EP0510105A1 - Surface-treatment method for tin-plated drawn and ironed cans. - Google Patents

Surface-treatment method for tin-plated drawn and ironed cans.

Info

Publication number
EP0510105A1
EP0510105A1 EP91903769A EP91903769A EP0510105A1 EP 0510105 A1 EP0510105 A1 EP 0510105A1 EP 91903769 A EP91903769 A EP 91903769A EP 91903769 A EP91903769 A EP 91903769A EP 0510105 A1 EP0510105 A1 EP 0510105A1
Authority
EP
European Patent Office
Prior art keywords
oligomer
water
sprayed
seconds
cans
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91903769A
Other languages
German (de)
French (fr)
Other versions
EP0510105B1 (en
Inventor
Shigeo Tanaka
Tomoyuki Aoki
Masayuki Nihon Parkeri Yoshida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Henkel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Publication of EP0510105A1 publication Critical patent/EP0510105A1/en
Application granted granted Critical
Publication of EP0510105B1 publication Critical patent/EP0510105B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C23C22/07—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
    • C23C22/23—Condensed phosphates

Definitions

  • the invention of Japanese Patent Application Laid Open [Ko ai or Unexamined] Number 1-100281 [100,281/89] is an example of a surface treatment liquid for tin plated DI cans.
  • This teaching of the prior art employs a film form ⁇ ing liquid for the treatment of metal surfaces.
  • This solu ⁇ tion has a pH of 2 to 6 and contains 1 to 50 gram per liter ("g/L") of phosphate, 0.2 to 20.0 g/L of oxyacid ions, 0.01 to 5.0 g/L of tin ions, and 0.01 to 5.0 g/L of condensed phosphate.
  • Treatment with this conversion treatment solu ⁇ tion afforded a highly corrosion resistant phosphate film on the surface of tin-plated DI cans.
  • Treatment methods intended to provide corrosion re ⁇ sistance and adhesivity through the use of water soluble resin are exemplified by the invention in Japanese Patent Application Laid Open Number 1-172406 [172,406/89].
  • This invention provided as an example of the prior art comprises a method in which the metal surface is treated with a solu ⁇ tion which contains an effective derivative of a polyhydric phenol compound.
  • the disclosed method does not generate a satisfactorily stable corrosion resistance.
  • the metal can manufacturing process often suffers from a problem with transfer or transport: the slideability of the outer surface of the can during convey ⁇ or transport of the can may be poor due to a high friction coefficient of the outer surface, so that the can may be tipped over sideways.
  • the invention of Japanese Patent Application Laid Open Number 64-85292 [85,292/89] comprises a method for improving this slideability.
  • the reference teaches a surface treatment composition for metal cans which contains water-soluble organic material selected from phosphate esters, alcohols, monobasic, and polybasic fatty acids, fatty acid deriva ⁇ tives, and mixtures of the foregoing. While the disclosed method does in fact generate an increase in the slideabil- ity, it does not improve the corrosion resistance or paint adhesion.
  • the principal goal of the invention is to provide a single treatment for DI cans that will result in increased corrosion resistance, good adhesion to subsequently applied paint or similar organic coatings, and a low coefficient of friction on the outside can surface, for efficient process- ing in automated can processing lines using high speed con ⁇ veyors and printers.
  • a liquid treating composition is prepared by dissolv ⁇ ing in water an oligomer having a chemical composition specified by the general formula:
  • n is a number with a value between 10 and 30 and each of X and Y independently represents hydrogen or a group Z, wherein Z has a chemical composition conforming to the general formula:
  • each of R_ and is an alkyl or hydroxyalkyl group having from 1 to 5 carbon atoms, except that at least 25 % of the total of all the X and Y groups in the oligomer are Z rather than hydrogen.
  • the pH of the surface treatment solution containing the oligomer described in item (1) is adjusted to a value between 4 and 6 by the addition of orthophos- phoric acid and/or condensed phosphoric acid.
  • the surface treatment liquid as prepared in step (2) is heated to a temperature of at least 40 but prefer ⁇ ably to not more than 60 degrees Centigrade and the ably to not more than 60 degrees Centigrade and the heated surface treatment liquid is then sprayed on the cleaned surface of tin plated DI can for a time of at least 5 and preferably not more than 60 seconds.
  • the aforesaid spray treatment is followed by thermal drying or by a water rinse and then thermal drying.
  • the sprayed cans drain under the influence of gravity, and/or to remove some of the liquid from the can surface by mechanical means such as an air flow, rollers under slight pressure, or the like, to avoid the presence of excessive amounts of the surface treatment liquid on the surface during drying.
  • n in the general formula given above for the oligomer dissolved in the surface treatment liquid is 10 to 30. At values of n below 10, little or no improve ⁇ ment in corrosion resistance will be observed on DI tin plated cans. A value of 31 or more for n results in a poorly stable aqueous solution which cannot readily be used in practical applications.
  • R. and R repre ⁇ sent alkyl or hydroxyalkyl groups having 1 to 5 carbon atoms. When they contain six or more carbons, the stabil ⁇ ity of the aqueous solution is reduced.
  • the introduction ratio for the group Z should be 25 to 100 mole % referred to the total number of X and Y groups in the oligomer.
  • the water solubility of the oligomer may not be adequate when over 75 % of the total of X and Y groups present are hydro ⁇ gen.
  • the oligomer solids content in the treatment liquid preferably is from 0.1 to 0.5 % by weight ("w/o") of the total liquid. Below 0.1 w/o, it is very difficult to form a stable film on a DI tin can surface. On the other hand, the treatment solution is costly above 0.5 w/o, with little or no additional technical benefit.
  • the pH of the treatment solution should be adjusted to 4 to 6 through the use of orthophosphoric acid and/or a condensed phosphoric acid such as pyrophosphoric acid. Substantial etching of the can surface occurs at a pH below 4 and impairs film formation. At a pH above 6, the solu ⁇ tion has a short life because the oligomer tends to pre ⁇ cipitate and sediment.
  • the pH can normally be adjusted into the range of 4 to 6 by the addition of 0.05 to 0.3 w/o orthophosphoric acid or 0.03 to 0.2 w/o pyrophosphoric acid referred to the total surface treatment liquid.
  • Other con ⁇ densed phosphoric acids and mixtures of condensed acids or of condensed and orthophosphoric acids can also be used.
  • the treatment liquid should be heated to at least 40 degrees Centigrade during use.
  • the treatment liquid is poorly reactive below 40 degrees Centigrade, and this works against the formation of a highly corrosion re ⁇ sistant film.
  • little or no benefit due to heating is observed when the liquid is heated to above 60 degrees Centigrade, and unnecessary heating is expen- sive.
  • the spraying time should be at least 5 seconds. Only an inadequate reaction is obtained at less than 5 seconds, and a strongly corrosion resistant film is not developed. On the other hand, treatment times in excess of 60 seconds do not afford any increase in performance and increase the expense.
  • a small sprayer was used for the degreasing and sur ⁇ face treatment of the cans. This small sprayer was de- signed to give spray conditions identical to those encount ⁇ ered in spray treatment with the can washers which are cur ⁇ rently in use in the can manufacturing industry.
  • the corrosion resistance of a treated can was evaluat ⁇ ed through the iron exposure value ("IEV") , which was mea- sured according to the directions in United States Patent 4,332,646.
  • IEV iron exposure value
  • the paint adhesiveness was evaluated as follows: an epoxy-urea can paint was coated to a film thickness of 5 to 7 micrometers (microns) on the surface of the treated can, which was subsequently baked for 4 minutes at 215 degrees Centigrade; the can was then cut into a 5 x 150 millimeter (“mm") strip, onto which was hot-pressed polyamide film in order to afford a test specimen; and this was then peeled in a 180" peel test to give the peel strength. Higher peel strength values correspond to a better adhesiveness.
  • n had an average value of 20 and X represented hydrogen.
  • This oligomer was synthesized as follows: 100 grams ("g") of CellosolveTM solvent (the monoethyl ether of ethylene glycol) was introduced into a 1 liter reaction flask equipped with a condenser, nitrogen inlet tube, over- head stirrer, and thermometer, and 60 g of poly ⁇ 4-vinyl phenol ⁇ with an average molecular weight of 2,500 was added and dissolved; 40 grams of 2-methylamino ethanol and 100 g of deionized water were added, and the contents of the flask were heated to 50 degrees Centigrade; 40 g of 37% formaldehyde solution in water was added over 1 hour, fol ⁇ lowed by stirring at 50 degrees Centigrade for 2 hours and by further heating to 80 degrees Centigrade and stirring for an additional 3 hours at that temperature; the reaction product was cooled, 15 g of 85 % orthophosphoric acid was added, and 700 g of deionized water was also added
  • Tin plated steel sheet was drawn and ironed to afford tin plated DI cans, which were spray-rinsed with a hot 1% aqueous solution of a weakly alkaline degreaser (FINE CLEANERTM 4361A from Ninon Parkerizing Company, Limited, Tokyo) and then rinsed with water.
  • Cans were then sprayed for 40 seconds with surface treatment liquid 1 (described below) , heated to 50 degrees Centigrade, followed by a wash with tap water, then a 10 second spray with deionized water (with a specific resistance of at least 3,000,000 ohm*cm) , then drying for 3 minutes in a hot air dryer at 180 degrees Centigrade.
  • Surface-treatment liquid 1 had the following composition: oligomer solids 0.2 weight % 75% orthophosphoric acid 0.1 weight % water 99.7 weight % pH 5.5
  • Example 2 Example 2
  • Tin plated DI cans werer cleaned as in Example 1, then spray treated for 40 seconds with surface treatment liquid
  • Example 2 heated to 50 degrees Centigrade. This was followed by a water wash and drying as in Example 1.
  • the composition of surface treatment liquid 2 was: oligomer solids 0.2 weight %
  • the oligomer used was the same as in Example 1.
  • Tin plated DI cans were cleaned as in Example 1, then spray treated for 10 seconds with the above described surface treatment liquid 1 (cf. Example 1) , which had been heated to 50 degrees Centigrade. This was followed by a water wash and drying as in Example 1.
  • Tin plated DI can was cleaned as in Example 1, then spray treated for 40 seconds with the above described sur ⁇ face treatment liquid 1 (cf. Example 1) , which had been heated to 50 degrees Centigrade. This was followed by draining, without water rinsing, and then drying in a hot air dryer at 180 degrees Centigrade for 3 minutes.
  • Tin plated DI cans were cleaned as in Example 1, spray treated for 40 seconds with comparison surface treat ⁇ ment liquid 1, heated to 50 degrees Centigrade, then washed with water and dried as in Example 1.
  • Comparison surface treatment liquid 1 had the following composition: oligomer solids 0.2 weight % 75% orthophosphoric acid 1.5 weight % water 98.3 weight % pH 2.0 The oligomer used was the same as in Example 1.
  • Comparison Example 2
  • Tin plated DI cans were cleaned as in Example 1, spray treated for 2 seconds with the above described sur ⁇ face treatment liquid 1 (cf. Example 1) , which had been heated to 50 degrees Centigrade, then washed with water and dried as in Example 1.
  • sur ⁇ face treatment liquid 1 cf. Example 1
  • Tin plated DI cans were cleaned as in Example 1, then spray treated for 40 seconds with the Comparison surface treatment liquid 2, heated to 50 degrees Centigrade, then washed with water and dried as in Example 1.
  • the composi ⁇ tion of Comparison surface treatment liquid 2 was: oligomer solids 0.2 weight %
  • the oligomer used for Comparison surface treatment liquid 2 was not the same as that used for the Examples and the preceding Comparison examples, but instead had the ap- proximate formula:
  • n has an average value of 20 and X represents hydrogen.
  • S0_ liquid sulfur trioxide

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

On peut obtenir une surface avec une bonne adhésion à la peinture, une bonne résistance à la corrosion et une faible friction sur des boîtes étamées, embouties et étirées en appliquant par pulvérisation sur la surface de la boîte, pendant 5 à 60 secondes, à une température entre et 40 et 60 °C, un liquide aqueux de traitement ayant un pH compris entre 4 et 6 et comprenant (i) de l'acide orthophosphorique et/ou des acides phosphoriques condensés et (ii) une concentration d'au moins 0,1 w/o d'un oligomère soluble dans l'eau de formule générale (I) dans laquelle n est un nombre ayant une valeur comprise entre 10 et 30 et X et Y représentent indépendamment l'hydrogène ou un groupe Z, Z ayant une composition chimique de formule (II) dans laquelle chacun des R1 et R2 est un groupe alkyle ou hydroxyalkyle de 1 à 5 atomes de carbone, sauf qu'au moins 25 % du total de tous les groupes X et Y dans l'oligomère sont Z plutôt que l'hydrogène; puis en séchant la surface, éventuellement après avoir rincé à l'eau au préalable la surface revêtue par pulvérisation.A surface with good paint adhesion, good corrosion resistance and low friction can be obtained on tinned, stamped and drawn cans by spraying the surface of the can, for 5 to 60 seconds, at a temperature between 40 and 60°C, an aqueous treatment liquid having a pH between 4 and 6 and comprising (i) orthophosphoric acid and/or condensed phosphoric acids and (ii) a concentration of at least 0 ,1 w/o of a water-soluble oligomer of general formula (I) in which n is a number having a value between 10 and 30 and X and Y independently represent hydrogen or a group Z, Z having a chemical composition of formula (II) wherein each of R1 and R2 is an alkyl or hydroxyalkyl group of 1 to 5 carbon atoms, except that at least 25% of the total of all X and Y groups in the oligomer are Z rather than hydrogen; then drying the surface, optionally after first rinsing the spray-coated surface with water.

Description

SϋRFACE-TREATMENT METHOD FOR TIN-PLATED DRAWN AND IRONED CANS
TECHNICAL FIELD
The present invention relates to a novel surface treatment method for tin plated DI cans, i.e., cans formed by the drawing and ironing of tin plated steel sheet. The method imparts excellent corrosion resistance and paint ad- hesivity to the surface of the can prior to its being painted or printed, and also imparts the excellent slide- ability (low frictional resistance) that is required for smooth transport of the can by automatic conveying equip- ment, particularly modern high speed conveying equipment. BACKGROUND ART
The invention of Japanese Patent Application Laid Open [Ko ai or Unexamined] Number 1-100281 [100,281/89] is an example of a surface treatment liquid for tin plated DI cans. This teaching of the prior art employs a film form¬ ing liquid for the treatment of metal surfaces. This solu¬ tion has a pH of 2 to 6 and contains 1 to 50 gram per liter ("g/L") of phosphate, 0.2 to 20.0 g/L of oxyacid ions, 0.01 to 5.0 g/L of tin ions, and 0.01 to 5.0 g/L of condensed phosphate. Treatment with this conversion treatment solu¬ tion afforded a highly corrosion resistant phosphate film on the surface of tin-plated DI cans.
However, in recent years tin-plated DI cans have been produced using low levels of tin plating in response to economic considerations, and this has required that its surface treatment provide far more corrosion resistance than before. Moreover, when treatment is conducted by prior methods, in some cases the gloss of the base metal is degraded due to etching of the base metal. Accordingly, there is a demand for a surface treatment which does not damage the external appearance by reducing the gloss.
Treatment methods intended to provide corrosion re¬ sistance and adhesivity through the use of water soluble resin are exemplified by the invention in Japanese Patent Application Laid Open Number 1-172406 [172,406/89]. This invention provided as an example of the prior art comprises a method in which the metal surface is treated with a solu¬ tion which contains an effective derivative of a polyhydric phenol compound. However, the disclosed method does not generate a satisfactorily stable corrosion resistance. In addition, the metal can manufacturing process often suffers from a problem with transfer or transport: the slideability of the outer surface of the can during convey¬ or transport of the can may be poor due to a high friction coefficient of the outer surface, so that the can may be tipped over sideways. Can transport to the printer in the most modern high speed can lines is a particular problem in this regard. Accordingly, there is demand in the can manu¬ facturing industry for a reduction in the static friction coefficient of the outer surface of cans, which at the same time does not cause any adverse effects on the adhesion of any paint or lacquer subsequently coated on the can. The invention of Japanese Patent Application Laid Open Number 64-85292 [85,292/89] comprises a method for improving this slideability. The reference teaches a surface treatment composition for metal cans which contains water-soluble organic material selected from phosphate esters, alcohols, monobasic, and polybasic fatty acids, fatty acid deriva¬ tives, and mixtures of the foregoing. While the disclosed method does in fact generate an increase in the slideabil- ity, it does not improve the corrosion resistance or paint adhesion.
United States Patent 4,517,028 teaches in general terms treatment of metals with aminated derivatives of poly{vinyl phenols}. This reference, however, makes no specific reference to treating tin plate or DI cans. DESCRIPTION OF THE INVENTION Problem to Be Solved by the Invention
The principal goal of the invention is to provide a single treatment for DI cans that will result in increased corrosion resistance, good adhesion to subsequently applied paint or similar organic coatings, and a low coefficient of friction on the outside can surface, for efficient process- ing in automated can processing lines using high speed con¬ veyors and printers. Summary of the Invention
It was discovered that a film with excellent corrosion resistance, paint adhesion, and slideability could be formed on a DI can surface by controlling the conditions of treating the surface as follows:
(1) A liquid treating composition is prepared by dissolv¬ ing in water an oligomer having a chemical composition specified by the general formula:
—(CH—CH2)n—
wherein n is a number with a value between 10 and 30 and each of X and Y independently represents hydrogen or a group Z, wherein Z has a chemical composition conforming to the general formula:
H R,
I /
wherein each of R_ and , is an alkyl or hydroxyalkyl group having from 1 to 5 carbon atoms, except that at least 25 % of the total of all the X and Y groups in the oligomer are Z rather than hydrogen.
(2) The pH of the surface treatment solution containing the oligomer described in item (1) is adjusted to a value between 4 and 6 by the addition of orthophos- phoric acid and/or condensed phosphoric acid. (3) The surface treatment liquid as prepared in step (2) is heated to a temperature of at least 40 but prefer¬ ably to not more than 60 degrees Centigrade and the ably to not more than 60 degrees Centigrade and the heated surface treatment liquid is then sprayed on the cleaned surface of tin plated DI can for a time of at least 5 and preferably not more than 60 seconds. (4) The aforesaid spray treatment is followed by thermal drying or by a water rinse and then thermal drying. Preferably, there is no water rinse before drying aft¬ er contact of the surface of the DI can with the heated surface treatment liquid as specified above. If there is water rinsing before drying, it is preferred that at least the last such water rinse be with deionized or other puri¬ fied water substantially free from dissolved solids. If there is no rinsing with water before drying, it is nor¬ mally preferred to let the sprayed cans drain under the influence of gravity, and/or to remove some of the liquid from the can surface by mechanical means such as an air flow, rollers under slight pressure, or the like, to avoid the presence of excessive amounts of the surface treatment liquid on the surface during drying. Details of Preferred Embodiments of the Invention
The value of n in the general formula given above for the oligomer dissolved in the surface treatment liquid is 10 to 30. At values of n below 10, little or no improve¬ ment in corrosion resistance will be observed on DI tin plated cans. A value of 31 or more for n results in a poorly stable aqueous solution which cannot readily be used in practical applications.
In the general formula for group Z, R. and R repre¬ sent alkyl or hydroxyalkyl groups having 1 to 5 carbon atoms. When they contain six or more carbons, the stabil¬ ity of the aqueous solution is reduced. The introduction ratio for the group Z should be 25 to 100 mole % referred to the total number of X and Y groups in the oligomer. The water solubility of the oligomer may not be adequate when over 75 % of the total of X and Y groups present are hydro¬ gen.
The oligomer solids content in the treatment liquid preferably is from 0.1 to 0.5 % by weight ("w/o") of the total liquid. Below 0.1 w/o, it is very difficult to form a stable film on a DI tin can surface. On the other hand, the treatment solution is costly above 0.5 w/o, with little or no additional technical benefit.
The pH of the treatment solution should be adjusted to 4 to 6 through the use of orthophosphoric acid and/or a condensed phosphoric acid such as pyrophosphoric acid. Substantial etching of the can surface occurs at a pH below 4 and impairs film formation. At a pH above 6, the solu¬ tion has a short life because the oligomer tends to pre¬ cipitate and sediment. The pH can normally be adjusted into the range of 4 to 6 by the addition of 0.05 to 0.3 w/o orthophosphoric acid or 0.03 to 0.2 w/o pyrophosphoric acid referred to the total surface treatment liquid. Other con¬ densed phosphoric acids and mixtures of condensed acids or of condensed and orthophosphoric acids can also be used.
In addition, the treatment liquid should be heated to at least 40 degrees Centigrade during use. The treatment liquid is poorly reactive below 40 degrees Centigrade, and this works against the formation of a highly corrosion re¬ sistant film. On the other hand, little or no benefit due to heating is observed when the liquid is heated to above 60 degrees Centigrade, and unnecessary heating is expen- sive.
The spraying time should be at least 5 seconds. Only an inadequate reaction is obtained at less than 5 seconds, and a strongly corrosion resistant film is not developed. On the other hand, treatment times in excess of 60 seconds do not afford any increase in performance and increase the expense.
The surface treatment method of the present invention is described below through several illustrative examples of particularly preferred embodiments of the invention, and its usefulness will be demonstrated by comparison with com¬ parison examples. The examples are not to be regarded as limiting the invention, except in so far as noted in the claims.
General Conditions for Examples
A small sprayer was used for the degreasing and sur¬ face treatment of the cans. This small sprayer was de- signed to give spray conditions identical to those encount¬ ered in spray treatment with the can washers which are cur¬ rently in use in the can manufacturing industry.
The corrosion resistance of a treated can was evaluat¬ ed through the iron exposure value ("IEV") , which was mea- sured according to the directions in United States Patent 4,332,646. The corrosion resistance is better at lower IEV values.
The paint adhesiveness was evaluated as follows: an epoxy-urea can paint was coated to a film thickness of 5 to 7 micrometers (microns) on the surface of the treated can, which was subsequently baked for 4 minutes at 215 degrees Centigrade; the can was then cut into a 5 x 150 millimeter ("mm") strip, onto which was hot-pressed polyamide film in order to afford a test specimen; and this was then peeled in a 180" peel test to give the peel strength. Higher peel strength values correspond to a better adhesiveness.
The slideability of treated cans was evaluated by measurement of the coefficient of static friction of the outer surface of the can. Values of this coefficient of static friction of less than or equal to 0.9 are preferred, while values within the range of 0.7 to 0.8 are particular¬ ly preferred.
The oligomer used in all the examples below according to the invention had the average general formula: 0H
—(CH—CH2)„—
wherein n had an average value of 20 and X represented hydrogen. This oligomer was synthesized as follows: 100 grams ("g") of Cellosolve™ solvent (the monoethyl ether of ethylene glycol) was introduced into a 1 liter reaction flask equipped with a condenser, nitrogen inlet tube, over- head stirrer, and thermometer, and 60 g of poly{4-vinyl phenol} with an average molecular weight of 2,500 was added and dissolved; 40 grams of 2-methylamino ethanol and 100 g of deionized water were added, and the contents of the flask were heated to 50 degrees Centigrade; 40 g of 37% formaldehyde solution in water was added over 1 hour, fol¬ lowed by stirring at 50 degrees Centigrade for 2 hours and by further heating to 80 degrees Centigrade and stirring for an additional 3 hours at that temperature; the reaction product was cooled, 15 g of 85 % orthophosphoric acid was added, and 700 g of deionized water was also added. After reaction with these added ingredients, the oligomer was precipitated by the addition of 10% sodium hydroxide solution until the pH reached 8 to 9. The precipitated oligomer was then filtered off, washed with water, and dried to afford the oligomer used.
Example 1
Tin plated steel sheet was drawn and ironed to afford tin plated DI cans, which were spray-rinsed with a hot 1% aqueous solution of a weakly alkaline degreaser (FINE CLEANER™ 4361A from Ninon Parkerizing Company, Limited, Tokyo) and then rinsed with water. Cans were then sprayed for 40 seconds with surface treatment liquid 1 (described below) , heated to 50 degrees Centigrade, followed by a wash with tap water, then a 10 second spray with deionized water (with a specific resistance of at least 3,000,000 ohm*cm) , then drying for 3 minutes in a hot air dryer at 180 degrees Centigrade. Surface-treatment liquid 1 had the following composition: oligomer solids 0.2 weight % 75% orthophosphoric acid 0.1 weight % water 99.7 weight % pH 5.5 Example 2
Tin plated DI cans werr cleaned as in Example 1, then spray treated for 40 seconds with surface treatment liquid
2, heated to 50 degrees Centigrade. This was followed by a water wash and drying as in Example 1. The composition of surface treatment liquid 2 was: oligomer solids 0.2 weight %
50% pyrophosphoric acid 0.1 weight % water 99.7 weight % pH 5.5
The oligomer used was the same as in Example 1.
Example 3
Tin plated DI cans were cleaned as in Example 1, then spray treated for 10 seconds with the above described surface treatment liquid 1 (cf. Example 1) , which had been heated to 50 degrees Centigrade. This was followed by a water wash and drying as in Example 1.
Example 4
Tin plated DI can was cleaned as in Example 1, then spray treated for 40 seconds with the above described sur¬ face treatment liquid 1 (cf. Example 1) , which had been heated to 50 degrees Centigrade. This was followed by draining, without water rinsing, and then drying in a hot air dryer at 180 degrees Centigrade for 3 minutes.
Comparison Example 1
Tin plated DI cans were cleaned as in Example 1, spray treated for 40 seconds with comparison surface treat¬ ment liquid 1, heated to 50 degrees Centigrade, then washed with water and dried as in Example 1. Comparison surface treatment liquid 1 had the following composition: oligomer solids 0.2 weight % 75% orthophosphoric acid 1.5 weight % water 98.3 weight % pH 2.0 The oligomer used was the same as in Example 1. Comparison Example 2
Tin plated DI cans were cleaned as in Example 1, spray treated for 2 seconds with the above described sur¬ face treatment liquid 1 (cf. Example 1) , which had been heated to 50 degrees Centigrade, then washed with water and dried as in Example 1.
Comparison Example 3
Tin plated DI cans were cleaned as in Example 1, then spray treated for 40 seconds with the Comparison surface treatment liquid 2, heated to 50 degrees Centigrade, then washed with water and dried as in Example 1. The composi¬ tion of Comparison surface treatment liquid 2 was: oligomer solids 0.2 weight %
70% orthophosphoric acid 0.1 weight % water 99.7 weight % pH 5.5
The oligomer used for Comparison surface treatment liquid 2 was not the same as that used for the Examples and the preceding Comparison examples, but instead had the ap- proximate formula:
—(CH—CH2)n—
wherein n has an average value of 20 and X represents hydrogen. This oligomer was synthesized as follows: 100 g of poly{4-vinylphenol} (average molecular weight = 2,500) was charged to a 1 liter reaction flask equipped with a condenser, nitrogen inlet tube, overhead stirrer, and thermometer, and it was then dissolved by the addition of 500 g of 1,4-dioxane. This solution was maintained at approximately 10 degrees Centigrade, and 80 g of liquid sulfur trioxide (S0_) was added over 1 hour. This was followed by heating to 80 degrees Centigrade and reaction for 4 hours with stirring. Neutralization with 10% sodium hydroxide solution and removal of the solvent by distilla¬ tion afforded the oligomer used above. Table 1 reports the results of the Examples and Com¬ parison Examples, which confirm an excellent corrosion re¬ sistance, adhesiveness, and slideability for the conditions according to the present invention and superiority over all the Comparison Examples. Thus, treatment of DI tin cans according to the present invention provides an excellent corrosion resistance and paint adhesion to the surface of tin plated cans and also imparts the excellent slideability that is required for a smooth conveyor transport of the cans.
Table 1 TEST RESULTS OF THE EXAMPLES AND COMPARISON EXAMPLES
Example 1 Example 2
Example 3
Example 4
Comparison Example 1
Comparison Example 2
Comparison Example 3

Claims

1. A method for treating at least the outer surface of a tin plated DI can, characterized in that the precleaned surface to be treated is sprayed for at least 5 seconds at a temperature of at least 40 β C with an aqueous sur¬ face treatment liquid having a pH between 4 and 6 and comprising (i) acids selected from the group consisting of orthophosphoric acid and condensed phosphoric acids and (ii) a concentration of at least 0.1 w/o of a water soluble oligomer according to the general formula:
—(CH—CH2)„-
wherein n is a number with a value between 10 and 30 and each of X and Y independently represents hydrogen or a group Z, wherein Z has a chemical composition conforming to the general formula:
H R, l /
Z - —C—N
I \ H R2
wherein each of R. and R_ is an alkyl or hydroxyalkyl group having from 1 to 5 carbon atoms, except that at least 25 % of the total of all the X and Y groups in the oligomer are Z rather than hydrogen; and drying the sur¬ face thus sprayed, optionally after having first rinsed the sprayed surface with water.
2. A method according to claim 1, wherein the concen¬ tration of oligomer in the aqueous surface treatment li- quid is not more than 0.5 w/o.
3. A method according to claim 2, wherein the time of spraying is not more than 60 seconds.
4. A method according to claim 1, wherein the time of spraying is not more than 60 seconds.
5. A method according to any of claims 1, 2, 3, or 4, wherein the water soluble oligomer has a chemical struc¬ ture according to the formula:
—(CH—CH2)n—
wherein n has an average value of 20 and X represents hydrogen.
6. A method according to any of claims 1, 2, 3, or 4, wherein the sprayed can surface is not rinsed with water before drying.
7. A method according to claim 6, wherein the water soluble oligomer has a chemical structure according to the formula:
—(CH—CH2)„—
wherein n has an average value of 20 and X represents hydrogen.
8. A method according to any of claims 1, 2, 3, or 4 wherein the sprayed can surface is rinsed with deionized water as the last step before drying.
9. A method according to claim 8, wherein the water soluble oligomer has a chemical structure according to the formula:
—(CH CH2)„—
wherein n has an average value of 20 and X represents hydrogen.
EP91903769A 1990-01-10 1991-01-10 Surface-treatment method for tin-plated drawn and ironed cans Expired - Lifetime EP0510105B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP320090A JPH03207766A (en) 1990-01-10 1990-01-10 Surface treatment of tin di can
JP3200/90 1990-01-10
PCT/US1991/000202 WO1991010756A1 (en) 1990-01-10 1991-01-10 Surface-treatment method for tin-plated drawn and ironed cans

Publications (2)

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EP0510105A1 true EP0510105A1 (en) 1992-10-28
EP0510105B1 EP0510105B1 (en) 1994-10-26

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JP (1) JPH03207766A (en)
AU (1) AU642468B2 (en)
BR (1) BR9105932A (en)
CA (1) CA2072258A1 (en)
DE (1) DE69104825T2 (en)
ES (1) ES2063494T3 (en)
WO (1) WO1991010756A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991019828A1 (en) * 1990-06-19 1991-12-26 Henkel Corporation Liquid composition and process for treating aluminium or tin cans to impart corrosion resistance and reduced friction coefficient
JPH04187782A (en) * 1990-11-21 1992-07-06 Nippon Parkerizing Co Ltd Surface treating solution for di can made of tin plate
JP2771110B2 (en) * 1994-04-15 1998-07-02 日本パーカライジング株式会社 Surface treatment composition for aluminum-containing metal material and surface treatment method
CA2226524A1 (en) * 1995-07-10 1997-01-30 Toshiaki Shimakura Metal surface treatment agent and method and metallic materials treated with the same
JP3544761B2 (en) * 1995-10-13 2004-07-21 日本パーカライジング株式会社 Surface treatment composition for aluminum-containing metal material and surface treatment method

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Publication number Priority date Publication date Assignee Title
GB2112409B (en) * 1981-12-22 1985-07-03 Pyrene Chemical Services Ltd Phenolic compounds and their use in metal finishing processes
US4433015A (en) * 1982-04-07 1984-02-21 Parker Chemical Company Treatment of metal with derivative of poly-4-vinylphenol
US4457790A (en) * 1983-05-09 1984-07-03 Parker Chemical Company Treatment of metal with group IV B metal ion and derivative of polyalkenylphenol
HU29370A (en) * 1983-08-29

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Title
See references of WO9110756A1 *

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ES2063494T3 (en) 1995-01-01
AU7224391A (en) 1991-08-05
JPH03207766A (en) 1991-09-11
BR9105932A (en) 1992-11-24
AU642468B2 (en) 1993-10-21
DE69104825D1 (en) 1994-12-01
DE69104825T2 (en) 1995-05-24
EP0510105B1 (en) 1994-10-26
CA2072258A1 (en) 1991-07-11
WO1991010756A1 (en) 1991-07-25

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