step of adding an oxidizing agent to the pretreatment bath in (b).
(Item 10)
Item 10. The method according to Item 9, wherein the oxidizing agent comprises a peroxide compound.
(Item 11)
The method according to item 1, further comprising the step of filtering the pretreatment bath in (c).
(Item 12)
Item 2. The method according to Item 1, wherein the method is performed in the absence of an article to be coated with the pretreatment composition.
(Item 13)
Item 2. The method of item 1, wherein the Group IIIB and / or Group IVB metal comprises zirconium.
(Item 14)
Item 2. The method according to Item 1, wherein the pretreatment composition further comprises phosphate ions.
(Item 15)
A method for removing iron from a pretreatment bath containing a pretreatment composition comprising a Group IIIB and / or Group IVB metal comprising:
(A) adding an acid to the pretreatment bath to reduce the pH of the pretreatment composition to less than 4.0;
(B) adding a phosphate ion to the pretreatment bath in (a);
And (c) increasing the pH of the pretreatment bath from 4 to 5.5 in (b).
(Item 16)
16. A method according to item 15, wherein the acid comprises hexafluorozirconic acid.
(Item 17)
16. The method of item 15, wherein the phosphate source comprises monosodium phosphate.
(Item 18)
Item 16. The method according to Item 15, further comprising the step of adding an oxidizing agent to the pretreatment bath in (b).
(Item 19)
19. A method according to item 18, wherein the oxidizing agent comprises a peroxide compound.
(Item 20)
Item 16. The method according to Item 15, further comprising the step of filtering the pretreatment bath in (c).
(Item 21)
Item 15. The pretreatment composition in the pretreatment bath after step (c) comprises a weight ratio of 1: 1 to 1.7: 1 parts by weight of phosphate to ferric ions. The method described.
(Item 22)
Item 16. The method according to Item 15, which is performed in the absence of an article to be coated with the pretreatment composition.
(Item 23)
16. The method of item 15, wherein the pretreatment composition further comprises phosphate ions.

1 and 2 are graphical representations of the observed results of Example 3. FIG. 1 and 2 are graphical representations of the observed results of Example 3. FIG.

FIG. 3 is a graphical representation of the observed results of Example 4.

FIG. 4 is a graphical representation of the observed results of Example 5.

FIG. 5 is a graphical representation of the observed results of Example 6.

DETAILED DESCRIPTION OF THE INVENTION For purposes of describing in detail below, it is understood that the present invention can assume various alternative variations and process sequences, unless the contrary is clearly indicated. The In addition, all numerical values representing amounts of ingredients used in the specification and claims, for example, in all cases other than those described in any operational examples or where otherwise indicated, are in all cases. Is understood to be modified by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought by the present invention. . At the very least, it is not intended to limit the application of the equivalent doctrine to the claims, and each numeric parameter is at least in light of the reported number of significant digits and by applying normal rounding techniques. Should be interpreted.

  Although the numerical ranges and parameters describing the broad scope of the invention are approximate, the numerical values set forth in the specific examples are reported as accurate as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

  Also, any numerical range recited herein should be understood to include all subranges subsumed therein. For example, a range of “1 to 10” is between the indicated minimum value 1 and the indicated maximum value 10 (and includes these values), ie, a minimum value equal to or greater than 1 and 10 It shall include all subranges with maximum values equal or less.

  In this application, the use of the singular includes the plural and the plural includes the singular unless specifically stated otherwise. Further, in this application, the use of “or” means “and / or” unless specifically indicated otherwise, even if “and / or” may be clearly used in a particular case.

  In this application, the term “offshift” means that the article to be coated with the pretreatment composition is not in the pretreatment bath and does not necessarily mean that the pretreatment bath is removed from the process line.

In this application, the term “total iron” or “total Fe” means the total amount of iron in the pretreatment bath, including but not limited to ferric (Fe ⁺² ) iron and primary (Fe ⁺³ ) iron. .

  In this application, unless stated to the contrary, if a pretreatment composition describes a “substantially free” of a particular component, the material being considered is incidental, if any. Means present in the composition as a minor impurity. In other words, since the material is carried over as an impurity as part of the intended composition component, it is not intentionally added to the composition and may be present at low or negligible levels. Further, when a pretreatment composition is described as being “completely free” of a particular component, it means that the material under consideration is not present at all in the composition.

  As mentioned above, certain embodiments of the present invention are directed to methods for processing ferrous metal substrates. Ferrous metal substrates suitable for use in the present invention include automobile bodies, automobile parts, and other articles, such as small metal parts, such as fasteners, ie nuts, bolts, screws, pins, nails, Includes those often used in assembling clips and buttons. Specific examples of suitable ferrous metal substrates include cold-rolled steel, hot-rolled steel, steel coated with zinc metal, zinc compounds, or zinc alloys, such as electrogalvanized steel, hot-dip galvanized steel, galvanil This includes, but is not limited to, steel and steel plated with zinc alloys. Furthermore, the iron substrate treated by the method of the present invention may be the edge of the substrate that is treated in other ways and / or the remaining part of its surface is coated. The metallic iron substrate coated by the method of the present invention may take the form of, for example, a metal plate or a fabricated part.

  The iron substrate treated by the method of the present invention may first be cleaned so that oil, dirt, or other foreign matter is removed. This is often done by using weak or strong alkaline detergents that are commercially available and conventionally used in metal pretreatment processes. Examples of alkaline detergents suitable for use in the present invention are each PPG Industries, Inc. Chemklen ™ 163, 177, 611L, and 490MX, commercially available from

  As already indicated, certain embodiments of the present invention are directed to a method for treating a metal substrate comprising the step of contacting the metal substrate with a pretreatment composition comprising a Group IIIB and / or Group IVB metal. To do. As used herein, the term “pretreatment composition” refers to a composition that, when in contact with a substrate, reacts and chemically changes with the substrate surface to bond to the surface to form a protective layer.

  Often the pretreatment composition comprises a carrier, often an aqueous medium, and thus the composition may take the form of a solution or dispersion in which a IIIB and / or Group IVB metal compound is added to the carrier. In these embodiments, the solution or dispersion is applied by any of a variety of known techniques such as dipping or impregnation, spraying, intermittent spraying, post-dipping spraying, post-spraying dipping, brushing, or roll coating. You may make it contact a board | substrate. In certain embodiments, the solution or dispersion as deposited on the metal substrate is at a temperature ranging from 50 to 150 ° F. (10 to 65 ° C.). The contact time is often 2 seconds to 5 minutes, for example 30 seconds to 2 minutes.

  As used herein, the term “Group IIIB and / or Group IVB metal” refers to Group IIIB or IVB of the CAS element periodic table, as shown, for example, in the Handbook of Chemistry and Physics, 63rd Edition (1983). Refers to a group element. If available, the metal itself may be used. In some embodiments, Group IIIB and / or Group IVB metal compounds are used. As used herein, the term “Group IIIB and / or Group IVB metal compound” refers to a compound comprising at least one element of Group IIIB or Group IVB of the CAS element periodic table.

  In some embodiments, the IIIB and / or IVB metal compound used in the pretreatment composition may be a compound of zirconium, titanium, hafnium, or a mixture thereof. Suitable compounds of zirconium include hexafluorozirconic acid, its alkali metal and ammonium salts, ammonium zirconium carbonate, basic zirconium carbonate, zirconyl nitrate, zirconium carboxylate, and zirconium hydroxycarboxylate such as hydrofluorozirconic acid, zirconium acetate , Zirconium oxalate, ammonium zirconium glycolate, ammonium zirconium lactate, ammonium zirconium citrate, and mixtures thereof, but are not limited thereto. Suitable compounds of titanium include, but are not limited to, fluorotitanic acid and its salts. Suitable compounds of hafnium include, but are not limited to, hafnium nitrate.

  In certain embodiments, the Group IIIB and / or Group IVB metal compound is measured at least 10 ppm metal, such as at least 20 ppm metal, at least 30 ppm metal content, or in some cases at least 50 ppm metal content (measured as elemental metal). Present in the bath of the pretreatment composition. In some embodiments, the IIIB and / or Group IVB metal compound is pretreated with a metal content of 500 ppm or less, such as a metal content of 150 ppm or less, or in some cases a metal content of 80 ppm or less (measured as elemental metal). Present in the bath of the composition. The amount of Group IIIB and / or Group IVB metal in the pretreatment composition can range between any combination of the indicated values and include the indicated values.

  As already indicated, the pretreatment composition used in certain embodiments of the method of the present invention comprises phosphate ions. In certain embodiments, the source of phosphate ions is phosphate, for example 75% phosphate, although other sources of phosphate ions are contemplated by the present invention, such as monosodium phosphate or diphosphate. There is sodium. In certain other embodiments, the pretreatment composition of the method of the present invention is substantially free of phosphate ions.

As already mentioned, in certain embodiments of the method of the invention, phosphate ions are present in the bath of the pretreatment composition in an amount sufficient to essentially prevent the formation of insoluble rust in the bath. Maintained. As used herein, the term “maintained” means that the amount of phosphate ions is regulated and adjusted as necessary to essentially prevent the formation of insoluble rust. . As used herein, the term “essentially prevents the formation of insoluble rust” refers to insoluble rust, ie hydrated iron (III) oxide (Fe ₂ O ₃ .nH ₂ O) and / or water. Including, but not limited to, iron (III) oxide oxide (FeO (OH)) in the bath to the extent that the orange or reddish brown appearance indicating the formation of such compounds in the bath is not visible to the naked eye. It means to prevent the formation. Rather, in certain embodiments of the present invention, phosphate ions comprise soluble iron etched from the surface of an iron metal substrate that has been treated to form iron (III) phosphate (FePO ₄ ) in the bath. Sufficient to form a complex, maintained in the bath, resulting in a bath with a whitish appearance rather than an orange or reddish brown appearance associated with the presence of rust, using conventional filtration equipment Insoluble sludge is formed that can be removed from the bath. Thus, certain embodiments of the present invention may be deposited on a substrate and sent to subsequent processing equipment such as downstream spray nozzles, pumps, rinse baths, and electrocoating baths for depositing organic coatings. Limit the amount of ferric iron (Fe ⁺³ ) in the bath (from the iron metal substrate) that can be used to become insoluble rust that may be generated. As already mentioned, such cross-contamination can have a detrimental effect on the performance of subsequently deposited coatings.

In certain embodiments of the method of the invention, phosphate ions are also present on the iron metal substrate at a coverage (at least 10 mg / m ² , such as at least 100 mg / m ² , or in some cases 100 to 500 mg / m ² ). Maintained in the pretreatment composition bath in an amount insufficient to prevent deposition of a IIIB or IVB metal coating having a total coating weight). In particular, at the pH of the bath used in the present invention, phosphate ions complexed with soluble iron etched from the iron metal substrate to form iron phosphate as desired, and on the iron metal substrate. There is a delicate balance between the complexed phosphate ions and the IIIB or IVB metal present in the bath, which is undesirable because it is believed to prevent the deposition of sufficient IIIB or IVB metal coatings Was discovered.

For every 1 part by weight of ferric (Fe ⁺³ ) ions in the composition, 1 to 1.8, for example 1.2 to 1.6 parts by weight of phosphate ions are present, so It is sufficient to essentially prevent the formation of rust, but to prevent deposition of IIIB or IVB metal coatings having a coverage on the ferrous metal substrate of at least 100 mg / m ² , for example at least 10 mg / m ^2. Was found to be inadequate. As a result, in certain embodiments of the method of the present invention, phosphate ions are in the bath and the weight ratio of phosphate ions to ferric ions is 1 to 1.8: 1, in some cases from 1.2. Maintained at a level resulting in 1.6: 1. When the weight ratio of phosphate ion to ferric ion is less than 1: 1, very little is present in the bath to essentially prevent the formation of insoluble rust in the bath as described above. Phosphate may be present. When the weight ratio of phosphate ions to ferric ions is greater than 1.8: 1, the amount of phosphate ions is sufficient to prevent deposition of sufficient IIIB or IVB metal coatings on the iron metal substrate. It may be sufficient. The ratio of phosphate ions to ferric ions in the pretreatment composition can range between any combination of the listed values, including any of the listed values.

  Further, in certain embodiments of the methods of the present invention, the phosphate ions are at least 50: 1, in some cases at least 25: 1, in a weight ratio of IIIB and / or IVB metal to phosphate ions in the bath. Maintained in the bath at a level that provides at least 12.5: 1 in some cases, at least 3: 1 in some cases, and at least 2: 1 in some cases. If the weight ratio of group IIIB and / or group IVB metal to phosphate ions is less than 2: 1, a great deal of phosphate may be present in the bath, so that on the iron metal substrate It adversely affects the ability to deposit sufficient IIIB or IVB metal coatings.

  As will be apparent, the pretreatment compositions of the present invention may comprise 20 to 500 ppm of Group IIIB and / or IVB metal, for example 30 to 150 ppm, or in some cases 30 to 80 ppm of Group IIIB and / or IVB. In some embodiments of the methods of the present invention because of the inclusion of metals, relatively few phosphate ions are often present in the bath, which in some embodiments is the presence of IIIB and / or IVB in the bath. By maintaining the weight ratio of group metal to phosphate ions in the bath at a level that provides at least 2: 1, in some cases at least 3: 1. As a result, in certain embodiments, such baths contain no more than 30 ppm, eg, 10 to 30 ppm phosphate ions. Further, the presence of low levels of phosphate ions may remove iron from the pretreatment bath, for example, by preventing the formation of insoluble rust in the pretreatment bath for up to months or years in some embodiments. Have a dramatic effect on the useful bath life.

As discussed above, when processing a ferrous metal substrate with a pretreatment composition based on a IIIB or IVB metal compound, the concentration of secondary (Fe ⁺³ ) iron in the pretreatment composition bath is: Increasing with time, as more iron-based metals are processed. The result is that such baths accumulate insoluble rust that can accumulate on the substrate being processed and are carried to subsequent processing steps. To avoid this, such baths must often be changed regularly, sometimes once a week. However, the low levels of phosphate described above are insoluble without preventing sufficient formation of IIIB and / or IVB metal coatings so that they can be operated for months without possibly changing the bath, possibly indefinitely. It was also surprisingly found that rust formation can be prevented. It was surprising and unexpected that such low levels of phosphate could extend the bath life to a significant degree. In addition, the presence of phosphate ions in such small amounts resulted in the formation of a minimum amount of sludge that was well offset by the prevention of insoluble rust, so that waste disposal problems were not a significant concern. .

In certain embodiments, the pretreatment composition also includes a positive metal. As used herein, the term “positive metal” refers to a metal that is more positive than the metal substrate. This means that for the purposes of the present invention, the term “positive metal” includes metals that do not oxidize much more easily than the metal of the metal substrate being processed. As understood by those skilled in the art, the tendency of a metal to oxidize is called the oxidation potential, expressed in volts and measured against a standard hydrogen electrode, which is arbitrarily assigned an oxidation potential of zero. The oxidation potential for several elements is shown in the table below. In the following table, an element does not oxidize as easily as another element if it has a voltage value E ^* greater than the element being compared.

  Thus, as is apparent, when the metal substrate includes iron metal, as in the present invention, suitable positive metals for inclusion in the pretreatment composition include, for example, nickel, tin, copper, silver , And gold, and mixtures thereof.

  In certain embodiments, the source of positive metal in the pretreatment composition is a water-soluble metal salt. In some embodiments of the invention, the water soluble metal salt is a water soluble copper compound. Specific examples of water-soluble copper compounds suitable for use in the present invention include copper cyanide, potassium copper cyanide, copper sulfate, copper nitrate, copper pyrophosphate, copper thiocyanide, ethylenediaminetetraacetic acid disodium copper tetra Hydrate, copper bromide, copper oxide, copper hydroxide, copper chloride, copper fluoride, copper gluconate, copper citrate, copper lauroyl sarcosinate, copper formate, copper acetate, copper propionate, copper butyrate, copper lactate , Copper oxalate, copper phytate, copper tartrate, copper malate, copper succinate, copper malonate, copper maleate, copper benzoate, copper salicylate, copper aspartate, copper glutamate, copper fumarate, copper glycerophosphate, Sodium copper chlorophyllin, copper fluorosilicate, copper fluoroborate, and copper iodate, as well as the copper salt of formic acid to decanoic acid, a family of polybasic acids of the family And copper salts of suberic acid from, but are glycolic acid, lactic acid, tartaric acid, malic acid and copper salts of citric acid hydroxycarboxylic acids, including, and not limited to.

  When copper ions supplied from such water-soluble copper compounds precipitate as impurities in the form of copper sulfate, copper oxide, etc., they suppress copper ion precipitation and thus stabilize copper ions in solution as copper complexes It is considered preferable to add a complexing agent.

In certain embodiments, the copper compound is added as a copper complex salt such as K ₃ Cu (CN) ₄ or Cu-EDTA, which can stably exist in its own composition, and it unique and dissolution It is also possible to form a copper complex that can be stably present in the composition by combining a difficult compound to the complexing agent. Examples include a copper cyanide complex formed by a combination of CuCN and KCN or a combination of CuSCN and KSCN or KCN, and a Cu-EDTA complex formed by a combination of CuSO ₄ and EDTA · 2Na. .

  With respect to the complexing agent, compounds that can form complexes with copper ions can be used; examples include polyphosphates such as sodium tripolyphosphate and hexametaphosphoric acid; ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, And aminocarboxylic acids such as nitrilotriacetic acid; hydroxycarboxylic acids such as tartaric acid, citric acid, gluconic acid, and salts thereof; amino alcohols such as triethanolamine; sulfur compounds such as thioglycolic acid and thiourea; and nitrilotrimethylenephosphones Acids, phosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), and hydroxyethylidenephosphonic acid are included.

  In certain embodiments, a positive metal such as copper is included in the pretreatment composition in an amount (measured as elemental metal) of at least 1 ppm, such as at least 5 ppm, or in some cases at least 10 ppm of total metal. In certain embodiments, the positive metal is included in such pretreatment compositions in an amount (measured as elemental metal) of 500 ppm or less, such as 100 ppm or less, or in some cases 50 ppm or less of the total metal. The amount of positive metal in the pretreatment composition can range between any combination of the listed values, including the listed values.

  As shown, the working pH of the pretreatment composition used in the method of the invention is from 4.0 to 5.5, in some cases from 4.0 to 5.0, from 4.5 to 5.5. Or in other cases, ranging from 4.5 to 5.0. The pH of the pretreatment composition may be adjusted, for example, by using any acid or base as required.

  In addition to the ingredients already mentioned, the pretreatment composition used in the method of the present invention may comprise any of a variety of additional optional ingredients. For example, in one embodiment, the pretreatment composition used in the methods of the present invention is from US Pat. No. 6,805,756, column 3, line 9, which is incorporated herein by reference. Polyhydroxy functional cyclic compounds as described in column 4, line 32. However, in other embodiments, the pretreatment composition used in the methods of the present invention is substantially free or in some cases completely free of any such polyhydroxy-functional cyclic compound.

  In certain embodiments, the pretreatment composition used in the methods of the present invention is a U.S. Pat. No. 6,805,756, column 4, lines 52 to 5, which is incorporated herein by reference. Column 13 line and an oxidant as described in US Pat. No. 6,193,815, column 4, lines 62 to 5, line 39, incorporated herein by reference. Contains an accelerator. In contrast, in other embodiments, the pretreatment composition is substantially free or in some cases completely free of any such oxidizer-accelerator.

  In certain embodiments, the pretreatment composition is an organic, such as a reaction product of an alkanolamine and an epoxy functional material containing at least two epoxy groups, as disclosed in US Pat. No. 5,653,823. A film-forming resin; a resin containing β-hydroxyester, imide, or sulfide functional groups incorporated by using dimethylolpropionic acid, phthalimide, or mercaptoglycerin as an additional reactant in preparing the resin; Diglycidyl ether of bisphenol A (sold by Shell Chemical Company as EPON 880), dimethylolpropionic acid, and diethanolamine in a molar ratio of 0.6 to 5.0: 0.05 to 5.5: 1; A reaction product; U.S. Pat. No. 3,91 Water-soluble and water-dispersible polyacrylic acid disclosed in US Pat. No. 5,662,746; phenol formaldehyde resin described in US Pat. No. 5,662,746; disclosed in WO 95/33869 A water-soluble polyamide such as; a copolymer of maleic acid or acrylic acid and allyl ether described in Canadian Patent Application 2,087,352; discussed in US Pat. No. 5,449,415, And water soluble and dispersible resins including epoxy resins, aminoplasts, phenol-formaldehyde resins, tannins, and polyvinylphenol. In contrast, in other embodiments, the pretreatment composition is substantially free or in some cases completely free of any organic film-forming resin, such as one or more of the above materials.

  In certain embodiments, the pretreatment composition used in the methods of the present invention is described in US Pat. No. 6,805,756, column 6, lines 7-23, which is incorporated herein by reference. Contains fluoride ions, as described. In certain embodiments, fluoride ions are introduced into the composition by IIIB and / or Group IVB metal compounds. In certain embodiments, the pretreatment composition is substantially free of, or in some cases complete, any fluoride ions introduced into the pretreatment composition from sources other than IIIB and / or Group IVB metal compounds. Not included.

  In certain embodiments, the pretreatment composition used in the methods of the present invention is a U.S. Pat. No. 6,805,756, column 6, lines 53-64 and incorporated herein by reference. Polysaccharides as described in international application WO2005 / 001158, page 3, lines 17-23. In contrast, in other embodiments, the pretreatment composition is substantially free or in some cases completely free of any such polysaccharide.

  In certain embodiments, the pretreatment composition used in the methods of the present invention is a water-soluble polyethylene glycol ester of phosphate ester, fatty acid and / or nitric acid, the cited part of which is incorporated herein by reference. US Pat. No. 5,139,586, column 6, lines 31-63. In contrast, in other embodiments, the pretreatment composition is substantially free or in some cases completely free of water-soluble polyethylene glycol esters of phosphate esters, fatty acids and / or nitric acid.

  In certain embodiments, the pretreatment composition used in the methods of the present invention is a U.S. Pat. No. 4,992,115, column 2, lines 47 to 3, which is incorporated herein by reference. It contains vanadium and / or cerium ions as described in column 29 and US Patent Application Publication No. 2007/0068602. In contrast, in other embodiments, the pretreatment composition is substantially free or in some cases completely free of vanadium and / or cerium ions.

  In certain embodiments, the pretreatment composition used in the methods of the present invention is described in US Pat. No. 5,728,233, column 4, lines 24-37, which is incorporated herein by reference. Including phosphorous acid, hypophosphorous acid, and / or salts thereof, as described. In contrast, in other embodiments, the pretreatment composition is substantially free or in some cases completely free of phosphorous acid, hypophosphorous acid, and / or salts thereof.

  In certain embodiments, the pretreatment composition used in the methods of the present invention is described in US Pat. No. 5,380,374, column 3, lines 25-33, which is incorporated herein by reference. Group IIA metals as described, and / or US Pat. No. 5,441,580, column 2, line 66 to column 3, line 4, incorporated herein by reference. Group IA metals as described. In contrast, in other embodiments, the pretreatment composition is substantially free or in some cases completely free of any Group IIA metal and / or any Group IA metal.

In one embodiment, the pretreatment composition used in the method of the invention is a British patent application GB 2
259 920 A, including molybdenum compounds. In contrast, in other embodiments, the pretreatment composition is substantially free or in some cases completely free of any molybdenum compound.

  In certain embodiments, the pretreatment composition used in the method of the present invention is a U.S. Pat. No. 5,104,577, column 2, lines 60 to 3, which is incorporated herein by reference. A metal selected from the group consisting of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, as described in column 26. One or more ions. In contrast, in other embodiments, the pretreatment composition is from the group consisting of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Substantially free or in some cases completely free of any ions of the selected metal.

  The pretreatment composition may optionally contain other materials such as nonionic surfactants and auxiliaries conventionally used in the field of pretreatment. In an aqueous medium, there is a water-dispersible organic solvent, for example, an alcohol having up to about 8 carbon atoms such as methanol, isopropanol; or a glycol ether such as a monoalkyl ether such as ethylene glycol, diethylene glycol, or propylene glycol You may do it. The water-dispersible organic solvent, if present, is typically used in an amount up to about 10 volume percent based on the total volume of the aqueous medium.

  Other optional materials include surfactants that function as antifoams or substrate wetting agents.

  In certain embodiments, the pretreatment composition also includes a filler, such as a siliceous filler. Non-limiting examples of suitable fillers include silica, mica, montmorillonite, kaolinite, asbestos, talc, diatomaceous earth, vermiculite, natural and synthetic zeolites, cement, calcium silicate, aluminum silicate, sodium aluminum silicate, Polyaluminum silicate, alumina silica gel, and glass particles are included. In addition to the siliceous filler, other particulate substantially water-insoluble fillers may be used. Examples of such optional fillers include carbon black, charcoal, graphite, titanium oxide, iron oxide, copper oxide, zinc oxide, antimony oxide, zirconia, magnesia, alumina, molybdenum disulfide, zinc sulfide, barium sulfate. Strontium sulfate, calcium carbonate, and magnesium carbonate. In contrast, in other embodiments, the pretreatment composition is substantially free or in some cases completely free of any such filler.

  In certain embodiments, the pretreatment composition is substantially free or in some cases completely free of heavy metal phosphates such as chromate and / or zinc phosphate. As used herein, the term “substantially free” when used in reference to the absence of chromate and / or heavy metal phosphates in a pretreatment composition makes these substances environmentally friendly. It means not present in the composition to such an extent as to give a load. As used herein, the term “completely free” when used in reference to the absence of heavy metal phosphate and / or chromate, the heavy metal phosphate and / or chromate is a composition. It means nothing at all.

  As will be appreciated, in certain embodiments, the pretreatment composition utilized in the methods of the invention comprises (a) a Group IIIB and / or IVB metal compound such as a zirconium compound; (b) a phosphoric acid such as phosphoric acid. A source of ions; and (c) consisting essentially of or in some cases consisting of water. In certain other embodiments, the pretreatment composition utilized in the methods of the invention consists of (a) or consists essentially of a Group IIIB and / or Group IVB metal compound such as a zirconium compound; and (c) water. In the case it consists of the above. In certain embodiments, such pretreatment compositions include fluoride ions that have been introduced into the pretreatment composition using IIIB and / or Group IVB metal compounds. As used herein, the phrase “consisting essentially of” means that the composition does not include any other ingredients that may significantly affect the basic and novel features of the invention. . For the purposes of the present invention, this means that the pretreatment composition does not contain any ingredients that can significantly affect the ability of the pretreatment composition to be successfully used in the method of the present invention.

In certain embodiments, the remaining film coverage (total film weight) of the pretreatment coating composition is at least 10 milligrams per square meter (mg / m ² ), such as 100 to 500 mg / m ² , or in some cases at least 50 mg / m ² . The thickness of the pretreatment coating can vary, but is generally very thin, often having a thickness of less than 1 micrometer, in some cases 1 to 500 nanometers, and in other cases 10 To 300 nanometers, for example 20 to 100 nanometers.

  In certain embodiments, the offshift method removes soluble iron from the pretreatment bath so that the pretreatment bath is substantially free of iron at the end of the offshift method, thereby enabling the pretreatment composition during operation of the pretreatment composition. Used to ensure that insoluble rust formation is essentially prevented in the bath. The term “substantially free” as used herein means that all iron is present in an amount of less than 10 ppm when used with respect to iron in the bath during operation of the pretreatment composition. To do. As described herein, in certain embodiments, the bath of the pretreatment composition is used, for example, before the presence of phosphate in the pretreatment bath can adversely affect the deposition of the pretreatment composition on the substrate. As in the treatment system, it is substantially free of phosphate ions when the bath is operating. In such an embodiment, the off-shift method of removing iron from the pretreatment bath is a method that substantially prevents the formation of insoluble rust in the pretreatment bath as a method that substantially prevents the formation of insoluble rust. It is considered particularly useful in processing systems. Further, as described herein, in certain other embodiments, the bath of the pretreatment composition may include phosphate ions as a method of essentially preventing the formation of insoluble rust within the pretreatment bath. including. In such embodiments, the off-shift method of removing iron from the pretreatment bath is believed to be particularly useful as an additional or supplemental method that essentially prevents the formation of insoluble rust in the pretreatment bath.

  As already indicated, in certain embodiments, the pretreatment bath has a working pH greater than 4.0, such as between 4.2 and 5.5, preferably between 4.5 and 5.0, most preferred. Has a working pH of 4.8. In certain embodiments, the first step of the off-shift method of removing iron from the pretreatment bath includes reducing the pH of the pretreatment bath by at least 0.2, such as at least 0.5, or at least 1.0, For example, the pH of the pretreatment bath is reduced between 1.0 and 3.8, preferably between 2.5 and 3.3. In certain embodiments, the pH of the pretreatment bath is reduced by adding an acid to the pretreatment bath, which includes, as a non-limiting example, a Group IVB fluoro metal acid, such as hexafluorozircon. Acids and hexafluorotitanic acid, phosphoric acid, sulfuric acid, sulfamic acid, nitric acid, and mixtures thereof are included.

  In one embodiment of the off-shift method of removing iron from the pretreatment bath, the first step of reducing the pH of the pretreatment bath is to pre-add a sufficient amount of acid to reduce the pH, as discussed above. This is realized by adding to the treatment bath.

  In certain embodiments of the offshift method of removing iron from the pretreatment bath, the second step includes adding phosphate ions to the pretreatment bath. In certain embodiments, the source of phosphate ions includes alkali metal and ammonium orthophosphate present as either monohydrogen or dihydrogen forms, including, for example, monosodium phosphate, disodium phosphate, and mixtures thereof. It may be a salt. In one embodiment, Zircobond Additive P, or PPG Industries, Inc. A monosodium phosphate solution, commercially available from Euclid, Ohio, is used as the source of phosphate ions.

  In some embodiments of the offshift method of removing iron from the pretreatment bath, the third step includes adding an oxidant to the pretreatment bath. In such embodiments, the oxidant is a peroxide compound, air, sodium nitrite, sodium bromate, and mixtures thereof. In a preferred embodiment, the peroxide compound is hydrogen peroxide.

  In one embodiment of the off-shift method of removing iron from the pretreatment bath, a source of phosphate ions and an oxidizing agent are each added in an amount sufficient to provide a pretreatment bath that is substantially free of iron.

  In some embodiments of the off-shift method of removing iron from the pretreatment bath, the fourth step includes increasing the pH of the pretreatment bath by at least 0.2. In an embodiment, the pH is higher than 4.0, for example from 4.2 to 5.2, from 4.5 to 5.0, and to 4.8. In certain embodiments, the pH is increased by adding a sufficient amount of an alkaline composition to the pretreatment bath, including, as non-limiting examples, caustic soda, caustic potash, and sodium hydroxide. In an embodiment, the alkaline composition is Chemfil Buffer, PPG Industries, Inc. Commercially available products from Euclid, Ohio, can be used in an amount sufficient to achieve the desired working pH.

In one embodiment of the off-shift method of the present invention, phosphate ions are soluble iron etched from the surface of an iron metal substrate that is treated to form iron (III) phosphate (FePO ₄ ) in a bath. Sufficient to form a complex with the pretreatment bath, resulting in a bath with a whitish appearance rather than the orange or reddish brown appearance associated with the presence of rust, using conventional filtration equipment Insoluble sludge is formed which can be removed from the bath. In some embodiments of the offshift method of the present invention, the fifth step comprises pretreating a solid material from the pretreatment bath, i.e., iron phosphate, iron oxide, iron hydroxide, or any other insoluble fludge. To filter the pretreatment bath using such conventional filtration equipment. In certain embodiments, the filtering step may be immediately after raising the pH of the pretreatment bath by at least 0.2. In certain other embodiments, the filtering step may be after an equilibration period, i.e., an equilibration period during which the insoluble sludge settles to the bottom of the pretreatment bath, e.g., the pH of the pretreatment bath. It may be 1 to 10 hours after raising.

  Thus, the off-shift method of the present invention is an insoluble solution that can be deposited on a substrate and transferred to subsequent processing equipment such as downstream spray nozzles, pumps, rinse baths, and electrocoating baths for depositing organic coatings. Remove soluble iron in the bath (from the ferrous metal substrate) that can become rusted. As already indicated, such cross-contamination can have a detrimental effect on the performance of such subsequently deposited coatings. Surprisingly, however, the iron in the bath is essentially removed by lowering the pH of the pretreatment bath below the working pH and then adding the aforementioned low levels of phosphate and optionally an oxidizing agent. Thereby preventing the formation of insoluble rust within the pretreatment without preventing significant IIIB and / or IVB metal coating formation after the bath pH has increased to the working level, and Results We have found that this bath can be operated for several months, possibly indefinitely, without replacement. It was surprising and unexpected that such a process was able to extend the life of the bath to such a significant degree.

  After contacting the pretreatment solution, the substrate may be rinsed with water and dried.

  In certain embodiments of the method of the present invention, the substrate is contacted with the pretreatment composition and then contacted with the coating composition comprising a film-forming resin. Any suitable technique for contacting the substrate with such a coating composition may be used including techniques such as brushing, dipping, flow coating, and spraying. However, in certain embodiments, such contact includes an electrocoating step in which the electrodepositable composition is deposited on the metal substrate by electrodeposition, as described in more detail below.

  As used herein, the term “film-forming resin” refers to a self-supporting continuous, at least horizontal plane of the substrate after removal of any diluent or carrier present in the composition or after curing at ambient or elevated temperature. It refers to a resin that can form a film. Conventional film-forming resins that may be used include, among others, automotive OEM coating compositions, automotive repaint coating compositions, industrial coating compositions, architectural coating compositions, coil coating compositions, and aerospace applications. This includes, but is not limited to, those typically used in coating compositions.

  In certain embodiments, the coating composition includes a thermosetting film-forming resin. As used herein, the term “thermosetting” refers to a resin that irreversibly “cures” after curing or crosslinking and in which the polymer chains of the polymer components are joined together by covalent bonds. This property is usually associated with a cross-linking reaction of the components of the composition often induced, for example, by heat or radiation. The curing or crosslinking reaction may be performed under ambient conditions. After curing or crosslinking, the thermosetting resin does not melt upon application of heat and is insoluble in the solvent. In other embodiments, the coating composition comprises a thermoplastic film-forming resin. As used herein, the term “thermoplastic” refers to a resin that includes polymer components that are not covalently joined together, thereby being capable of liquid flow upon application of heat and being soluble in a solvent.

  As already indicated, in some embodiments, the substrate and the coating composition comprising a film-forming resin are contacted by an electrocoating process in which the electrodepositable composition is deposited on the metal substrate by electrodeposition. In the electrodeposition process, a treated metal substrate serving as an electrode and an electrically conductive counter electrode are placed in contact with an ionic electrodepositable composition. By passing an electric current between the electrode and the counter electrode in contact with the electrodepositable composition, an adhesive film of the electrodepositable composition is deposited on the metal substrate in a substantially continuous state. Will be.

  Electrodeposition is usually performed at a constant voltage in the range of 1 to thousands of volts, typically 50 to 500 volts. Current density is typically between 1.0 and 15 amps per square foot (10.8 to 161.5 amps per square meter) and tends to decrease rapidly during the electrodeposition process, which is a continuous self-insulating coating Shows that it forms.

  Electrodepositable compositions utilized in certain embodiments of the present invention often include a resinous phase dispersed in an aqueous medium, the resinous phase comprising (a) an ionic electrodepositable resin containing active hydrogen groups And (b) a curing agent having a functional group that reacts with the active hydrogen group of (a).

  In certain embodiments, the electrodepositable composition utilized in certain embodiments of the present invention contains an active hydrogen-containing ionic, often cationic, electrodepositable resin as the main film-forming polymer. A wide variety of electrodepositable film-forming resins are known, and in the present invention, so long as the polymer is “water-dispersible”, ie, adapted to be solubilized, dispersed, or emulsified in water. Can be used. A water-dispersible polymer is ionic in nature, i.e. the polymer will contain anionic functional groups to give a negative charge or, as often preferred, to give a positive charge. It will contain ionic functional groups.

  Examples of film-forming resins suitable for use in anionic electrodepositable compositions include base solubilized carboxylic acid-containing polymers such as reaction products of drying oils or semi-drying fatty acid esters with dicarboxylic acids or anhydrides Or an adduct; a reaction product that is a fatty acid ester, an unsaturated acid or anhydride, and any additional unsaturated modifying material that is further reacted with a polyol. Also suitable are at least partially neutralized interpolymers of hydroxy-alkyl esters of unsaturated carboxylic acids, unsaturated carboxylic acids, and at least one other ethylenically unsaturated monomer. Yet another suitable electrodepositable film-forming resin comprises an alkyd-aminoplast excipient, ie, an excipient containing an alkyd resin and an amine-aldehyde resin. Yet another anionic electrodepositable resin composition is described in US Pat. No. 3,749,657, column 9, lines 1-75 and column 10, column 1, which is incorporated herein by reference. To 13 in a mixed ester of a resinous polyol. Other acid functional polymers such as phosphorylated polyepoxides or phosphorylated acrylic polymers known to those skilled in the art can also be used.

  As mentioned above, it is often desirable that the active hydrogen-containing ionic electrodepositable resin (a) is cationic and can be deposited on the cathode. Examples of such cationic film-forming resins are described in US Pat. Nos. 3,663,389; 3,984,299; 3,947,338; and 3,947,339. Included are amine base-containing resins such as acid solubilization reaction products of polyepoxides with primary or secondary amines. Often these amine base-containing resins are used in combination with a blocked isocyanate curing agent. The isocyanate can be completely blocked as described in US Pat. No. 3,984,299, or the isocyanate can be partially blocked as described in US Pat. No. 3,947,338. And can react with the main chain of the resin. Moreover, the one-component composition described in US Pat. No. 4,134,866 and DE-OS 2,707,405 can also be used as a film-forming resin. In addition to the epoxy-amine reaction product, the film-forming resin can also be selected from cationic acrylic resins as described in US Pat. Nos. 3,455,806 and 3,928,157. .

  In addition to amine base-containing resins, organic polyepoxides and tertiary amine salts described in US Pat. Nos. 3,962,165; 3,975,346; and 4,001,101 Quaternary ammonium base-containing resins such as formed from the reaction can also be used. Examples of other cationic resins are ternary sulfonium base-containing resins and quaternary phosphonium base-containing resins described in US Pat. Nos. 3,793,278 and 3,984,922, respectively. It is like. It is also possible to use film-forming resins that cure via transesterification as described in European Application 12463. In addition, cationic compositions prepared from Mannich bases as described in US Pat. No. 4,134,932 can be used.

  In certain embodiments, the resin present in the electrodepositable composition is as described in US Pat. Nos. 3,663,389; 3,947,339; and 4,116,900. A positively charged resin containing primary and / or secondary amine groups. In U.S. Pat. No. 3,947,339, a polyketimine derivative of a polyamine such as diethylenetriamine or triethylenetetraamine is reacted with a polyepoxide. When the reaction product is neutralized with an acid and dispersed in water, free primary amine groups are generated. Also, when the polyepoxide reacts with excess polyamine such as diethylenetriamine or triethylenetetraamine, an equivalent product is also formed, as described in US Pat. Nos. 3,663,389 and 4,116,900. In addition, excess polyamine is vacuum stripped from the reaction mixture.

  In certain embodiments, the active hydrogen-containing ionic electrodepositable resin is present in the electrodepositable composition in an amount of 1 to 60 weight percent, for example 5 to 25 weight percent, based on the total weight of the electrodeposition bath. Exists.

  As indicated, the resinous phase of the electrodepositable composition often further comprises a curing agent adapted to react with the active hydrogen groups of the ionic electrodepositable resin. For example, both blocked organic polyisocyanates and aminoplast curing agents are suitable for use in the present invention, but blocked isocyanates are often preferred for cathodic electrodeposition.

  Aminoplast resins, which are often preferred curing agents for anionic electrodeposition, are condensation products of amines or amides with aldehydes. Examples of suitable amines or amides are melamine, benzoguanamine, urea, and similar compounds. Generally, the aldehyde used is formaldehyde, but the product can be made from other aldehydes such as acetaldehyde and furfural. The condensation product contains methylol groups or similar alkylol groups depending on the particular aldehyde used. Often these methylol groups are etherified by reaction with alcohols such as monohydric alcohols containing 1 to 4 carbon atoms such as methanol, ethanol, isopropanol, and n-butanol. Aminoplast resins are available from American Cyanamid Co. From the trademark CYMEL, and Monsanto Chemical Co. Commercially available under the trademark RESIMENE.

  The aminoplast curing agent contains active hydrogen in an amount ranging from 5 weight percent to 60 weight percent, for example ranging from 20 weight percent to 40 weight percent, based on the total weight of resin solids in the electrodepositable composition. Often used in conjunction with an anionic electrodeposition resin.

  As indicated, blocked organic polyisocyanates are often used as curing agents in cathode electrodeposition compositions. The polyisocyanate can be completely blocked as described in US Pat. No. 3,984,299, column 1, lines 1 to 68, column 2, and column 3, lines 1 to 15, Or partially blocked and reacted with the polymer backbone as described in US Pat. No. 3,947,338, column 2, lines 65-68, column 3, and column 4, lines 1-30. The citations of these documents are hereby incorporated by reference. “Blocked” means that the isocyanate group reacts with the compound, and the resulting blocked isocyanate group is stable to active hydrogen at ambient temperature, but usually in a film-forming polymer at a high temperature of 90 ° C. to 200 ° C. It means to react with active hydrogen.

  Suitable polyisocyanates include aromatic and aliphatic polyisocyanates including alicyclic polyisocyanates, representative examples include diphenylmethane-4,4′-diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), mixtures thereof, p-phenylene diisocyanate, tetramethylene and hexamethylene diisocyanate, dicyclohexylmethane-4,4 ′ diisocyanate, isophorone diisocyanate, phenylmethane-4,4′- A mixture of diisocyanate and polymethylene polyphenyl isocyanate is included. Higher polyisocyanates such as triisocyanates can be used. Examples would include triphenylmethane-4,4 ′, 4 ″ -triisocyanate. Polyols such as neopentyl glycol and trimethylol propane, and polycaprolactone diols and triols (NCO / OH It is also possible to use an isocyanate () -prepolymer having a polymer polyol such as an equivalence ratio greater than 1.

  The polyisocyanate curing agent is an active hydrogen-containing positive agent in an amount ranging from 5 weight percent to 60 weight percent, for example from 20 weight percent to 50 weight percent, based on the total weight of the resin solids of the electrodepositable composition. Typically used in conjunction with an ionic electrodepositable resin.

  In certain embodiments, a coating composition that includes a film-forming resin also includes yttrium. In certain embodiments, yttrium is present in such a composition in an amount of 10 to 10,000 ppm of total yttrium, such as 5,000 ppm or less, in some cases 1,000 ppm or less (measured as elemental yttrium). Exists.

  Both soluble and insoluble yttrium compounds may serve as a source of yttrium. Examples of suitable yttrium sources for use in lead-free electrodepositable coating compositions include soluble organic and yttrium acetate, yttrium chloride, yttrium formate, yttrium carbonate, yttrium sulfamate, yttrium lactate, and yttrium nitrate. Inorganic yttrium salt. When yttrium is added as an aqueous solution to the electrocoating bath, yttrium nitrate, a readily available yttrium compound, is the preferred yttrium source. Other yttrium compounds suitable for use in the electrodepositable composition include organic and inorganic yttrium such as yttrium oxide, yttrium bromide, yttrium hydroxide, yttrium molybdate, yttrium sulfate, yttrium silicate, and yttrium oxalate. A compound. Organic yttrium complexes and yttrium metals can also be used. When yttrium is incorporated into the electrocoating bath as a component of the pigment paste, yttrium oxide is often the preferred source of yttrium.

  The electrodepositable composition described herein takes the form of an aqueous dispersion. The term “dispersion” is considered a two-phase transparent, translucent or opaque resinous system in which the resin is in the dispersed phase and water is in the continuous phase. The average particle size of the resinous phase is generally less than 1.0 microns, usually less than 0.5 microns, often less than 0.15 microns.

  The concentration of the resinous phase in the aqueous medium is often at least 1 weight percent, for example 2 to 60 weight percent, based on the total weight of the aqueous dispersion. When such compositions are in the form of resin concentrates, they generally have a resin solids content of 20 to 60 weight percent based on the weight of the aqueous dispersion.

  The electrodepositable compositions described herein are composed of two components: (1) an active hydrogen-containing ionic electrodepositable resin, i.e., a main film-forming polymer, a curing agent, and any additional water dispersible non-colored. A transparent resin supply comprising components; (2) one or more colorants (described below), a water dispersible ground resin that can be the same as or different from the main film-forming polymer, and Often supplied as a pigment paste, which generally contains additives such as optionally wetting or dispersing aids.

  In one embodiment, the two-component electrodepositable composition is embodied in the form of an electrodeposition bath as is well known to those skilled in the art, and components (1) and (2) are aqueous and usually comprise a fusion solvent. Distributed on the medium. The advantage of the method according to the invention is that, as already indicated, such a bath can be prevented from being contaminated with rust even in the absence of a filtration facility.

  As described above, in addition to water, the aqueous medium may contain a fusion solvent. Useful fusion solvents are often hydrocarbons, alcohols, esters, ethers, and ketones. Preferred coalescing solvents are often alcohols, polyols, and ketones. Specific fusion solvents include isopropanol, butanol, 2-ethylhexanol, isophorone, 2-methoxypentanone, ethylene and propylene glycol, monoethyl monobutyl and monohexyl ethers of ethylene glycol. The amount of fusion solvent is generally from 0.01 to 25 weight percent, for example from 0.05 to 5 weight percent, based on the total weight of the aqueous medium.

  In addition, colorants and, if desired, various additives such as surfactants, wetting agents, or catalysts can be included in the coating composition comprising the film-forming resin. As used herein, the term “colorant” means any substance that imparts color and / or other opacity and / or other visual effects to a composition. The colorant can be added to the composition in any suitable form, such as individual particles, dispersions, solutions, and / or flakes. A single colorant or a mixture of two or more colorants can be used.

  Exemplary colorants include pigments, dyes, and colours, such as those used in the paint industry and / or listed in the Dry Color Manufacturers Association (DCMA), as well as special effects compositions Things are included. The colorant may comprise, for example, a fine solid powder that is insoluble but wettable under the conditions of use. The colorant can be organic or inorganic and can be agglomerated or not agglomerated. Colorants can be incorporated through the use of grinding excipients such as acrylic grinding excipients, which use will be familiar to those skilled in the art.

  Exemplary pigments and / or pigment compositions include carbazole dioxazine crude pigment, azo, monoazo, diazo, naphthol AS, salt type (lake), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline, And polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavantron, pyratron, anthrone, dioxazine, triarylcarbonium, quinophthalone pigment, diketopyrrolopyrrole red ("DPPBO red"), titanium dioxide, carbon black, and mixtures thereof, but are not limited to these. The terms “pigment” and “colored filler” can be used interchangeably.

  Exemplary dyes include, but are not limited to, those based on solvents and / or aqueous bases, such as phthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum, and quinacridone. is not.

Exemplary shades include Degussa, Inc. Commercially available from AQUA-CHEM
896, Eastman Chemical, Inc. Include, but are not limited to, pigments dispersed in water-based or water-miscible carriers, such as CHARISMA COLORANTS and MAXIONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions divisions.

  As noted above, the colorant can take the form of a dispersion, including but not limited to a nanoparticle dispersion. The nanoparticle dispersion can include one or more highly dispersed nanoparticle colorants and / or colored particles that provide the desired visible color and / or opacity and / or visual effect. The nanoparticle dispersion can include a colorant such as a pigment or dye having a particle size of less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles can be produced by milling stock organic or inorganic pigments with grinding media having a particle size of less than 0.5 mm. Exemplary nanoparticle dispersions and methods for making them are disclosed in US Pat. No. 6,875,800 (B2), incorporated herein by reference. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and chemical abrasion (ie, partial dissolution). In order to minimize reagglomeration of the nanoparticles within the coating, a dispersion of nanoparticles coated with resin can be used. As used herein, “a dispersion of nanoparticles coated with a resin” refers to a continuous phase in which individual “composite microparticles” comprising nanoparticles and a resin coating on the nanoparticles are dispersed. Exemplary resin-coated nanoparticle dispersions and methods for making them are described in US Patent Application Publication No. 2005-2005, filed June 24, 2004, which is also incorporated herein by reference. No. 0287348 (A1), US Provisional Application No. 60 / 482,167 filed on June 24, 2003, and US Patent Application No. 11 / 337,062 filed on January 20, 2006 Has been.

  Exemplary special effects compositions that may be used include one such as reflectance, pearl foil, metallic luster, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism, and / or color change. Alternatively, pigments and / or compositions that exhibit multiple appearance effects are included. Additional special effect compositions can provide other perceptible properties, such as opacity or texture. In certain embodiments, the special effects composition can provide a color shift such that the color of the coating changes when the coating is viewed from different angles. Exemplary color effect compositions are disclosed in US Pat. No. 6,894,086, incorporated herein by reference. Additional color effect compositions may include transparent coated mica and / or synthetic mica, coated silica, coated alumina, transparent liquid crystal pigments, liquid crystal coatings, and / or any composition, i.e., interfering refractive in the material. Compositions can be included that arise from the rate difference and are not due to the refractive index difference between the surface of the material and the air.

  In certain embodiments, photosensitive and / or photochromic compositions that reversibly change their color when exposed to one or more light sources can be used. The photochromic and / or photosensitive composition can be activated by exposure to radiation of a specified wavelength. When the composition is excited, the molecular structure changes and the altered structure exhibits a new color that is different from the original color of the composition. When exposure to radiation is removed, the photochromic and / or photosensitive composition can return to a quiescent state where the original color of the composition is restored. In certain embodiments, the photochromic and / or photosensitive composition can be colorless in the unexcited state and can exhibit color in the excited state. A complete color change can appear within milliseconds to a few minutes, for example within 20 seconds to 60 seconds. Exemplary photochromic and / or photosensitive compositions include photochromic dyes.

  In certain embodiments, the photosensitive composition and / or photochromic composition can be associated and / or at least partially attached to the polymer and / or polymeric material of the polymerizable component, such as by a covalent bond. In contrast to some coatings in which the photosensitive composition can migrate out of the coating and crystallize into the substrate, and / or associated with a polymer and / or polymerizable component according to certain embodiments of the invention. At least partially bonded photosensitive and / or photochromic compositions have minimal migration out of the coating. Exemplary photosensitive compositions and / or photochromic compositions and methods for making them are described in US application Ser. No. 10 / 892,919 filed Jul. 16, 2004, which is incorporated herein by reference. Will be revealed.

  In general, the colorant can be present in the coating composition in any amount sufficient to provide the desired visual and / or color effect. The colorant may comprise 1 to 65 weight percent, such as 3 to 40 weight percent, or 5 to 35 weight percent, based on the total weight of the composition.

  After deposition, the coating is often heated to cure the deposited composition. The heating or curing operation is often performed at a temperature in the range of 120 to 250 ° C., for example 120 to 190 ° C., for a time ranging from 10 to 60 minutes. In certain embodiments, the resulting coating thickness is 10 to 50 microns.

As will be appreciated from the foregoing description, certain embodiments of the present invention are also directed to a method for preventing rust contamination of a coating facility, even in the absence of a filtration facility in the process of coating a ferrous metal substrate. To do. In certain embodiments, such a method has a pH of 4 to 5.5 and includes: (a) a Group IIIB and / or IVB metal compound; (b) a phosphate ion; and (c) water. In some cases, it includes a step of utilizing a pretreatment composition consisting essentially of these. In such embodiments of the method of the present invention, phosphate ions are: (i) sufficient to essentially prevent the formation of insoluble rust in the bath; and (ii) coating on the iron metal substrate. Maintained in the pretreatment composition bath in an amount insufficient to prevent deposition of IIIB and / or IVB metal coatings having a rate of at least 10 mg / ft ² . In certain other embodiments, such methods may include Group IIIB and / or Group IVB metals, which in some embodiments are substantially free of phosphate ions during operation and in certain other embodiments include phosphate ions. Including an off-shift method of removing iron from the pretreatment bath. The offshift method comprises (a) reducing the pH of the pretreatment bath by at least 0.2; (b) adding phosphate ions to the pretreatment bath in (a); (c) pretreatment bath in (b). And (d) increasing the pH of the pretreatment bath by at least 0.2 in (d) and (c). In such an off-shift process that removes iron from the pretreatment bath, insoluble rust may be essentially removed from the pretreatment bath. In certain embodiments, the offshift method further includes filtering the pretreatment bath using a filtration facility.

  As will also be appreciated, the present invention is also directed to a method for coating a ferrous metal substrate. In certain embodiments, these methods comprise (a) an iron metal substrate, a pH of 4 to 5.5, and (i) a IIIB and / or IVB group metal compound, (ii) phosphate ions, and (ii) ) Contact with an aqueous pretreatment composition comprising water, or in some cases consisting essentially of water, wherein phosphate ions are insoluble in the bath of the pretreatment composition A coated metal substrate that exhibits corrosion resistance properties by contacting the substrate with a coating composition that includes a film-forming resin; Forming the step. In certain other embodiments, such a method comprises: (a) removing iron from the pretreatment bath when the pretreatment bath is off-shift; and (b) an iron metal substrate and a pH of from 4 Contacting the aqueous pretreatment composition comprising 5.5 and (i) a Group IIIB and / or Group IVB metal and (ii) water, or in some cases essentially consisting of water, comprising: A coating composition, which in one embodiment is substantially free of phosphate ions; and then (c) contacting the substrate with a coating composition comprising a film-forming resin to provide a coated metal exhibiting corrosion resistance properties Forming a substrate. In such methods, the step of removing iron from the pretreatment bath when the pretreatment bath is off-shift comprises: (a) reducing the pH of the pretreatment bath by at least 0.2; and (b) (a) Adding a phosphate ion to the pretreatment bath in (c) and (b); adding an oxidizing agent to the pretreatment bath in (c) and (b); and (d) adjusting the pH of the pretreatment bath to at least 0.2 in (c). And in some cases consists essentially of these. As used herein, the term “corrosion resistance” refers to a measure of corrosion protection for metal substrates utilizing the test described in ASTM B117 (Salt Spray Test). In this test, a bare metal substrate is exposed by scratching the coated substrate with a knife according to ASTM D1654-92. A scratched substrate is placed in a test chamber and an aqueous salt solution is continuously sprayed onto the substrate. Maintain the chamber at a constant temperature. The coated substrate is exposed to a salt spray environment for a specified period of time, for example 250, 500, or 1000 hours. After exposure, the coated substrate is removed from the test chamber and evaluated for corrosion along the wound. Corrosion is measured by "scribe creep", defined as the total distance traveled from end to end of the wound, expressed in millimeters. When the substrate is said to “show corrosion resistance”, the scribe creep indicated by the ferrous metal substrate is PPG Industries, Inc. as PCT79111 according to the manufacturer's instructions. Means 3 mm or less after testing with ASTM B117 for 500 hours in a salt spray environment.

  The invention is illustrated by the following examples, which are not to be considered as limiting the invention in detail. All parts and percentages in the examples and throughout the specification are by weight unless otherwise indicated.

Example 1
In one experiment, five clean steel panels were placed in an aqueous solution having a pH of about 1.8-2.4 and containing fluorozirconic acid and phosphoric acid (Zr 90 ppm, and PO ₄ ^-3 10 ppm). After increasing the ferrous iron concentration to about 30 ppm, the panel was removed from the clear solution and divided into 1 gallons (3.78 liters).

  The first gallon was further subdivided into 700 ml portions, and (75 wt%) phosphoric acid was added thereto, resulting in a series of baths with phosphate ions of 10, 25, 50, 75, and 100 ppm. . The same series of phosphate levels was repeated with 125, 150, and 200 ppm zirconium.

  The pH of all sample baths was adjusted to 5.0. Baths containing 30 ppm ferrous iron and varying amounts of zirconium and phosphate ions were left stationary for 2 days. Two days later, the appearance of the individual baths was noted. The results summarized in Table 1.0 below demonstrate that in this example a zirconium bath containing 30 ppm total iron is converted from a brown to white appearance in the presence of 25 to 50 ppm phosphate ions. . The brown appearance indicates the formation of iron oxide or iron oxyhydroxide.

The resulting matrix showed that all of the 10 ppm PO ₄ ^-3 baths produced rust-colored water and almost brown precipitates to the same extent, ie independent of Zr levels. The next lighter colors were all 25 ppm PO ₄ ^-3 baths, again with lightly colored precipitates. All 50 ppm PO ₄ ^-3 baths were nearly colorless with barely off-white crystalline precipitate. The 75 and 100 ppm PO ₄ ^-3 baths were all colorless and had a white crystalline precipitate. This white precipitate was ferric phosphate and probably had insignificant amounts of zirconium compounds.

In this example, the weight ratio of phosphate to ferric iron is at least 1: 1, such as at least 1.2: 1, such as 1 to 1.8: 1, and the bath treats the iron metal substrate. When used to do so, it is essentially sufficient to prevent the formation of insoluble rust in pretreatment baths containing Group IIIB and / or Group IVB metals.

(Example 2)
The steel panel is cleaned using a conventional alkali-based detergent, rinsed twice with tap water and treated in a bath containing zirconium in the range of 10-150 ppm and phosphate in the range of 10-100 ppm, Then it was subsequently rinsed with tap water. Both treated steel panels and PPG
Industries Inc. A P590 cationic epoxy electrodeposition coating or a PCT 79111 triglycidyl isocyanurate-polyester powder coating commercially available from Corrosion performance was determined by exposing the zirconium treated and painted panels to a neutral salt spray for the times shown in Table 2.0 according to ASTM B117. The acceptable performance of the cationic epoxy electrodeposition coating at 1000 hours of neutral salt spray exposure in this test was a ½-width scribe loss of 4.0-5.0 mm. The acceptable performance of TGIC-polyester powder at 500 hours neutral salt spray exposure was a ½-width scribe loss of 2.0-3.0 mm. The following results demonstrate that acceptable corrosion performance can be obtained when phosphate ions are added to the zirconium treatment bath. As shown in Example 1.0, at low phosphate ion concentrations, the treatment bath turns brown indicating the presence of iron oxide or iron oxyhydroxide.

(Example 3)
A pretreatment solution was prepared, and a large amount of hexafluorozirconic acid was added thereto. The bath pH was adjusted to 4.7 before coating the cold rolled steel panel. Panels obtained from ACT Labs (Hillsdale, MI) were first spray-cleaned with alkaline detergent (PPG Industries Chemkleen 611L, 2% and 140-150 ° F.), rinsed twice and then entered the pretreatment zone I let you. A zirconium bath was sprayed onto the panel at 9 psi for 60 seconds. They were then rinsed with tap water and finally rinsed with deionized water halo before proceeding to the infrared drying process.

  Panel samples were obtained at 0, 10, 15, 20, 50, and 80 ppm zirconium bath levels. Each cross section was analyzed via XPS (X-ray photoelectron spectroscopy) to determine the layer thickness of zirconium in the coating. The depth of the zirconium layer was determined to be nanometers where the profile dropped back to the atomic percent level of 10%. The resulting table for depth was graphed against zirconium bath concentration as shown in FIG.

  Using the same series of panels, PPG Industries, Inc. as Powercron 395. After anionic acrylic electrocoating, commercially available from U.S.A., was applied to three panels at each level, corrosion tests were performed according to ASTM B117 and D1654-92. The results are shown in FIG. The results confirm that a good degree of corrosion protection is reached, from a bath with 20 ppm zirconium, consistent with the minimum thickness realization.

Example 4
Indeed, a bath that is heavily contaminated with rust turns to an opaque brownish red after the appearance of a translucent orange solution, indicating that it was first converted to an insoluble ferric complex. In one experiment, a 10 gallon low pH bath (about 2.7) containing 100 ppm zirconium was sprayed onto the steel panel for several hours until total iron reached 50 ppm. Ferrous iron was about 40 ppm. The bath contained 10 ppm soluble ferric ions, but it was clear and colorless. A large sample was divided into several portions to which a high level of phosphate was added to determine a level that could prevent initial bleaching of the bath after the pH had increased to 5. For the control sample without phosphate, the ferric iron level increased to 24 ppm and immediately after that the bath began to change color. The experimental results are shown in Table 3.0.

At high PO ₄ levels, the color change is longer and not as dark as the zero phosphate control. Furthermore, after storage overnight, the pH dropped to the level shown in the table, indicating the end of the oxidation and precipitation steps. The pH drop was less than when more phosphate was used. After a certain level of phosphate, the pH remains constant, indicating that it is in excess of that required for ferric iron. Over the course of several days, the quality of the precipitate was evident as described in Table 3.0. If there was not enough phosphate in the system, the precipitate developed as a coagulated brown oxide, resulting in a significant drop in pH. With enough phosphate, the precipitate was white and its density was such that iron removal was facilitated before it could be carried downstream.

  Zirconium levels were also checked to determine the effect of any excess phosphate. FIG. 3 shows that some zirconium has been depleted from the system, but the loss is not significant. Since phosphate converts a soluble ferric complex to insoluble ferric phosphate, the equivalent point of addition of phosphate to ferric is known by the pH plateau. This occurred when the phosphate was about 35-40 ppm with respect to 24 ppm ferric iron.

  Thus, in the above working bath, only 25-35 ppm phosphate per 24 ppm ferric iron is considered sufficient to prevent the development of a reddish brown bath with very little zirconium depletion. It is done. The bath life of this example is believed to be significantly longer than that typically found in competing industrial baths based on IIIB and / or Group IVB metals but without phosphate ions. The ratio of phosphate to ferric iron is in the range of 1: 1 to 1.8: 1 on a weight basis. Higher ratios may begin to deplete so much zirconium.

(Example 5)
A concentrate containing iron was obtained by suspending a clean steel panel for 2 days in a solution of hexafluorozirconic acid in deionized water and no phosphate. The final ferrous level was about 900 ppm and ferric was 33 ppm. The concentrate was then diluted with tap water to give about 20 ppm ferrous and 3 ppm ferric. Various amounts of phosphoric acid were added, followed by sufficient hydrogen peroxide to convert all ferrous iron to ferric iron. The pH was then adjusted to 4.7 for each bath. After standing at rest for 1 day, the bath was analyzed for phosphate and zirconium. The results are plotted in FIG. As is apparent, about 30 ppm phosphate is considered sufficient to remove 20 ppm ferric while maintaining most of the original 65 ppm zirconium in solution.

(Example 6)
Example 6 was performed to demonstrate that ferric iron (Fe ⁺³ ) can be removed from the off-shift pretreatment bath.

  A stock solution was prepared from 3 liters of tap water and 1.2 g of fluorozirconic acid solution (45%). The stock solution had a target of 85 ppm Zr. To this, 0.38 ml of ferric sulfate (50% solution) was added to obtain a target solution having 20 ppm ferric ions. The pH of the stock solution was 2.9.

The stock solution was divided into baths A to D, each containing 900 ml of stock solution. As described in more detail below, a Hach meter was used in this example (and in Examples 6 and 7) to measure ferrous (Fe ⁺² ) and total iron concentrations at various times. . When it was desired to obtain a ferric (Fe ⁺³ ) concentration in a particular bath, the ferric concentration was calculated as the difference between the total iron concentration and the ferrous concentration. In Example 6, none of the baths A to D contained any ferrous iron (Fe ⁺² ) at any time point measured.

Bath A served as a control and was compared to ferric (Fe ⁺³ ) and total iron concentrations (ppm) in baths B, C, and D (treated as described below).

Chemfil buffer, 0.1 g, ie PPG Industries, Inc. A commercially available alkaline solution from was added to Control Bath A as a source of alkalinity to obtain pH 3.4. As shown in FIG. 5, the ferric (Fe ⁺³ ) concentration (ppm) of Bath A was about 18.6 ppm during the duration of the 72 hour experiment. There was a barely colored rust colored precipitate formed in bath A. These data confirm that ferric iron (Fe ⁺³ ) is very stable at a pH range of about 3.4.

0.5 grams of Chemfil buffer was added to the 900 ml stock solution of Bath B to raise the pH of the bath to 4.8, which is the standard for baths containing the pretreatment composition described herein. It was within the range of action. As shown in FIG. 5, the ferric (Fe ⁺³ ) concentration in bath B is from about 21 ppm initial concentration to about 2 ppm concentration in 2 hours after raising the pH of the pretreatment bath to 4.8. Diminished. These data indicate that most of the soluble ferric iron has been converted to rust or ferric oxide insoluble in the pretreatment composition. A rust-like precipitate could be seen in bath B 2 hours after the pH increase.

PPG Industries, Inc. 0.09 g (45 wt%) of monosodium phosphate solution provided as Zircobond Additive P, available from Euclid, OH, was added to the 900 ml stock solution in Bath C. Bath C contained 14 ppm phosphate, its pH was 2.9 and was stable for the 72 hour duration of the experiment. As shown in FIG. 5, the ferric (Fe ⁺³ ) concentration in bath C decreased from about 18 ppm to about 12 ppm during the first 2 hours of the experiment, and then continued to decrease gradually over the duration of 72 hours. The final concentration was 7 ppm. A white precipitate was seen in bath C within the first few hours of the experiment and by the end of the experiment a slightly tan precipitate was formed, but this was at a pH below the normal level of action. , Indicating that the removal of ferric iron was gradual and incomplete.

0.09 g (45 wt%) of the monosodium phosphate solution provided as Zircobond Additive P was added to the 900 ml stock solution in Bath D. Bath D contained 34 ppm phosphate. As shown in FIG. 5, the ferric (Fe ⁺³ ) concentration in bath D was 20 ppm. As 0.5 g Chemfil buffer was added to Bath D to raise the pH to 4.75, the bath immediately became cloudy. After settling of crystals, the bath sample was filtered through a 5 micron syringe filter and the filtrate was checked for total iron. The ferric concentration of bath D was 2 ppm, and after 2 hours (at the end of the experiment) was 1.9 ppm. The bath was clear and had a small white precipitate.

  The data of Experiment 6 show that the addition of phosphate to the pretreatment bath removed most of the ferric iron at low pH and soon after the pH rose to its original working range, Demonstrate that everything has been removed. These data confirm that ferric iron can be removed from the pretreatment bath when the bath is off-shift.

(Example 7)
The data shown in FIG. 5 and described in Example 6 demonstrated that ferric acid was removed from the pretreatment bath by adding phosphate to the low pH pretreatment bath. In practice, however, pretreatment baths that have been used to treat substrates often contain ferrous iron that must be converted to ferric iron for removal from the pretreatment bath. Example 7 and the data shown in Table 4 and described herein show that the addition of an oxidizing agent to the pretreatment bath improves the removal of iron that was originally in the ferrous state. Demonstrate.

A stock solution was prepared from 3 liters of tap water and 1.2 g of fluorozirconic acid solution (45%). The stock solution had a target of 85 ppm Zr. To this, 0.32 g of ferrous sulfate heptahydrate was added to make a target solution having 20 ppm ferric ions (Fe ⁺² ) and 23 ppm total iron. The pH of the stock solution was 3.1.

The stock solution was divided into baths EG, each containing 900 ml of stock solution. Bath E served as a control and was compared to ferrous (Fe ⁺² ) and total iron concentrations (ppm) in baths F and G (treated as described below). Using a Hach meter, ferrous and total iron concentrations were monitored in each bath at periodic intervals during the 44 hour duration of the experiment.

Bath E served as a control. Bath E had an initial pH of 3.1. A few drops of Chemfil buffer was added to the bath to raise the pH to 3.5, which remained stable for the duration of the experiment, as shown in Table 4. As also shown in Table 4, the total iron concentration (ppm) in bath E dropped from the original 22.8 ppm to 22.1 ppm at the end of the 44 hour experiment. The ferrous (Fe ⁺² ) concentration was initially 19.8 ppm and dropped to 15.7 ppm at the end of the 44 hour experiment. The bath remained clear for the duration of the experiment and there was no red formation. These data indicate that all of the iron in the bath continued to be in solution as ferrous and there was only a small amount of conversion from ferrous to ferric. These data demonstrate that there is minimal conversion from ferrous to ferric at low pH (ie, lower than the working pH).

0.093 g of monosodium phosphate (45% solution) was added to bath F to obtain a solution having 43 ppm phosphate and a PO ₄ : total iron ratio of about 1.8: 1. Chemfil buffer 0.5 g was then added to the bath to obtain pH 4.7. The pH of bath F dropped slightly over the duration of the experiment and was 4.38 at 44 hours. As shown in Table 4, the total iron concentration in Bath E decreased from the original 22.8 ppm to 18.5 ppm in 30 minutes and to 14.7 ppm at the end of the 44 hour experiment. The ferrous iron concentration was initially 19.8 ppm, decreased to 17.2 ppm in 30 minutes, and was 12.4 ppm at the end of the 44 hour experiment. Some white precipitate was formed in the bath during the duration of the experiment, indicating the formation of ferric phosphate. These data show that only a small portion of the soluble iron is removed as ferric phosphate by raising the pH between 4.38 and 4.7 after the addition of phosphate. The reason is that, without being bound by theory, the oxidation of ferrous iron by raising only the pH is relatively slow and limited by the pH related equilibrium.

As shown in Table 4, bath G had an initial pH of 3.0, a total iron concentration of 22.8 ppm, and a ferrous iron concentration of 19.8 ppm. 0.1 g of monosodium phosphate (45% solution) was added to bath G, followed immediately by 0.32 g of hydrogen peroxide (3% by weight solution). 15 minutes after the addition of hydrogen peroxide, the total iron concentration was reduced to 10.2 ppm, the ferrous concentration was reduced to 0.4 ppm, and the pH was 2.6. Some white precipitate was formed in the bath, indicating that the iron-phosphate complex was partially completed. Next, the pH of the bath was increased to 4.7 by adding 0.6 g Chemfil buffer, and after 15 minutes (ie 46 minutes after the start of the experiment), almost all of the iron was removed and all The iron concentration was 5 ppm and the ferrous iron concentration was 0.1 ppm. At the end of the experiment (ie, 44 hours after the start), the pH of the bath was 4.6, the total iron concentration was 0.24 ppm, and the ferrous concentration was 0.02 ppm. These data demonstrated that the addition of phosphate and hydrogen peroxide to the bath significantly improved the removal of iron from the bath at the working pH.

(Example 8)
In this example, a pretreatment bath was made by adding 3.60 g hexafluorozirconic acid to 3 liters of water to obtain a solution having 240 ppm zirconium. A sufficient amount of Chemfil buffer was added to raise the pH of the solution to 4.5. By adding 0.31 g of ferrous sulfate heptahydrate, 20 ppm of ferrous iron was obtained. In order to prevent the formation of rust particles, about 14 drops of hexafluorozirconic acid were immediately added to lower the pH to 3.3. The bath was clear. Using a Hach meter, the total iron concentration was measured to be 23.2 ppm and ferrous iron was 19.5 ppm.

  Phosphate was added to the bath at a molar ratio of about 1: 1 (or 1.8: 1 by weight) to the total iron to be precipitated. In this bath, 41.5 ppm of phosphate from 0.175 g of phosphoric acid solution (75% by weight) was added to exceed about 8-9 ppm. After mixing for 1 minute, 1.27 g of a hydrogen peroxide solution (3% by weight) was then added, based on a 1: 1 molar ratio to ferrous iron (slight excess). Ferrous iron was converted to ferric iron in less than 1 minute.

  To precipitate all of the ferric iron as ferric phosphate, the pH of the bath was slowly raised to 4.75 by adding Chemfil buffer dropwise. If the rise is too fast, some insoluble ferric oxide can be formed as rust instead of ferric phosphate. As the pH increased, the bath developed a white haze that eventually became a coagulum and settled within 10 minutes, resulting in a clear bath. This final solution contained 0.2 ppm total iron and no detectable ferrous iron. Residual phosphate was 8.5 ppm, which was consistent with mass balance calculations.

Those skilled in the art will appreciate that changes can be made to the embodiments described above without departing from the broad inventive concept thereof. Accordingly, it is to be understood that the invention is not limited to the particular embodiments disclosed, but encompasses modifications which are within the spirit and scope of the invention as defined by the appended claims.

Claims (12)

A method for coating a ferrous metal substrate, comprising:
(A) contacting the metal substrate with an aqueous pretreatment composition having a pH of 4 to 5.5,
The aqueous pretreatment composition is
(A) Group I VB metal compound,
(B) a phosphate ion, and (c) water, wherein the Group I VB metal compound is present in the pretreatment composition in a metal amount of 10 to 500 ppm, and the Group I VB in the pretreatment composition The weight ratio of metal to phosphate ion is at least 0.8: 1, and the phosphate ion essentially forms insoluble rust in the bath of the pretreatment composition, (i) in the bath. in an amount insufficient to prevent deposition of I VB metals coating with at least coverage of 10 mg / m ² in sufficient in amount, and (ii) the metal substrate to prevent manner, and ( iii) maintaining the weight ratio of phosphate ions to ferric ions in an amount that provides 1 to 1.8: 1;
(B) the substrate is contacted with the coating composition saw including a step of forming a coated metal substrate showing the corrosion properties including film forming resin,
Here, the group IVB metal is zirconium, titanium, hafnium or a mixture thereof.
Method.   The method of claim 1, wherein the phosphate ions comprise alkali metal orthophosphate, ammonium orthophosphate, and mixtures thereof.   The method of claim 1, wherein the phosphate ion comprises monosodium phosphate.   The method of claim 1, wherein the aqueous pretreatment composition is substantially free of iron.   The method of claim 1, wherein the aqueous pretreatment composition further comprises an oxidizing agent.   The method of claim 5, wherein the oxidizing agent comprises a peroxide compound. A method for coating a ferrous metal substrate, comprising:
(A) contacting the metal substrate with an aqueous pretreatment composition having a pH of 4 to 5.5,
The aqueous pretreatment composition is
(A) Group I VB metal compound,
(B) a phosphate ion, and (c) water, wherein the Group I VB metal compound is present in the pretreatment composition in a metal amount of 10 to 500 ppm, and the Group I VB in the pretreatment composition The weight ratio of metal to phosphate ion is at least 0.8: 1, and the phosphate ion essentially forms insoluble rust in the bath of the pretreatment composition, (i) in the bath. in an amount sufficient to prevent manner, in an amount insufficient to prevent deposition of I VB metals coating with at least coverage of 10 mg / m ² in (ii) the metal substrate, and (iii ) Maintaining a weight ratio of phosphate ions to additional soluble iron in the ferrous state in an amount ranging from 1.8 to 10: 1;
(B) the substrate is contacted with the coating composition saw including a step of forming a coated metal substrate showing the corrosion properties including film forming resin,
Here, the group IVB metal is zirconium, titanium, hafnium or a mixture thereof.
Method. The method of claim 7 , wherein the phosphate ion comprises alkali metal orthophosphate, ammonium orthophosphate, and mixtures thereof. The method of claim 7 , wherein the phosphate ion comprises monosodium phosphate. The method of claim 7 , wherein the aqueous pretreatment composition is substantially free of iron. The method of claim 7 , wherein the aqueous pretreatment composition further comprises an oxidizing agent. It said oxidizing agent comprises a peroxide compound, The method of claim 1 1.

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