US20060151071A1 - Quaternary ammonium salts as a conversion coating or coating enhancement - Google Patents

Quaternary ammonium salts as a conversion coating or coating enhancement Download PDF

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Publication number
US20060151071A1
US20060151071A1 US11/299,323 US29932305A US2006151071A1 US 20060151071 A1 US20060151071 A1 US 20060151071A1 US 29932305 A US29932305 A US 29932305A US 2006151071 A1 US2006151071 A1 US 2006151071A1
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paint
anions
quaternary ammonium
substituted
steel
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Thomas Bedard
Thomas Burleigh
Larry Hall
Joseph Kimler
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Lonza LLC
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Lonza LLC
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Priority to US11/299,323 priority Critical patent/US20060151071A1/en
Assigned to LONZA INC. reassignment LONZA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIMLER, JOSEPH, HALL, LARRY K., BEDARD, THOMAS C., BURLEIGH, THOMAS DAVID
Publication of US20060151071A1 publication Critical patent/US20060151071A1/en
Priority to US12/952,690 priority patent/US8337640B2/en
Priority to US13/726,495 priority patent/US8580154B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines

Definitions

  • the present invention relates to the use of quaternary ammonium salts containing non-halogen anions such as carbonate, bicarbonate, phosphate and glycolate as active ingredients of conversion coatings and as additives for paints and coatings.
  • Examples of metals prone to corrosion are found in stamped metal car parts made from ferrous alloys, abraded surfaces such as machined steel parts, and machine components made from cast iron.
  • Conversion coatings are used to inhibit corrosion and to assure good adhesion of paint to a metal surface, in particular to steel. Bare steel does not form a good bond with organic coatings.
  • chromate or phosphate conversion coatings are chemically reacted with the steel to form a rough surface structure with metal-phosphate platelets that provide both mechanical and chemical keying (adhesion) of the organic polymer to the metal surface. See, for example, Watson, J. “ A refresher: Understanding pretreatment”, Powder Coating 1996, 7(3) and Ferguson, D.; Monzyk, B., “Nonpolluting replacement for chromate conversion coating and zinc phosphate in powder coating applications”, Powder Coating 2001, 12(7).
  • a conversion coating is to be understood to mean a protective barrier film or layer on the metal substrate surface simultaneously capable of both corrosion inhibition and paint adhesion and comprised of either (i) an organic film, (ii) an inorganic oxide resulting from a metal etching and redeposition process, (iii) an inorganic oxide resulting from a true deposition process, or (iv) any mixture of inorganic and organic materials from (i), (ii) and (iii).
  • the most widely used conversion coatings are chromating, phosphochromating and zinc phosphatizing processes. It is believed that chromating gives better corrosion inhibition, while phosphochromating gives better paint adhesion.
  • the metal surface Prior to applying the conversion coating to the metal surface, the metal surface must be cleaned in order to remove any grease on the metal surface.
  • the conversion coating can then be applied by either immersion or spraying. Chromate and phosphochromate conversion coatings are the most common chemical conversion coatings, but because of health, safety and environmental concerns other types of conversion coatings are needed.
  • quaternary ammonium salts containing non-halogen anions such bicarbonate, carbonate, phosphate and glycolate, more specifically, dialkyl dimethyl ammonium salts containing bicarbonate, carbonate, phosphate or glycolate as the anion, and various combinations thereof, have applicability as a conversion coating for metal surfaces and steel in particular. Additionally it has been discovered that said quaternaries are capable of effecting a desirable surface transformation such as the growth of desirable surface oxides (i.e. magnetite, Fe 3 O 4 ) on steel substrates. This oxide formation results in distinct crystallite domains which adhere to the metal substrate and to which coatings such as paints are expected to exhibit improved adhesion. In addition, said quaternary ammonium salts can be added directly to paints to provide better adhesion of the paint to the metal surface and thereby improving corrosion resistance.
  • desirable surface transformation such as the growth of desirable surface oxides (i.e. magnetite, Fe 3 O 4 ) on steel substrates. This oxide formation results in distinct crystallite domain
  • the raw metal is passivated with oil to prevent flash rust.
  • the metal surface is treated with conversion coating solutions (acidic, heavy metal containing chemicals) and cured before the final coating is applied.
  • conversion coating solutions acidic, heavy metal containing chemicals
  • Coiled sheet steel treated according to the present invention is resistant to the edge staining that occurs when moisture condenses on the edges of the coils.
  • steel sheet is sprayed with a light oil prior to storage or transportation. This oil must be removed prior to additional surface treatments or coatings.
  • the oxide film formed according to the present invention has the potential of being an under-paint conversion coating or primer for steel. Bare steel does not form a good bond with organic coatings. To improve the metal/organic coating bond, chromate or phosphate conversion coatings are chemically reacted with the steel to form a rough surface structure with metal-phosphate platelets that provide both mechanical and chemical keying (adhesion) of the organic polymer to the metal surface.
  • the conversion coatings and anticorrosive paints of the present invention exhibit certain self-healing properties on scratching, which means that even the “bare” metal surface in a scratch shows some passivation that may be due to migration of the quaternary ammonium salt from the surrounding coating. In some cases, a permanent oxide transformation is also observed resulting in long term passivation of a scratched area. This is an effect that is similar to the self-healing observed on chromium coated metal surfaces.
  • the present invention relates to a method for applying a conversion coating to the surface of a metal substrate, said method comprising the step of contacting the substrate with a composition comprising
  • the composition includes from about 0.05 to about 2% by weight and more preferably from about 0.1 to about 1% by weight of the quaternary ammonium salt(s) containing non-halogen anion(s), based upon 100% total weight of the composition.
  • the quaternary ammonium salt has the formula wherein R 1 is an optionally aryl-substituted C 1-20 alkyl group, and R 2 is an optionally aryl-substituted C 1-20 alkyl group, R 3 and R 4 independently of each other are C 1-4 alkyl groups, X n ⁇ is an anion selected from the group consisting of hydroxide, carbonate, bicarbonate, phosphates, phosphites, hypophosphite, nitrate, sulfates, borates, anions of saturated and unsaturated acyclic C 1-20 monocarboxylic acids, anions of saturated and unsaturated C 2-20 dicarboxylic acids, and anions of hydroxy-substituted carboxylic acids, and n denotes the appropriate number of negative charges of said anion.
  • C 1-20 alkyl groups are linear or branched alkyl groups having 1 to 20 carbon atoms, including, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, isononyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl.
  • Aryl-substituted C 1-20 alkyl groups are any of the above groups bearing an aryl group, in particular phenyl, as a substituent.
  • Preferred examples of aryl-substituted C 1-20 alkyl groups are benzyl, phenylethyl and phenylpropyl.
  • phosphates is to be understood as including both acid and neutral salts of phosphoric acid, namely, dihydrogenphosphates (H 2 PO 4 ⁇ , monohydrogenphosphates (HPO 4 2 ⁇ ) and phosphates (PO 4 3 ⁇ ), as well as salts of oligo- and polyphosphoric acids such as diphosphates (pyrophosphates) and triphosphates.
  • dihydrogenphosphates H 2 PO 4 ⁇
  • monohydrogenphosphates HPO 4 2 ⁇
  • phosphates PO 4 3 ⁇
  • salts of oligo- and polyphosphoric acids such as diphosphates (pyrophosphates) and triphosphates.
  • Phosphites are salts of phosphorous acids containing the anions H 2 PO 3 ⁇ and/or HPO 3 2 ⁇ .
  • Sulfates are hydrogensulfate (HSO 4 ⁇ ) and sulfate (SO 4 2 ⁇ ) as well as disulfate (S 2 O 7 2 ⁇ ) and related anions.
  • Borates are any anions derived from boric acid (H 3 BO 3 ) and the various polyboric acids.
  • Saturated and unsaturated acyclic C 1-20 monocarboxylic acids are in particular alkanoic acids, such as formic, acetic, propionic, butyric, pentanoic, hecanoic, octanoic, decanoic, dodecanoic, tetradecanoic, hexadecanoic, octadecanoic and icosanoic acids, or alkenoic acids, such as acrylic, methacrylic, oleic and linolic acid.
  • alkanoic acids such as formic, acetic, propionic, butyric, pentanoic, hecanoic, octanoic, decanoic, dodecanoic, tetradecanoic, hexadecanoic, octadecanoic and icosanoic acids
  • alkenoic acids such as acrylic, methacrylic, oleic and lino
  • Saturated and unsaturated acyclic C 2-20 dicarboxylic acids are in particular alkanedioic acids, such as oxalic, malonic, succinic, glutaric and adipic acid, or alkenedioic acids such as fumaric or maleic acid.
  • Hydroxy-substituted carboxylic acids are any carboxylic acids bearing at least one hydroxy group in addition to the carboxylate group(s), such as glycolic, malic, citric or salicylic acid.
  • More preferred quaternary ammonium salts exhibiting the effect described above are quaternary ammonium carbonates, quaternary ammonium bicarbonates, quaternary ammonium phosphates and quaternary ammonium glycolates.
  • R 3 and R 4 in the quaternary ammonium salt of formula I are methyl groups.
  • R 1 is methyl
  • R 2 is benzyl or phenylethyl.
  • R 1 and R 2 are the same C 1-20 alkyl groups.
  • R 1 and R 2 are C 10 alkyl groups.
  • R 1 and R 2 are n-C 10 alkyl groups.
  • the quaternary ammonium salt is di-n-decyldimethylammonium carbonate and/or di-n-decyldimethylammonium bicarbonate.
  • the metal substrate is steel.
  • the steel is coiled sheet steel.
  • Another object of the invention is an article of manufacture comprising a metal substrate treated according to the above described method or any of its preferred embodiments.
  • the preferred metal substrate is steel.
  • Still another object of the invention is an anticorrosive paint comprising
  • the anticorrosive paint includes from about 0.05 to about 2% by weight and more preferably from about 0.1 to about 1% by weight of the quaternary ammounium salt(s) containing non-halogen anions, based upon 100% total weight of the paint.
  • the quaternary ammonium salt in the anticorrosive paint preferably has the formula wherein R 1 is an optionally aryl-substituted C 1-20 alkyl group, and R 2 is an optionally aryl-substituted C 1-20 alkyl group, R 3 and R 4 independently of each other are C 1-4 alkyl groups, X n ⁇ is an anion selected from the group consisting of hydroxide, carbonate, bicarbonate, phosphates, nitrate, sulfates, borates, anions of saturated and unsaturated acyclic C 1-20 monocarboxylic acids, anions of saturated and unsaturated C 2-12 dicarboxylic acids, and anions of hydroxy-substituted carboxylic acids, and n denotes the appropriate number of negative charges of said anion.
  • the binder is selected from the group consisting of acrylic resins, casein (milk protein), vinyl resins, latex resins, acetate resins, epoxy resins and mixtures thereof.
  • the anticorrosive paint is a latex paint.
  • the anticorrosive paint is an enamel spray paint.
  • the anticorrosive paint is an E-Coating paint.
  • the anticorrosive paint is an acrylic paint.
  • Still another object of the invention is an article of manufacture comprising a metal substrate painted with the above described anticorrosive paint. All preferred embodiments regarding the nature of the anticorrosive paint, the ammonium salt being comprised in said paint, and the metal substrate apply likewise to said article of manufacture.
  • Still another object of the invention is the use of a quaternary ammonium salt having the formula wherein R 1 is an optionally aryl-substituted C 1-20 alkyl group, and R 2 is an optionally aryl-substituted C 1-20 alkyl group, R 3 and R 4 independently of each other are C 1-4 alkyl groups, X n ⁇ is an anion selected from the group consisting of hydroxide, carbonate, bicarbonate, phosphates, phosphites, hypophosphite, nitrate, sulfates, borates, anions of saturated and unsaturated acyclic C 1-20 monocarboxylic acids, anions of saturated and unsaturated acyclic C 2-20 dicarboxylic acids and anions of hydroxy-substituted carboxylic acids, and n denotes the appropriate number of negative charges of said anion as an anticorrosive additive in paints or coatings.
  • FIG. 1 is a SEM micrograph of a steel surface after two weeks immersion in 3.5% aqueous NaCl solution containing 0.1% di-n-decyldimethylammonium carbonate. Note the formation of hexagonal platelets on the surface.
  • FIG. 2 is a SEM micrograph of a steel surface after two months immersion in 3.5% aqueous NaCl solution containing 0.1% di-n-decyldimethylammonium carbonate. The surface is covered with platelets and spherical particles. One of these phases is ferromagnetic (magnetite, Fe 3 O 4 ).
  • FIG. 3 is a SEM micrograph of a steel surface after 48 h immersion at 70° C. in a 0.1% solution of di-n-decyldimethylammonium glycolate in tap water.
  • FIG. 4 is a SEM micrograph of a steel surface after 1 h immersion at 70° C. in tap water (control experiment).
  • FIG. 5 depicts the results of paint peel back tests with several E-coated steel samples after salt spray exposure.
  • FIG. 6 depicts the results of salt spray tests of steel samples painted with latex paint made anticorrosive by addition of quaternary ammonium salts.
  • FIG. 7 depicts the results of salt spray tests of steel samples painted with gloss protective spray enamel with various amounts of quaternary ammonium salts.
  • a Conversion Coating Study (Reference: NB5751-001 through 018) was done with the objective to prepare steel panels (S-46, purchased from Q-Panel Lab Products, Cleveland, Ohio) with various aqueous treatments of either CarboShield® 1000 (di-n-decyldimethylammonium bicarbonate/carbonate), “Phosphoquat” (di-n-decyldimethylammonium phosphates), and various related controls.
  • CarboShield® 1000 di-n-decyldimethylammonium bicarbonate/carbonate
  • Phosphoquat di-n-decyldimethylammonium phosphates
  • a plastic tank being 27.9 cm (11′′) in diameter and 27.9 cm (11′′) in height was used to treat the panels.
  • the plastic tank was filled with 9,600 grams of test solution.
  • 10.16 cm ⁇ 15.24 cm ⁇ 1.59 mm (4′′ ⁇ 6′′ ⁇ 1/16′′) steel (S-46) panels with a hole of 6.35 mm (1 ⁇ 4′′) in diameter located 6.35 mm (1 ⁇ 4′′) from the top edge were treated by placing a plastic pipette through the hole in the panel. Up to three panels were skewed using the same pipette. This allowed for the panels to stand upright, with only the bottom of the panel touching the bottom of the tank. The tank was then placed in an oven which was at 70° C. for one hour.
  • CarboShield® 1000 is a 50% aqueous solution of di-n-decyldimethylammonium (bi)carbonate (90 mol % bicarbonate, 10 mol % carbonate).
  • Glycoquat is a solution of di-n-decyldimethylammonium glycolate(s) prepared by adding the amount of glycolic acid required to obtain the specified pH to CarboShield® 1000.
  • the steel panels were treated with the test solutions, they were painted using three different painting processes. Two panels were painted for each painting process. In one of the painting processes, the steel panels were spray painted using Rust-Oleum®'s Professional High Performance Enamel (Hunter Green) spray paint. Four steel panels were laid flat end to end and spray painted with approximately 18 g of paint applied to the top surface of the steel panels and allowed to dry overnight. The bottom of the panels were treated in a similar manner the next day. A second set of panels were painted using Rust-Oleum®'s Painters Touch (Hunter Green) latex paint. The paint was applied with a foam roller to the steel panels. A total of two coats of paint were applied to each side of the steel panels.
  • Rust-Oleum®'s Professional High Performance Enamel Heunter Green
  • a third set of panels were painted using a commercial painting process known as E-Coating (a polymer based coating). These samples were painted at Royal E-Coat (Costa Mesa, Calif.), using a proprietary process.
  • E-Coating a commercial painting process known as E-Coating (a polymer based coating). These samples were painted at Royal E-Coat (Costa Mesa, Calif.), using a proprietary process.
  • a fourth set of steel panels (untreated) were also painted using Rust-Oleum®'s Painters Touch® (Hunter Green) latex paint to which CarboShield® 1000 was added at either 0.1%, 0.5% or 1.0%.
  • a fifth set of steel panels (untreated) were also painted using Rust-Oleum®'s Gloss Protective Spray Enamel (Hunter Green) paint to which CarboShield® 1000, phosphoquat, or glycoquat was added at indicated levels.
  • Sample G1 Time 0.1% CS Sample G3
  • Sample G5 Sample A5 (h) Spike, Brush 0.5% CS Spike 1% CS Spike Brushed, Untreated 24 1 1 1 1 48 1 1 1 1 120 20 144 15 20 30 192 25 216 25 45 288 35 3 80 312 5 35 336 10 360 45 85 456 75 15 40 95 Samples were prepared by brush application.
  • Example 2 Two latex paints were formulated according to the amounts and order of ingredients and process steps listed in Table 7.
  • Example 2 contained CarboShield® 1000 while the other one (Comparative Example 1) contained a combination of a nonionic surfactant (Triton X-100) and a conventional corrosion inhibitor (Canguard® 327).
  • Example 327 a nonionic surfactant
  • Canguard® 327 a conventional corrosion inhibitor
  • Example 2 Water 57.34 L 57.34 L Propylene glycol 15.42 kg 15.42 kg Natrosol ® 250 HBR 816.5 g 816.5 g Mix 30 minutes Tamol ® 850 4.536 kg 4.536 kg Triton ® X-100 1.043 kg — CarboShield ® 1000 — 1.043 kg Drewplus ® L-493 861.8 g 861.8 g Canguard ® 327 1.021 kg — AMP-95 TM 453.6 g 453.6 g Mix Ti-Pure ® R-931 87.32 kg 87.32 kg Imsil ® A-15 87.32 kg 87.32 kg High speed stir at 4,000 RPM for 30 min, then decrease speed to 1,000 RPM UCAR ® 123 latex 154.0 kg 154.0 kg Texanol ® 3.080 kg 3.080 kg Drewplus ® L-493 997.9 g 997.9 g Acrosol ® RM-825 90
  • Tamol ® 850 is a sodium polyacrylate of Rohm and Haas Co., Philadelphia, Pennsylvania.
  • Triton ® X-100 is an octylphenol ethoxylate of The Dow Chemical Company.
  • Drewplus ® L-493 is a defoamer of Ashland Specialty Chemical Co., Boonton, New Jersey.
  • Canguard ® 327 is an oxazolidine-based corrosion inhibitor of ANGUS Chemical Company, a subsidiary of The Dow Chemical Company.
  • AMP-95 TM is 2-amino-2-methyl-1-propanol containing 5% water, obtainable from ANGUS Chemical Company.
  • Ti-Pure ® R-931 is a rutile titanium dioxide pigment of DuPont Titanium Technologies, Wilmington, Delaware.
  • Imsil ® A-15 is a microcrystalline silica of Unimin Specialty Minerals Inc., Tamms, Illinois.
  • UCAR ® 123 is a high-solids styrene-acrylic binder of UCAR Emulsion Systems, Cary, North Carolina.
  • Texanol ® is 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate of Eastman Chemical Company, Kingsport, Tennessee.
  • Acrosol ® RM-825 is an acrylate copolymer-based rheology modifier of BASF AG, Ludwigshafen, Germany.
  • Table 7 The formulations of Table 7 were tested for storage stability and viscosity as well as scrub resistance and hide of paint films on metal surfaces.
  • Example 2 The formulation of Example 2 was stable for several days, even better than that of Comparative Example 1, with less separation. The formulation was also “creamier” (more desirable) than the comparative formulation. This observation confirms that CarboShield® 1000 is compatible in latex systems.
  • the scrub resistance of the paint film prepared from the formulation of Example 2 was 480 cycles to failure while that of the film prepared from the formulation of Comparative Example 1 was only 370 cycles to failure. This is a significant ca. 30% improvement. Scrub resistance was measured using standard ASTM D2486 methodology.
  • the Stormer viscosity of the Formulation of Example 2 was significantly higher than that of Comparative Example 1, 83 KU vs. 73 KU. This allows to reduce the amount of associative thickener added to the formulation.

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US20080197112A1 (en) * 2007-02-21 2008-08-21 Houghton Technical Corp. Chemical assisted lapping and polishing of metals
US20110124738A1 (en) * 2008-01-28 2011-05-26 Sven Schroeder Chromate-free corrosion protection for fuel tanks
US8580154B2 (en) * 2004-12-09 2013-11-12 Lonza, Inc. Quaternary ammonium salts as a conversion coating or coating enhancement
US9080064B2 (en) 2003-05-28 2015-07-14 Lonza Inc. Method of applying a coating composition of quaternary ammonium salts containing non-halogen anions as anticorrosive agents

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9080064B2 (en) 2003-05-28 2015-07-14 Lonza Inc. Method of applying a coating composition of quaternary ammonium salts containing non-halogen anions as anticorrosive agents
US9394617B2 (en) 2003-05-28 2016-07-19 Lonza Inc. Method of inhibiting corrosion using a composition of quaternary ammonium salts containing non-halogen anions
US8580154B2 (en) * 2004-12-09 2013-11-12 Lonza, Inc. Quaternary ammonium salts as a conversion coating or coating enhancement
US20080197112A1 (en) * 2007-02-21 2008-08-21 Houghton Technical Corp. Chemical assisted lapping and polishing of metals
US7820068B2 (en) 2007-02-21 2010-10-26 Houghton Technical Corp. Chemical assisted lapping and polishing of metals
US20110124738A1 (en) * 2008-01-28 2011-05-26 Sven Schroeder Chromate-free corrosion protection for fuel tanks
US9279055B2 (en) 2008-01-28 2016-03-08 Mankiewicz Gebr. & Co. Gmbh & Co. Kg Chromate-free corrosion protection for fuel tanks

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