Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
AQUEOUS METAL COATING COMPOSITION AND PROCESS WITH IMPROVED WETTING OF OILY OR SIMILARLY SOILED SURFACES
Document Type and Number:
WIPO Patent Application WO/1996/011247
Kind Code:
A1
Abstract:
A fluorinated carboxylate salt anionic surfactant and/or a perfluoroalkyl poly(oxyethylene) nonionic surfactant enables polymer containing aqueous liquid treating agents for metals wet both clean and oil-contaminated surfaces, while most other surfactants, including other fluorinated surfactants, fail to provide this desirable property. These excellent wetting surfactants are usefully used together with a combination of sulfur-free azoles, preferably benzotriazole and tolytriazole, and sulfur-containing azoles, preferably 2-mercaptobenzothiazole or mercaptobenzimidazole, to prevent discoloration, staining, or corrosion of metal surfaces being coated with an organic protective coating from aqueous dispersion or solution.

Inventors:
CHURCH, Richard, J.
Application Number:
PCT/US1995/011666
Publication Date:
April 18, 1996
Filing Date:
September 21, 1995
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
HENKEL CORPORATION.
International Classes:
B21C9/02; B21J3/00; C08J3/03; C09D5/08; C09D135/06; C09D171/02; C10M173/02; B21B45/02; (IPC1-7): C10M173/00; B21B45/02; C10M173/02
Foreign References:
US5218031A1993-06-08
US5300142A1994-04-05
US5428095A1995-06-27
Other References:
See also references of EP 0784663A1
Download PDF:
Claims:
W096/11247The invention claim
1. ed is: An aqueous liquid composition suitable for protectively coating a metal substrate, said aqueous liquid composition comprising water and: (A) dissolved or dispersed constituents, including at least some dissolved, dispersed, or both dissolved and dispersed organic film forming polymer molecules, that are capable of reacting with one another, with a metal surface being treated, or both, or of spontaneously coalescing, or of both reacting and spontaneously coalescing, during or after at least one of (i) contact of the aqueous liquid composition with a metal surface, (ii) separation of a metal surface from such contact, and (iii) re moval of water from any liquid film remaining on the metal after such contact and subsequent removal from contact of the metal with the aqueous liquid com¬ position; said contact of the aqueous liquid composition with the metal surface and said removal of water from any liquid film remaining on the metal after such contact and subsequent removal from contact of the metal with the aqueous liquid composition both occurring at a temperature not less than 20° C, so as to form on the surface of the metal being treated an adherent protective film; and (B) a wetting effective amount of a surfactant component selected from the group consisting of fluoriπated alkyl carboxylate anionic surfactants and perfluoroalkyl ethoxylate nonionic surfactants.
2. An aqueous liquid composition according to claim 1, wherein the concentration of component (B) is from about 0.0008 % to about 0.4 %.
3. An aqueous liquid composition according to claim 2, comprising a dissolved, dis¬ persed, or both dissolved and dispersed film forming ethoxylated alcohol polymer and a conosion inhibitor component (C) that includes: (C. l) a primary inhibitor component selected from the group consisting of organic triazoles; and (C.2) a secondary inhibitor component selected from the group consisting of organic azoles that also contain mercapto moieties.
4. An aqueous liquid composition according to claim 3, wherein: the concentration of component (B) is from about 0.045 % to about 0.18 %, component (C. l) is benzo¬ triazole, tolyltriazole, or a mixture thereof; component (C.2) is mercaptobenzimidazole, mercaptobenzothiazole, or a mixture thereof; the concentration of each of benzotriazole and tolyltriazole is from about 45 to about 55 % of the total concentration of component (C.1); and the ratio of the concentration of component (C.2) to the concentration of com¬ ponent (C. l) is from about 0.021 : 1.0 to about 0.031 : 1.0.
5. An aqueous liquid composition according to claim 4, wherein the total solids con¬ centration is from about 11 to about 14 %, the pH value is from about 8.2 to about 8.8, and component (A) consists essentially of: (A. l .A) copolymers of styrene with (i) maleic anhydride, (ii) maleic acid, (iii) salts of maleic acid with ammonia, alkali metal hydroxides, and amines, or (iv) mixtures of any two or more of these, said copolymers having a molar ratio of styrene to maleic moieties in the range from 1.8: 1 to 2.3: 1, an average molecular weight from about 1600 to about 1750, a sufficient number of salt groups to be soluble or dispersible in water, no more than about 5 % of units derived from any monomers other than styrene and maleic moieties, and at least 91 mole % of the cations other than hydro¬ gen in the maleic moieties being substituted ammonium cations derived by adding a proton to amines that will dissolve in water to form at least 001 M solutions having a pH value of at least about 10; and (A.1 B) a component consisting of ethoxylated alcohol molecules that can be pro¬ duced by condensing ethylene oxide with primary straight chain alcohols having an average of from about 48 to about 52 carbon atoms per mole cule and from about 48 to about 51 % of their total weight in the portion of each molecule that has the chemical formula (CH2CH2O)n, where n is a positive integer, the ratio of the amount of component (A.1.A) to the amount of component (A 1 B) being from about 1.0: 1.9 to about 1.0:2.1 ; and (A.1.C) an inorganic boron containing component selected from the group con¬ sisting of boric acid and condensed boric acids and their alkali metal and ammonium salts, in an amount such that the ratio of the total stoichiomet ric equivalent as HjBO3 of the boron in this component to the total of the solids content in components (A 1 A) and (A 1 B) is from about 0 14 1 0 to about 0 34 1.0; and, optionally, one or more of (A l .D) an extreme pressure and conosion resistant additive component selected from the group consisting of partial esters and salts of partial esters of phosphoric acid with alcohols having a molecular formula that contains both (i) a part having the chemical formula (CHj)., where m is an inte¬ ger between 12 and 22 inclusive, and (ii) a part having the chemical form ula (CH2CH2O)p, where p is an integer having a sufficiently large value that the total alcohol is soluble in water to the extent of at least 1.3 %, (A. l E) a component of dispersed and/or dissolved solid lubricant selected from the group consisting of graphite, molybdenum disulfide, mica, and talc, and (A. I F) a component selected from oligomers of ethylene, propylene, or mixtures of ethylene and propylene having an average molecular weight in the range from about 750 to about 3000, wherein at least part of each of components (A.l A) and (A.1 B) is present in a chemical form other than esters formed by reaction with each other 6 An aqueous liquid composition according to claim 3, wherein the total solids con¬ centration is from about 6 to about 17 %, the pH value is from about 7.5 to about 9 0, and component (A) consists essentially of: (A. l . A) copolymers of styrene with (i) maleic anhydride, (ii) maleic acid, (iii) salts of maleic acid with ammonia, alkali metal hydroxides, and amines, or (iv) mixtures of any two or more of these, said copolymers having a molar ratio of styrene to maleic moieties in the range from 1.5: 1 to 2.6: 1, an average molecular weight from about 1600 to about 1950, a sufficient number of salt groups to be soluble or dispersible in water, no more than about 12 % of units derived from any monomers other than styrene and maleic moieties, and at least 78 mole % of the cations other than hydro¬ gen in the maleic moieties being substituted ammonium cations derived by adding a proton to amines that will dissolve in water to form at least 0.01 M solutions having a pH value of at least about 10; and (A.1 B) a component consisting of ethoxylated alcohol molecules that can be pro¬ duced by condensing ethylene oxide with primary straight chain alcohols having an average of from about 40 to about 60 carbon atoms per mole¬ cule and from about 40 to about 62 % of their total weight in the portion of each molecule that has the chemical formula (CH2CH2O)B, where n is a positive integer, the ratio of the amount of component (A.1 A) to the amount of component ( LB) being from about 2.5: 1.0 to about 1.0:2.5, and (A.1 C) an inorganic boron containing component selected from the group con¬ sisting of boric acid and condensed boric acids and their alkali metal and ammonium salts, in an amount such that the ratio of the total stoichiomet ric equivalent as H^Oj of the boron in this component to the total of the solids content in components (A.1.A) and (A 1 B) is from about 0.10: 1.0 to about 0.40: 1.0; and, optionally, one or more of: (A.1.D) an extreme pressure and conosion resistant additive component; (A.1.E) a component of dispersed and or dissolved solid lubricant, exclusive of inorganic boron containing materials; and (A.1.F) a component selected from solid and liquid hydrocarbons, wherein at least part of each of components (A.1 A) and (A 1 B) is present in a chemi form other than esters formed by reaction with each other. 7 An aqueous liquid composition according to claim 2, wherein the total solids co centration is from about 3 to about 20 %, the pH value is from about 6 to about 11 , a component (A) consists essentially of: (A. l . A) copolymers of styrene with (i) maleic anhydride, (ii) maleic acid, (i salts of maleic acid with ammonia, alkali metal hydroxides, and amin or (iv) mixtures of any two or more of these, said copolymers havin molar ratio of styrene to maleic moieties in the range from 4: 1 to 1 4, average molecular weight from about 1100 to about 2700, a suffici number of salt groups to be soluble or dispersible in water, no more th about 12 % of units derived from any monomers other than styrene a maleic moieties, and at least 50 mole % of the cations other than hyd gen in the maleic moieties being substituted ammonium cations deriv by adding a proton to amines that will dissolve in water to form at le 001 M solutions having a pH value of at least about 10; and (A.1 B) a component consisting of ethoxylated alcohol molecules that can be p duced by condensing ethylene oxide with primary straight chain alcoh having an average of from about 18 to about 75 carbon atoms per mo cule and from about 20 to about 80 % of their total weight in the porti of each molecule that has the chemical formula (CH2CH2O)n, wher is a positive integer, the ratio of the amount of component (A.1 A) to t amount of component (A 1 B) being from about 4: 1 to about 1 :4; and, tionally, one or more of: (A.1 C) an inorganic boron containing component; (A.1 D) an extreme pressure and conosion resistant additive component; (A.1 E) a component of dispersed and/or dissolved solid lubricant, exclusive inorganic boron containing materials; and (A.1.F) a component selected from solid and liquid hydrocarbons, wherein at least part of each of components (A 1 A) and (A.1 B) is present in a chemi form other than esters formed by reaction with each other.
6. An aqueous liquid composition according to claim 1, wherein component (A) comprises: (A. LA) an at least partially neutralized film forming copolymer of ethylene and acrylic acid, wherein the fraction of the mass of the copolymer made up s of ethylene residues is from about 60 to 96 % and the fraction of the mass of the copolymer made up of acrylic acid residues is from about 4 to about 40 %; and (A.1 B) a component consisting of ethoxylated alcohol molecules.
7. An aqueous liquid composition according to claim 4, wherein the total solids con o centration is from about 8.9 to about 15.1 %, the pH value is from about 9.0 to about 9.5, and component (A) consists essentially of: (A.2.A) an at least partially neutralized film forming copolymer of ethene and acrylic acid, wherein the fraction of the mass of the copolymer made up of ethene residues is from about 80 to 90 % and the fraction of the mass s of the copolymer made up of acrylic or substituted acrylic acid residues is from about 10 to about 14 %; and (A.2.B) a component consisting of ethoxylated alcohol molecules that can be pro¬ duced by condensing ethylene oxide with primary straight chain alcohols having an average of from about 48 to about 52 carbon atoms per mole 0 cule and from about 48 to about 51 % of their total weight in the portion of each molecule that has the chemical formula (CH2CH2O)n, where n is a positive integer, the ratio of the amount of component (A.2.A) to the amount of component (A.2.B) being from about 1.0: 1.10 to about 1.10: 1.0; and 5 (A.2.C) an inorganic boron containing component selected from the group con¬ sisting of boric acid and condensed boric acids and their alkali metal and ammonium salts, in an amount such that the ratio of the total stoichiomet ric equivalent as HjB03 of the boron in this component to the total of the solids content in components (A.2.A) and (A2.B) is from about 0.14: 1.0 o to about 0.34: 1.0; and, optionally, one or more of: (A.2.D) an extreme pressure and conosion resistant additive component selected from the group consisting of partial esters and salts of partial esters of phosphoric acid with alcohols having a molecular formula that contains both (i) a part having the chemical formula (CH2)m, where m is an inte¬ ger between 12 and 22 inclusive, and (ii) a part having the chemical form ula (CH CH2O)p, where p is an integer having a sufficiently large value that the total alcohol is soluble in water to the extent of at least 1.3 %; (A.2.E) a component of dispersed and/or dissolved solid lubricant selected from the group consisting of graphite, molybdenum disulfide, mica, and talc; and (A.2.F) a component selected from oligomers of ethene, propene, or mixtures of ethene and proene having an average molecular weight in the range from about 750 to about 3000. /11247 .
8. An aqueous liquid composition according to claim 3, wherein the total solids con¬ centration is from about 6.0 to about 17 %, the pH value is from about 8.5 to about 9.9, and component (A) consists essentially of: (A.2.A) an at least partially neutralized film forming copolymer of an alkene hav ing not more than 3 carbon atoms per molecule and an acrylic or substi¬ tuted acrylic acid having not more than 4 carbon atoms per molecule, wherein the fraction of the mass of the copolymer made up of alkene res¬ idues is from about 60 to 86 % and the fraction of the mass of the copoly¬ mer made up of acrylic or substituted acrylic acid residues is from about 4 to about 40 %; and (A.2.B) a component consisting of ethoxylated alcohol molecules that can be pro¬ duced by condensing ethylene oxide with primary straight chain alcohols having an average of from about 40 to about 60 carbon atoms per mole¬ cule and from about 40 to about 62 % of their total weight in the portion of each molecule that has the chemical formula (CH2CH2O)n, where n is a positive integer, the ratio of the amount of component (A.2. A) to the amount of component (A2.B) being from about 1.0: 1.5 to about 1.5: 1.0; and (A.2.C) an inorganic boron containing component selected from the group con sisting of boric acid and condensed boric acids and their alkali metal and ammonium salts, in an amount such that the ratio of the total stoichiomet ric equivalent as HjBO3 of the boron in this component to the total of the solids content in components (A.2.A) and (A.2.B) is from about 0.10: 1.0 to about 0.40: 1.0; and, optionally, one or more of: (A.2.D) an extreme pressure and conosion resistant additive component; (A.2.E) a component of dispersed and/or dissolved solid lubricant, exclusive of inorganic boron containing materials; and (A.2.F) a component selected from solid and liquid hydrocarbons.
9. An aqueous liquid composition according to claim 2, wherein the total solids con¬ centration is from about 3 to about 20 %, the pH value is from about 7 to about 1 1, and component (A) consists essentially of: (A.2. A) an at least partially neutralized film forming copolymer of an alkene hav ing not more than 4 carbon atoms per molecule and an acrylic or substi¬ tuted acrylic acid having not more than 6 carbon atoms per molecule, wherein the fraction of the mass of the copolymer made up of alkene res¬ idues is from about 55 to 97 % and the fraction of the mass of the copoly¬ mer made up of acrylic or substituted acrylic acid residues is from about 2 to about 40 %; and (A.2.B) a component consisting of ethoxylated alcohol molecules that can be pro¬ duced by condensing ethylene oxide with primary straight chain alcohols having an average of from about 28 to about 65 carbon atoms per mole¬ cule and from about 20 to about 80 % of their total weight in the portion of each molecule that has the chemical formula (CH2CH2O)n, where n is a positive integer, the ratio of the amount of component (A.2. A) to the amount of component (A.2.B) being from about 3: 1 to about 1 :3.5; and, optionally, one or more of: (A.2.C) an inorganic boron containing component; (A.2.D) an extreme pressure and conosion resistant additive component; (A.2.E) a component of dispersed and/or dissolved solid lubricant, exclusive of inorganic boron containing materials; and (A.2.F) a component selected from solid and liquid hydrocarbons.
10. An aqueous liquid composition according to claim 1, wherein component (A) comprises: (A.2. A) an at least partially neutralized film forming copolymer of an alkene and a comonomer that is an organic acid including the moiety C=CCOOH ; and (A.2.B) a component consisting of ethoxylated alcohol molecules.
11. A process of cold working a metal object, comprising steps of (i) applying an aqueous liquid lubricant composition to the surfaces of the metal object that are to be contacted with another hard surface during cold working so as to form a liquid coating on said surfaces of the metal object, (ii) drying the liquid coating formed in step (i) to form a solid coating on said surfaces of the metal object, and (iii) cold working the metal object, wherein the improvement comprises using as the aqueous liquid lubricant compo¬ sition a composition according to claim 12.
12. A process of cold working a metal object, comprising steps of (i) applying an aqueous liquid lubricant composition to the surfaces of the metal object that are to be contacted with another hard surface during cold working so as to form a liquid coating on said surfaces of the metal object, (ii) drying the liquid coating formed in step (i) to form a solid coating on said surfaces of the metal object, and (iii) cold working the metal object, wherein the improvement comprises using as the aqueous liquid lubricant compo¬ sition a composition according to claim 11 in an amount such that the addon mass of dry solid coating after step (ii) is from about 0.5 to about 50 g/m2.
13. A process of cold working a metal object, comprising steps of (i) applying an aqueous liquid lubricant composition to the surfaces of the metal object that are to be contacted with another hard surface during cold working so as to form a liquid coating on said surfaces of the metal object, (ii) drying the liquid coating formed in step (i) to form a solid coating on said surfaces of the metal object, and (iii) cold working the metal object, wherein the improvement comprises using as the aqueous liquid lubricant compo¬ sition a composition according to claim 10 in an amount such that the addon mass of dry solid coating after step (ii) is from about 1.4 to about 15 g/m2.
14. A process of cold working a metal object, comprising steps of (i) applying an aqueous liquid lubricant composition to the surfaces of the metal object that are to be contacted with another hard surface during cold working so as to form a liquid coating on said surfaces of the metal object, (ii) drying the liquid coating formed in step (i) to form a solid coating on said surfaces of the metal object, and (iii) cold working the metal object, wherein the improvement comprises using as the aqueous liquid lubricant compo sition a composition according to claim 9 in an. amount such that the addon mass of dry solid coating after step (ii) is from about 2.0 to about 10 g/m2.
15. A process of cold working a metal object, comprising steps of (i) applying a aqueous liquid lubricant composition to the surfaces of the metal object that are to b contacted with another hard surface during cold working so as to form a liquid coatin on said surfaces of the metal object, (ii) drying the liquid coating formed in step (i) t form a solid coating on said surfaces of the metal object, and (iii) cold working the meta object, wherein the improvement comprises using as the aqueous liquid lubricant compo sition a composition according to claim 8.
16. A process of cold working a metal object, comprising steps of (i) applying a aqueous liquid lubricant composition to the surfaces of the metal object that are to b contacted with another hard surface during cold working so as to form a liquid coatin on said surfaces of the metal object, (ii) drying the liquid coating formed in step (i) t form a solid coating on said surfaces of the metal object, and (iii) cold working the met object, wherein the improvement comprises using as the aqueous liquid lubricant compo sition a composition according to claim 7 in an. amount such that the addon mass of dr solid coating after step (ii) is from about 0.5 to about 50 g/m2.
17. A process of cold working a metal object, comprising steps of (i) applying a aqueous liquid lubricant composition to the surfaces of the metal object that are to b contacted with another hard surface during cold working so as to form a liquid coatin on said surfaces of the metal object, (ii) drying the liquid coating formed in step (i) t form a solid coating on said surfaces of the metal object, and (iii) cold working the met object, wherein the improvement comprises using as the aqueous liquid lubricant comp sition a composition according to claim 6 in an. amount such that the addon mass of dr solid coating after step (ii) is from about 1 4 to about 20 g/m2.
18. A process of cold working a metal object, comprising steps of (i) applying a aqueous liquid lubricant composition to the surfaces of the metal object that are to b contacted with another hard surface during cold working so as to form a liquid coatin on said surfaces of the metal object, (ii) drying the liquid coating formed in step (i) t form a solid coating on said surfaces of the metal object, and (iii) cold working the met object, wherein the improvement comprises using as the aqueous liquid lubricant comp sition a composition according to claim 5 in an. amount such that the addon mass of d solid coating after step (ii) is from about 2.0 to about 10 g/m2.
Description:
AQUEOUS METAL COATING COMPOSITION AND PROCESS WITH IMPROVED WETTING OF OB Y OR SIMILARLY SOILED SURFACES

BACKGROUND OF THE INVENTION Field of the Invention

This invention relates to aqueous liquid compositions suitable for forming a pro¬ tective coating containing an organic binder material on metal surfaces that are contacted with the compositions, either by direct deposition of a protective film on the metal while the liquid composition is in contact with the metal, or, more commonly, by depositing a liquid film of the liquid composition on the metal and converting this liquid film to a protective solid film by removing water from the initially deposited liquid film and, op¬ tionally, heating or otherwise causing the solid constituents of the liquid film to coalesce and/or react, so as to produce an adherent solid film on the metal surface. The solid film thus deposited may be protective against corrosion, damage during cold working of the underlying metal, or the like. The metal surfaces processed as described above may or may not have other surface layers, such as phosphate or chromate conversion coatings, coatings formed by anodization, complex oxide layers such as those that can be formed with a commercially available product named BONDERTTE® 770X from the Parker

Amchem Div. of Henkel Corp., Madison Heights, Michigan, or the like, underlying the coating produced on the surface by using this invention.

Statement of Related Art

Many aqueous liquid compositions that deposit protective coatings on metal sur¬ faces are known. Many of them contain organic polymers in solution or stable disper¬ sion, and it has been observed that most such polymer containing aqueous liquids do not readily wet any part of a metal surface that is soiled with oil, grease, or similar organic materials. It is therefore customary to perform thorough and often elaborate, multistep cleaning processes to prepare metal surfaces for the formation of good protective coat¬ ings.

DESCRIPTION OF THE INVENTION Objects of the Invention

A major object of this invention is to provide aqueous liquids containing dis¬ persed or dissolved organic polymer molecules that are able to wet surfaces bearing or¬ ganic soils more readily than otherwise similar solutions known from the prior art. A re¬ lated object is to reduce the need for at least some of the cleaning measures now custom- ary, particularly to reduce the number of separate cleaning process steps that are required, while still obtaining protective coatings at least as satisfactory as those now achieved from otherwise similar solutions. Another object is to provide compositions that avoid or at least reduce the generation of foam which often is characteristic of aqueous compo¬ sitions with good wetting power. A more particular object is to obtain some or all of the benefits noted above for particular types of aqueous compositions that provide metal, especially aluminum, copper, and most especially steel, surfaces with surface layers pro¬ tective against damage during cold working, drawing, or like mechanical processing General Principles of Description

Except in the claims and the operating examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word "about" in describing the broadest scope of the invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary: percent, "pans of, and ratio values are by weight; the term "polymer" includes "oligomer", "copoly- mer", "terpolymer", and the like and also includes any molecules containing a polymeric moiety that constitutes at least 20 % of the mass of the molecule, even if another part of the molecule, particularly one or more end groups, is not polymeric; the description of

a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the de- scription, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; specification of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole (any counterions thus implicitly specified should preferably be selected from among other constituents explicitly specified in ionic form, to the extent possible; otherwise such counterions may be freely selected, except for avoiding counterions that act adversely to the objects of the invention); and the term "mole" and its variations may be applied to elemental, ionic, and any other chemical species defined by number and type of atoms present, as well as to compounds with well defined molecules. Summary of the Invention It has been found that the use of surfactants selected from the group consisting of fluormated carboxylate salt anionic surfactants and perfluoroalkyl poly(oxyethylene) nonionic surfactants enables aqueous liquid compositions comprising dissolved and/or dispersed organic film forming polymer(s) satisfactorily to wet both clean and organical¬ ly soiled metal surfaces, while most other surfactants, including some other types of fluorinated surfactants and other chemical types of surfactants that are recommended for wetting improvement in general terms by their suppliers are far less effective. (A poly¬ mer is defined as "film forming" for the purposes of this description if, when a solution or suspension of the polymer in water, containing at least 10 % nonvolatile solids, is dried at a temperature of at least 25 β C from a liquid film thickness of 1 millimeter, a continuous and coherent film that is solid at 25° C is produced.) Aqueous liquid compo¬ sitions containing wetting effective amounts of the effective surfactants according to this invention are prone to foaming, but this tendency can be adequately controlled with addi¬ tion of proper antifoam agents.

More specifically, one embodiment of this invention is an aqueous liquid compo- sition suitable for protectively coating a metal substrate, said aqueous liquid composition comprising, preferably consisting essentially of, or more preferably consisting of, water and:

(A) dissolved or dispersed constituents, including at least some dissolved, dispersed, or both dissolved and dispersed organic film forming polymer molecules, that are capable of reacting with one another, with a metal surface being treated, or both, or of spontaneously coalescing, or of both reacting and spontaneously coalescing, during or after at least one of (i) contact of the aqueous liquid composition with a metal surface, (ii) separation of a metal surface from such contact, and (iii) re¬ moval of water from any liquid film remaining on the metal after such contact and subsequent removal from contact of the metal with the aqueous liquid com¬ position, said contact of the aqueous liquid composition with the metal surface and said removal of water from any liquid film remaining on the metal after such contact and subsequent removal from contact of the metal with the aqueous liquid composition both oαairring at a temperature not less than 20° C, so as to form on the surface of the metal being treated an adherent protective film, and

(B) a wetting effective amount of a surfactant component selected from the group consisting of fluorinated alkyl carboxylate anionic surfactants and perfluoroalkyl ethoxylate nonionic surfactants, and, optionally,

(C) one or more corrosion inhibitors

Embodiments of the invention include working aqueous liquid compositions suit¬ able for contacting directly with metal surfaces to provide protective coatings thereon as described above, liquid or solid concentrates that will form such working aqueous liquid compositions upon dilution with water only, processes of using working aqueous liquid compositions according to the invention as defined above to form protective coatings on metal surfaces, protective solid coatings on metal surfaces formed in such a process, and metal articles bearing such a protective coating Description of Preferred Embodiments

The total concentration in an aqueous coating composition of the surfactants char¬ acteristic of this invention, i e , component (B) as defined above, preferably is, with in¬ creasing preference in the order given, at least 0 0001, 00002, 00004, 0 0006, 0 0008, 0 0010, 0 0012, 00014, 0 0016, 00018, 0 0020, 0 0040, 0 0080, 0 015, 0 030, 0 045, 0 060, 0 070, 0 080, 0 090, or 0 10 % No harm has been found from using the surfact¬ ants characteristic of the invention in concentrations up to their solubility limit, but for purposes of economy, using no more than needed to obtain the desired degree of wetting

is naturally preferable. Thus, the concentration of surfactants characteristic of the inven¬ tion in an aqueous liquid composition independently preferably is, with increasing prefer¬ ence in the order given, not more than 0.8, 06, 04, 0.3, 0.25, 0.20, 0 18, 0 16, 0 14, 0.12, or 0.1 1 %. The chemical nature and amount of component (A) in a working aqueous liquid composition according to the invention depend on the purpose of the treatment and in general preferably are the same as or similar to the chemical nature and amount of mater¬ ials used for similar protective purposes in the prior art. Some specific examples partic¬ ularly suited to the present invention are given below, and any explicit specification here- in is to be understood as superseding any contrary teachings from the prior art.

The use of the surfactants characteristic of this invention has been found to be of particular value in aqueous compositions comprising, as at least one of the film forming polymers present, ethoxylated alcohol(s), more preferably those selected from the group consisting of alcohols having a chemical structure that can be produced by condensing ethylene oxide with primary, preferably straight chain, aliphatic alcohols having only one hydroxyl group and, with increasing preference in the order given, an average of at least 18, 25, 30, 35, 40, 43, 46 or 48 carbon atoms per molecule and independently, with in¬ creasing preference in the order given, an average of not more than 75, 65, 60, 57, 55, 52, or 51 carbon atoms per molecule. Independently, it is preferred that the molecules of eth- oxylated alcohols used in a composition according to this invention contain, with increas¬ ing preference in the order given, at least 20, 30, 35, 40, 43, 47, or 49 %, and independ¬ ently preferably contain, with increasing preference in the order given, not more than 80, 70, 62, 57, 54, or 51 % of their total mass in the oxyethylene units.

Independently of the particular structure of the ethoxylated alcohols present in a composition according to the invention, the total concentration of ethoxylated alcohols in a working composition, i.e., a liquid composition ready to be applied directly to a me¬ tallic surface to be protected by the solid coating formed after drying onto the metallic surface the liquid coating initially applied, preferably is, with increasing preference in the order given, not less than 1.0, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, or 6.3 % and independently preferably is not more than 50, 40, 35, 31, 28, 25, 22, 18, 17, 16, 15, 14,

13, 12, 11, 10, 9.0, 8.5, 8.0, 7.5, or 7.1 %.

Normally, the presence of component (C) in a composition according to this in-

vention that includes ethoxylated alcohols is preferred. A particularly preferred compon¬ ent (C) comprises, more preferably consists essentially of, or still more preferably con¬ sists of: (C. 1 ) a primary inhibitor component selected from the group consisting of non-sulfur- containing organic azole compounds, preferably organic triazoles, more preferab¬ ly benzotriazole or tolyltriazole; and (C.2) a secondary inhibitor component selected from the group consisting of organic azoles that also contain mercapto moieties, preferably mercaptobenzothiazole or mercaptobenzimidazole . In this preferred embodiment, the concentration of component (C.1 ) in a working aque¬ ous liquid composition according to this invention preferably is, with increasing prefer¬ ence in the order given, not less than 10, 40, 100, 200, 400, 800, 1200, 1400, 1500, 1600, 1700, 1750, 1800, 1850, 1900, 1925, 1950, or 1975 pans per million (hereinafter often abbreviated "ppm") of the total composition and independently preferably is, with in- creasing preference in the order given, not more than 20,000, 10,000, 5000, 3500, 3300,

3100. 2800, 2500, 2400, 2300, 2250, 2200, 2175, 2150, 2125, 2100, 2075, 2050, or 2025 ppm. Independently, as already noted above, it is preferred for component (C. 1) to be selected from benzotriazole and tolyltriazole, and in fact a mixture of these two is more preferred than either of them alone. The amount of each of benzotriazole and tolyltriaz- ole, expressed as a percentage of the total of component (C.1 ) preferably is, with increas¬ ing preference in the order given, independently for each of these two triazoles, not less than 5, 10, 15, 20, 25, 30, 35, 38, 41, 43, 45, 47, 48, or 49 % and independently preferab¬ ly is, with increasing preference in the order given, not more than 95, 90, 85, 80, 75, 70, 65, 62, 59, 57, 55, 53, 52, or 51 %. When present, the concentration of component (C.2) in a working aqueous liquid composition according to this invention preferably is, with increasing preference in the order given, not less than 1, 4, 10, 15, 20, 25, 30, 35, 38, 41, 43, 45, 47, or 49 ppm of the total composition and independently preferably is, with increasing preference in the order given, not more than 2000, 1000, 500, 350, 300, 250, 200, 175, 165, 155, 145, 135, 125, 120, 115, 110, 107, 110, 108, 106, 105, 104, 103, 102, or 101 ppm. The ratio of the con¬ centration of component (C.2) to the concentration of component (C. l) preferably is, with increasing preference in the order given, not less than 0.001: 1, 0.002: 1, 0.004: 1,

0 007 1 , 0 01 1 1 0, 0 015.1 0, 0 019 1 0, 0 020 1 0, 0 021 1 0, 0 022 1 0, 0 023 1 0, or 0 024 1.0 and independently preferably is, with increasing preference in the order given, not more than 2.1, 1.1, 0.5.1, 0.3.1, 0.2.1, 0 1 : 1, 0.09.1.0, 0 08 1.0, 0 07 1 0, 0 06 1.0, 0 05 1 0, 0 04 1 0, 0 035:1 00, 0.033 1 00, 0 031 1 00, 0 029 1 00, 0 028 1.00, 0 027 1.00, or 0 026 1 00 These ratios, unlike the concentration preferences stated above, apply to concentrates as well as to working compositions.

For various reasons it is often preferred that the compositions according to the in¬ vention be free from various materials often used in prior art coating compositions. In particular, compositions according to this invention in most instances preferably contain, with increasing preference in the order given, and with independent preference for each component named, not more than 5, 2, 1, 0.5, 025, 0.12, 0 06, 0 03, 0.015, 0.007, 0.003, 0.001 , 0 0005, 0.0002, or 0.0001 % of any of (i) hydrocarbons, (ii) fatty oils of natural origin, (iii) other ester oils and greases that are liquid at 25° C, (iv) metal salts of fatty acids, (v) hexavalent chromium, (vi) nickel cations, (vii) cobalt cations, (viii) copper cat- ions, (ix) manganese in any ionic form, (x) graphite, and (xi) molybdenum sulfide

One class of component (A) to which this invention is especially well adapted is materials that will form on treated metal a coating that is protective for cold working More particularly, a prefeπed component (A) according to a first prefened specific em¬ bodiment of this invention comprises, more preferably consists essentially of, or still more preferably consists of, the following subcomponents

(A.1 A) copolymers of styrene with (i) maleic anhydride, (ii) maleic acid, (iii) salts of maleic acid with ammonia, alkali metal hydroxides, and amines, or (iv) mixtures of any two or more of these, said copolymers containing a sufficient number of salt groups to be soluble and/or dispersible in wat- er; and

(A.1.B) a component consisting of ethoxylated alcohol molecules, and, optional¬ ly, one or more of: (A.1 C) an inorganic boron containing component;

(A.1 D) an extreme pressure and corrosion resistant additive component as known per se in the art;

(A.1.E) a component of dispersed or dissolved solid lubricant, exclusive of inor¬ ganic boron containing materials, as known er se in the art; and

(A.1 F) a component selected from solid and liquid hydrocarbons

In this first preferred specific embodiment, at least part of each of components (A. l .A) and (A.1 B) must be present in a chemical form other than esters formed by reaction with each other. For puφoses of this description, the term "maleic moiety" is defined as a portion of a polymer chain that conforms to one of the following general chemical formulas:

wherein each of Q 1 and Q 2 , which may be the same or different, is selected from the group consisting of hydrogen, alkali metal, ammonium, and substituted ammonium cat¬ ions. The copolymers of styrene and maleic moieties to be used in the first preferred spe¬ cific embodiment of the invention preferably have a molar ratio of styrene to the maleic moieties in the range from 1 : 1 to 3.1, more preferably in the range from 1.5: 1 to 2.6: 1, still more preferably in the range from 1.8: 1 to 2.3 : 1. Independently, the copolymers of styrene and maleic moieties to be used in the first preferred specific embodiment of the invention preferably are selected from polymers that have an average molecular weight in the range from 1 100 to 2700, more preferably in the range from 1600 to 1950, still more preferably in the range from 1650 to 1750. Preferably these copolymers of styrene and maleic moieties to be used in this first prefened specific embodiment of the inven¬ tion contain no more than 25, or with increasing preference no more than 12, 5, 3, or 0 5 % of units derived from other monomers.

The compositions according to this first preferred specific embodiment of this in- vention provide a very pliable and ductile lubricating film, thereby leading to superior cold forming processes.

Inorganic boron containing materials, optional component (A. l .C), and extreme pressure additives, optional component (A.1 D) above, are generally preferred compon¬ ents in compositions according to this first preferred specific embodiment of the inven- tion, while other solid lubricants and hydrocarbons, optional items (A.1.E) and (A_ 1.F) above, generally are preferably omitted, although they may be useful in some applicat-

ions.

Concentrates according to the first preferred specific embodiment of the invention preferably contain from 10 - 40 %, or more preferably from 20 - 40 %, of dispersed or dissolved solids. Lubricant compositions according to this first preferred specific em- s bodiment of the invention, suitable for direct application to metal surfaces to be lubricat¬ ed, preferably contain from 3 - 20, more preferably from 6 - 17, still more preferably from 10 - 14, % of total dissolved solids.

It is also preferred that the pH of the liquid compositions for direct application to metal surfaces (also denoted as "working compositions" herein) fall within the range o from 6 to 1 1, more preferably in the range from 7.5 to 9.0, or still more preferably from

8.2 to 8.8. If needed, alkaline materials, preferably ammonium, sodium, potassium, or lithium hydroxide, in addition to the amines noted above, may be added to the composi¬ tions in order to achieve a pH within these ranges.

The working compositions according to this first preferred specific embodiment s of the invention are often used at fairly high temperatures such as 70° C or more. At such temperatures, if the compositions contain unsubstituted ammonium cations, or other ammonium cations derived from high volatility amines, there is a substantial concentra¬ tion of ammonia or free amine in the vapor space over the liquid working composition at equilibrium. Such concentrations can be objectionable to workers using the process. 0 In an industrial application, ammonia and/or amine concentrations are conven¬ tionally measured by a Drager test apparatus, which gives readings in NH 3 equivalents, with amines as well as with ammonia itself It is preferred that the cations other than hy¬ drogen used in a composition according to this first preferred specific embodiment of the invention be chosen from ammonium ions of amines having sufficiently low volatility 5 that the equilibrium overpressure of NH 3 equivalents as measured by a Drager test appa¬ ratus in the atmosphere over compositions according to this first preferred specific em¬ bodiment of the invention at a temperature of 70° C is, with increasing preference in the order given, not more than 50, 35, 25, 14, 9, 6, or 4 parts per million (hereinafter "ppm") of ammonia equivalent.

30 Independently, it is preferred, with increasing preference in the order given, that at least 50, 78, or 91 mole percent of the cations other than hydrogen present in compon¬ ent (A. l.A) as described above be selected from the group consisting of substituted am-

momum cations derived by adding a proton to amines that will dissolve to form at least

0 01 M solutions, with a pH value of at least 10, in water More preferably, the amines contain at least one hydroxyl group per molecule Still more preferably, the substituted ammonium cations are selected from the cations formed by adding a proton to diethyleth- anol amine, dimethylethanol amine, diethanol amine, monoethanol amine, or Λsσ-prop- anol amine

Preferred characteristics for component (A.1 B) of compositions according to this first preferred specific embodiment of the invention have already been given above, under the general description of "ethoxylated alcohols" The ratio by weight of component (A.1.A) to component (A 1 B) in compositions according to this first preferred specific embodiment of the invention is preferably be¬ tween 6 1 and 1 6, or, in order of increasing preference, between 4 1 to 1 4, 2 5 1 to

1 2 5, 1 1 6 to I 2 5, or 1 1 9 to 1 2 1

Component (A_l C) of compositions according to this first prefeπed specific em- bodiment of the invention is preferably selected from the group consisting of bone acid and condensed boric acids, alkali metal and ammonium salts of boric acid and condensed bone acids; more preferably, component (A 1 C) is selected from boric acid, borax, and mixtures thereof, most preferably a mixture of boric acid and borax in a ratio of 2 0 1 0 is used When component (A 1 C) is used, the ratio of the total of the stoichiometric equivalent as HjBOj of the boron in component (A 1 C) to the total of the solids content in components (A.1 A) and (A 1 B) preferably is, with increasing preference in the order given, not less than 0 02 1 0, 0 04 1 0, 006 1 0, 0 08 1 0, 0 10 1 0, 0 12 1 0, 0 14 1 0, 0 16 1 0, 0 18.1 0, 0 19.1.0, 0 20.1 0, 0.21 1.0, 0.22 1 0, or 0 23 1 0 and independently preferably is, with increasing preference in the order given, not more than 2 5 1 0, 1.2 1 0, 0 8.1 0, 0 6 1 0, 0.40 1 0, 0 37.1 0, 0 34 1 0, 0 31 1 0, 0 29 1 0, 028 1 0,

0 27 1 0, 026 1 0, or 0.25.1.0

Component (A.1 D) of the compositions according to this first preferred specific embodiment of the invention is preferably selected from partial esters, or salts of partial esters, of phosphoric acid with alcohols having a molecular structure that contains both (i) a part having the structure -(CH j ),.,-, where m is an integer between 12 and 22 inclus¬ ive, more preferably between 16 and 22 inclusive, and (ii) a part having the structure (CH 2 -CH 2 -O) p , where p is an integer having a sufficiently large value that the total alco-

hol is soluble in water to the extent of, with increasing preference in the order given, at least 0. 1 , 0.4, 0.9, 1.3, 1.8, and 3 %. When component (A. I D) is used, it is preferably present in a ratio by weight to the total of components (A. l .A) and (A. I B) within the range from 1 : 10 to 1 :200, or more preferably from 1 :25 to 1 :70, still more preferably s from 1 :40 to 1 :55.

If component (A. I E) is used, it preferably is selected from the group consisting of graphite, molybdenum disulfide, mica, and talc.

If component (A.1 F) is used, it preferably is selected from substantially unsatur- ated aliphatic hydrocarbon compounds, including oligomers of ethene, propene, or mix- o tures of ethene and propene, with a molecular weight in the range from 750 - 3000, more preferably in the range from 1000 - 2000.

The specific area! density (also often called "add-on weight [or mass]") of a com¬ position according to this first prefened specific embodiment of this invention, or any other embodiment containing ethoxylated alcohols and intended to protect the metal sub- s strate to which it is applied during mechanical cold working, after application from a li¬ quid composition to the metal surface and air drying of liquid thus applied, preferably is, with increasing preference in the order given, at least O. l, 0.3, 0.5, 0.7, 0.9, 1. 1 , 1.3, 1.5, 1.7, or 1.9 and independently preferably is, with increasing preference in the order given, not more than 20, 15, 12, 10, 9, 8, 7, or 6 grams per square meter of surface ("g m 2 "). 0 For cold drawing of steel, a lubricant composition according to this first prefened specific embodiment of this invention preferably is used on clean bare steel without any intermediate coating. However, a lubricant composition according to this first prefened specific embodiment of this invention can also be used over an underlying phosphate conversion coating layer formed on the steel. The phosphate conversion coating may be 5 formed by methods known per se in the art, and iron and manganese phosphate conver¬ sion coatings, as well as the zinc based phosphate type conversion coating which is usual as the pretreatment before lubricating with stearate soaps, may be used with this inven¬ tion. Any phosphate conversion coating used before application of a lubricant composi¬ tion according to this first prefened specific embodiment of this invention preferably has 0 a specific areal density that is, with increasing preference in the order given, at least 0.2, 0.3, 0.5, 0.7, 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0 g m 2 and independently is, with increasing pref¬ erence in the order given, not more than 50, 30, 20, 15, 12, or 10 g/m 2 .

In a second prefened specific embodiment of this invention, component (A) as described above comprises, more preferably consists essentially of, or still more prefer¬ ably consists of, the following subcomponents: (A.2. A) an at least partially neutralized film forming copolymer of an alkene that

5 contains no carboxyl or carboxylate group and a comonomer that is an or¬ ganic acid including the moiety C=C-COOH, such at least partially neu¬ tralized polymers of organic acids often being denoted in the art generally and hereinbelow as "ionomers"; (A.2.B) a component consisting of ethoxylated alcohol molecules; and, optional- ιo ly, one or more of:

(A.2.C) an inorganic boron containing component,

(A.2.D) an extreme pressure and conosion resistant additive component as known per se in the art; (A.2.E) a component of dispersed or dissolved solid lubricant, exclusive of inor- i5 ganic boron containing materials, as known per se in the art; and

(A.2.F) a component selected from solid and liquid hydrocarbons.

Compositions according to this second prefened embodiment of the invention also provide a very pliable and ductile lubricating film, as does the first specific embodi¬ ment described above.

20 The pH value of working compositions according to this second prefened embod¬ iment of the invention preferably is, with increasing preference in the order given, not less than 3, 4, 5, 6, 7, 7.3, 7.6, 7.9, 8.1, 8.3, 8.5, 8 7, 8 8, 8 9, or 9 0 and independently preferably is, with increasing preference in the order given, not more than 12, 1 1 , 10 7, 10.4, 10.2, 10.0, 9.9, 9.8, 9.7, 9.6, or 9.5.

2 s The total solids content of a working composition according to this second pre¬ ferred specific embodiment of the invention preferably is, with increasing preference in the order given, not less than 1, 2, 3, 4, 5, 5.5, 6.0, 6.5, 7.0, 7.4, 7.7, 8.0, 8.3, 8.5, 8.7, 8.8, or 8.9 % and independently preferably is, with increasing preference in the order given, pot more than 50, 35, 25, 20, 18, 17, 16, 15.5, or 15.1 %.

30 The alkene polymerized to make component (A.2.A) preferably is selected from the group consisting of ethene (more commonly called "ethylene"), propene, 2-methyl propene, and 1- and 2-butenes; more preferably it is ethene or propene, most preferably

ethene. For the unsaturated organic acid comonomer to make component (A), acrylic acid is most prefened, and methacryiic acid and other homologs of acrylic acid, i e , mol¬ ecules differing from acrylic acid by the addition of one or more -CH 2 - groups, with not more than six, preferably not more than four, carbon atoms per molecule are next most prefened. The fraction of the mass of the polymer made up of alkene residues preferably is, with increasing preference in the order given, not less than 1, 2, 4, 15, 30, 40, 50, 55, 60, 65, 70, 75, 80, or 84 %; independently, the fraction of the mass of the polymer made up of alkene residues preferably is, with increasing preference in the order given, not more than 99, 97, 95, 92, 90, 89, 87, or 86 %. Independently, the fraction of the mass of the polymer made up of acrylic acid and/or acrylate residues preferably is, with increas¬ ing preference in the order given, not less than 1, 2, 4, 6, 8, 10, 11, 12, 13, or 14 %; inde¬ pendently, the fraction of the mass of the polymer made up of acrylic acid and/or acrylate residues preferably is, with increasing preference in the order given, not more than 50, 40, 35, 30, 25, 20, 18, or 16 %. Normally, commercially available polymers in latex form are prefened for com¬ ponent (A.2.A); a variety of such commercial products are available. Such products nor¬ mally contain small amounts of surfactants for stabilizing the polymers in suspension; these surfactants normally have no adverse effect on compositions according to this in¬ vention. The counterions for the neutralized acrylic acid units in the polymers are prefer¬ ably selected from the group consisting of magnesium, calcium, zinc, and alkali metal ions, with the divalent ions in this group more prefened. If alkali metal ions are used, the compositions preferably contain optional component (A.2.C) as described above. Even if other counterions are used, the compositions may contain component (A.2.C), but the favorable effect of this component is normally less than when the counterions are alkali metal ions.

The oxyalkylene units in component (A.2.B) of a composition according to this second prefened embodiment of this invention preferably have not more than 4, more preferably not more than 3, most preferably 2, carbon atoms per unit. Component (A.2.B) of the compositions according to this second prefened specific embodiment of the invention is preferably selected from molecules having a chemical structure that can be produced by condensing an alkylene oxide with primary, preferably straight chain, ali-

phatic alcohols having only one hydroxyl group and, with increasing preference in the order given, an average of at least 18, 25, 30, 35, 40, 43, 46 or 48 carbon atoms per mole¬ cule and independently, with increasing preference in the order given, an average of not more than 75, 65, 60, 57, 55, 52, or 51 carbon atoms per molecule. Independently, it is preferred that the molecules of component (A.2.B) contain, with increasing preference in the order given, at least 20, 30, 35, 40, 43, 47, or 49 %, and independently preferably contain, with increasing preference in the order given, not more than 80, 70, 62, 57, 54, or 51 % of their total mass in the oxyalkylene units.

The ratio by weight of component (A.2.A) to component (A.2.B) in compositions according to this second prefened embodiment of the invention preferably is, with in¬ creasing preference in the order given, at least 1:10, 1 :8, 1.0:6.5, 1.0:5.0, 1.0:3.5, 1.0:2.5, 1.0:2.0, 1.0:1.7, 1.0:1.5, 1.0:1.3, 1.0:1.20, 1.0:1.17, 1.0:1.12, 1.0: 1.10, 1.0: 1.07, 1 0 1 04, 1.0: 1.03, 1.0:1.02, or 1.0:1.01, and independently preferably is, with increasing prefer¬ ence in the order given, not more than 10: 1, 5:1.0, 3:1.0, 2.5:1.0, 2.0.1.0, 1.8 1 0, 1 6 1.0, 1.50: 1.0, 1.40:1.0, 1.35:1.0, 1.30: 1.0, 1.25:1.0, 1.20: 1.0, 1.15: 1.0, 1.12: 1.0, 1.09: 1.0,

1.07.1.0, 1.05:1.0, 1.03: 1.0, or 1.01: 1.0.

Component (A.2.C) of compositions according to this second prefened specific embodiment of the invention is preferably selected from the group consisting of boric acid and condensed boric acids, alkali metal and ammonium salts of boric acid and con- densed boric acids; more preferably, component (A.2.C) is selected from boric acid, bor¬ ax, and mixtures thereof; most preferably a mixture of boric acid and borax in a ratio of 2.0.1 0 is used. When component (A.2.C) is used, the ratio of the total of the stoichio- metric equivalent as H 3 BO 3 of the boron in component (A.2.C) to the total of the solids content in components (A.2.A) and (A.2.B) preferably is, with increasing preference in the order given, not less than 0.01 : 1.0, 0.02:1.0, 0.04: 1.0, 0.06:1.0, 0.08: 1.0, 0.10: 1.0,

0.11:1.0, 0.12: 1.0, 0.13: 1.0, 0.14.1.0, 0.15: 1.0, 0 16:1.0, or 0.17.1.0 and independently preferably is, with increasing preference in the order given, not more than 2.0: 1.0, 1.2:1.0, 0.8:1.0, 0.6:1.0, 0.4:1.0, 0.28:1.0, 0.25:1.0, 0.22.1.0, 0.21 : 1.0, 0.22.1.0, 0.21 : 1.0, 0.20: 1.0, 0.19:1.0, or 0.18:1.0. The add-on mass of a composition according to this second prefened specific em¬ bodiment of this invention present in place on the surface of metal to be cold worked preferably is, with increasing preference in the order given, not less than 0.1, 0.2, 0.4,

0 7, 1.0, 2.0, 2.5, 2.9, 3.2, 3.5, 3.7, 3.8, 3.9, 4.0, 4. 1, or 4.2 grams of solids per square meter of surface (hereinafter often abbreviated "g/m 2 ") and independently preferably is, with increasing preference in the order given, not more than 60, 40, 30, 20, 17, 15, 13, 12, 1 1, 10, 9.0, 8.5, 8.0, 7.7, 7.4, 7.1, 6.9, 6.7, or 6.6 g/m 2 . The practice of this invention may be further appreciated by consideration of the following, non-limiting, working examples, and the benefits of the invention may be fur¬ ther appreciated by reference to the comparison examples.

Examples and Comparison Examples Test panels containing both clean and soiled areas of metal were prepared by placing one drop of REACTOBOND® 909 Makeup (hereinafter often abbreviated as

"909M") combination conversion coating and lubricant film forming composition in each of two locations on a clean 10* 15 cm rectangular cold rolled steel panel commercially supplied in precleaned condition by ACT Laboratories, Hillsdale, Michigan, then smear¬ ing out each drop to form a circular spot about 3 centimeters in diameter; the original drops were placed far enough apart so that the spots formed in this manner did not over¬ lap. The 909M product, which contains over 50 % of mineral oil, is commercially avail¬ able from the Parker Amchem Div. of Henkel Corp., Madison Heights, Michigan, and it reacts with steel to form a lubricant soaked conversion coating which anchors the oily constituents of the 909M product strongly to the steel. Test panels prepared in this manner were then coated with one of two exemplary drawing lubricant forming solution having the compositions shown in Table 1 , to pro¬ duce dry add-on masses of 3.0 - 4.0 grams per square meter After coating, the panels were dried in an oven and then examined for visual evidence of dewetting on any part of the surface. The surfactants tested are shown in Table 2. PLURONIC™ and TETRONIC™ surfactants are available commercially from BASF Corp., Performance Chemicals Div. FLUORAD™ surfactants are available commercially from Minnesota Mining and Manu¬ facturing Co. TRITON™ surfactants are available commercially from Union Carbide Corp. ZONYL™ surfactants are available from E. I. du Pont de Nemours & Co. FLUO- WET™ surfactants are available from Hoechst Chemical Co.

The following additional information about some of the surfactants in Table 2 is taken from representations made by the supplier of the particular surfactant. FLUO-

Table 1 COMPOSITION OF THE TEST COATING COMPOSITIONS

Name of lngredient % of Solids from Ingredient in Composition Number:

1

"SMA 2000" styrene-maleic anhydride 3.3 copolymer

ACqua™ 250 5 0

Diethylethanolamine 2.7

NaOH 1.1

Benzotriazole 0 15 0.14

Tolyltriazole 0 15 0 14

2-mercaptobenzimidazole 0 015 002

ANTARA™ LB-400 phosphate ester 0.20

Borax 0 88 0 7

Boric acid 1 78 1 4

UNITHOX™ 750 ethoxylated alcohol 6 75

UNITHOX™ D-300 5 0

Surfactant 0 10 0 10

Notes for Table 1 UNITHOX™ 750 and D-300 are commercially supplied by Petrolitc Corp., Tulsa, Okla¬ homa, USA, "SMA 2000" is commercially available from ATOCHEM, INC., Malvern, PA, ANTARA™ LB-400 is commercially available from GAF, New York, NY and is rec¬ ommended as an extreme pressure lubricant. ACqua™ 250 is commercially supplied by Allied Signal Corp The balance of the compositions not shown above is water.

RAD™ FC-129 surfactant contains 32 % of water, 14 % of 2-butoxyethanol, and 4 % of ethanol, with the balance consisting of potassium fluoroalkyl carboxylates, including at least 40 % of the one having Chemical Abstracts Service Registry Number ("CASR#") 2991-51-7 but possibly also including one or more of those having CASR#'s 67584-62-7, 67584-53-6, 67584-52-5, and 67584-51-4 FLUORAD™ FC-430 surfactant contains 98.5 % of fluoroaliphatic polymeric esters and < 1.5 % of toluene. FLUORAD™ FC- 120 surfactant contains 25 % of ammonium perfluoroalkyl sulfonates and 37.5 % of each

Table 2: SURFACTANTS

Surfactant Name Type Brief Chemical Description

PLURONIC™ 25R2 Nonionic Block Copolymer of Ethylene Oxide and Propylene Oxide

PLURONIC™ L92 Nonionic Block Copolymer of Ethylene Oxide and Propylene Oxide

PLURONIC™ L81 Nonionic Block Copolymer of Ethylene Oxide and Propylene Oxide

TETRONIC™ 901 Nonionic Ethylene Oxide and Propylene Oxide Adduct with Ethylenediamine

FLUORAD™ FC-430 Nonionic Fluorinated Polymeric Ester

TRITON™ X- 100 Nonionic Ethoxylated Octyl Phenol

ZONYL™ FSN 100 Nonionic Perfluoroalkyl Ethoxylate

FLUORAD™ FC-129 Anionic Potassium Fluoroalkyl Carboxylate

FLUORAD™ FC- 120 Anionic Ammonium Perfluoroalkyl Sulfonate

FLUOWET™ PL80 Anionic Salt of Fluoroalkyl Phosphonic Acid

FLUORAD™ FC- 135 Cationic Fluoroalkyl Quaternary Ammonium Iodide

None (Comparison) . _

of water and 2-butoxyethanol. FLUORAD™ FC-135 surfactant contains 50 % of fluoro¬ chemical alkyl quaternary ammonium iodides, 34 % 2-propanol, and 16 % of water.

Of all the surfactants listed in Table 2, only those identified as perfluoroalkyl eth¬ oxylate and fluoroalkyl carboxylate produced compositions that were free from any vis¬ ually detectable evidence of dewetting, with either Test Composition 1 or 2. The "con¬ trol" with no surfactant also resulted in substantial dewetting.

"DK-100" defoamer, commercially available from Genessee Polymers of Flint, Michigan, at a concentration of 0.01 %, was effective in satisfactorily suppressing foam in compositions containing the prefened fluorochemical surfactants, without adversely affecting their other properties.