EP0510105B1 - Procede de traitement en surface pour boites etamees etirees et embouties - Google Patents

Procede de traitement en surface pour boites etamees etirees et embouties Download PDF

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Publication number
EP0510105B1
EP0510105B1 EP91903769A EP91903769A EP0510105B1 EP 0510105 B1 EP0510105 B1 EP 0510105B1 EP 91903769 A EP91903769 A EP 91903769A EP 91903769 A EP91903769 A EP 91903769A EP 0510105 B1 EP0510105 B1 EP 0510105B1
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EP
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Prior art keywords
oligomer
water
sprayed
seconds
cans
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EP91903769A
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German (de)
English (en)
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EP0510105A1 (fr
Inventor
Shigeo Tanaka
Tomoyuki Aoki
Masayuki Nihon Parkerizing Kibohgaoka Yoshida
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Henkel Corp
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Henkel Corp
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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 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 adhesivity to the surface of the can prior to its being painted or printed, and also imparts the excellent slideability (low frictional resistance) that is required for smooth transport of the can by automatic conveying equipment, particularly modern high speed conveying equipment.
  • the invention of Japanese Patent Application Laid Open [Kokai 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 forming liquid for the treatment of metal surfaces.
  • This solution 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 solution afforded a highly corrosion resistant phosphate film on the surface of tin-plated DI cans.
  • Treatment methods intended to provide corrosion resistance 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 solution 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 conveyor 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 manufacturing 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 derivatives, and mixtures of the foregoing. While the disclosed method does in fact generate an increase in the slideability, 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 processing in automated can processing lines using high speed conveyors and printers.
  • 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 improvement 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.
  • R1 and R2 represent alkyl or hydroxyalkyl groups having 1 to 5 carbon atoms. When they contain six or more carbons, the stability 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 hydrogen.
  • the oligomer solids content in the treatment liquid preferably is from 0.1 to 0.5 % by weight of the total liquid. Below 0.1 % by weight 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 % by weight 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 solution has a short life because the oligomer tends to precipitate and sediment.
  • the pH can normally be adjusted into the range of 4 to 6 by the addition of 0.05 to 0.3 by weight orthophosphoric acid or 0.03 to 0.2 % by weight pyrophosphoric acid referred to the total surface treatment liquid.
  • Other condensed 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 resistant film.
  • little or no benefit due to heating is observed when the liquid is heated to above 60 degrees Centigrade, and unnecessary heating is expensive.
  • 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 surface treatment of the cans. This small sprayer was designed to give spray conditions identical to those encountered in spray treatment with the can washers which are currently in use in the can manufacturing industry.
  • the corrosion resistance of a treated can was evaluated through the iron exposure value ("IEV"), which was measured 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.
  • 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 particularly preferred.
  • 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, overhead 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, followed 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
  • 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 Nihon 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
  • Tin plated DI cans werer 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.
  • 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 surface 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 treatment 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.
  • Tin plated DI cans were cleaned as in Example 1, spray treated for 2 seconds with the above described surface treatment liquid 1 (cf. Example 1), which had been heated to 50 degrees Centigrade, then washed with water and dried as in 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 composition 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 approximate formula: wherein n has an average value of 20 and X represents hydrogen.
  • Table 1 reports the results of the Examples and Comparison Examples, which confirm an excellent corrosion resistance, adhesiveness, and slideability for the conditions according to the present invention and superiority over all the Comparison Examples.
  • 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 IEV Peel Strength, Kg Force/5 mm Width Coefficient of Friction Example 1 100 2.0 0.8 Example 2 100 2.0 0.8 Example 3 100 2.0 0.8 Example 4 40 2.0 0.7 Comparison Example 1 350 1.5 1.0 Comparison Example 2 550 1.7 1.0 Comparison Example 3 700 1.5 1.0

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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.

Claims (9)

  1. Procédé pour le traitement d'au moins la surface extérieure de boîtes étamées pouvant être formées par étirage et emboutissage d'acier revêtu d'étain, caractérisé en ce que l'on pulvérise la surface prénettoyée à traiter pendant au moins cinq secondes à une température d'au moins 40°C à l'aide d'un liquide aqueux de traitement de surface ayant un pH entre 4 et 6 et comprenant (i) des acides choisis dans le groupe constitué par l'acide orthophosphorique et les acides phosphoriques condensés et (ii) une concentration d'au moins 0.1% en poids d'un oligomère hydrosoluble selon la formule générale :
    Figure imgb0015
     dans laquelle n est un nombre ayant une valeur entre 10 et 30 et chacun de X et Y représente indépendamment l'hydrogène ou un groupe Z, dans lequel Z a une composition chimique répondant à la formule générale :
    Figure imgb0016
     dans laquelle chacun de R₁ et de R₂ est un groupe alkyle ou hydroxyalkyle ayant 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 et non hydrogène ; et séchage de la surface ainsi pulvérisée, facultativement après avoir d'abord rincé à l'eau la surface pulvérisée.
  2. Procédé selon la revendication 1, dans lequel la concentration d'oligomères dans le liquide aqueux de traitement de surface n'est pas supérieure à 0.5% en poids.
  3. Procédé selon la revendication 2, dans lequel la durée de pulvérisation n'est pas supérieure à 60 secondes.
  4. Procédé selon la revendication 1, dans lequel la durée de pulvérisation n'est pas supérieure à 60 secondes.
  5. Procédé selon l'une quelconque des revendications 1, 2, 3 ou 4, dans lequel l'oligomère hydrosoluble possède une structure chimique selon la formule :
    Figure imgb0017
     dans laquelle n a une valeur moyenne de 20 et X représente l'hydrogène.
  6. Procédé selon l'une quelconque des revendications 1, 2, 3 ou 4 dans lequel la surface de la boîte pulvérisée n'est pas rincée à l'eau avant séchage.
  7. Procédé selon la revendication 6, dans lequel l'oligomère hydrosoluble possède une structure chimique selon la formule :
    Figure imgb0018
     dans laquelle n a une valeur moyenne de 20 et X représente l'hydrogène.
  8. Procédé selon l'une quelconque des revendications 1, 2, 3 ou 4, dans lequel la surface soumise à pulvérisation de la boîte est rincée à l'eau désionisée à la dernière étape avant séchage.
  9. Procédé selon la revendication 8, dans lequel l'oligomère hydrosoluble possède une structure chimique selon la formule
    Figure imgb0019
     dans laquelle n a une valeur moyenne de 20 et X représente l'hydrogène.
EP91903769A 1990-01-10 1991-01-10 Procede de traitement en surface pour boites etamees etirees et embouties Expired - Lifetime EP0510105B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP3200/90 1990-01-10
JP320090A JPH03207766A (ja) 1990-01-10 1990-01-10 ぶりきｄｉ缶の表面処理方法
PCT/US1991/000202 WO1991010756A1 (fr) 1990-01-10 1991-01-10 Procede de traitement en surface pour boites etamees etirees et embouties

Publications (2)

Publication Number Publication Date
EP0510105A1 EP0510105A1 (fr) 1992-10-28
EP0510105B1 true EP0510105B1 (fr) 1994-10-26

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EP91903769A Expired - Lifetime EP0510105B1 (fr) 1990-01-10 1991-01-10 Procede de traitement en surface pour boites etamees etirees et embouties

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EP (1) EP0510105B1 (fr)
JP (1) JPH03207766A (fr)
AU (1) AU642468B2 (fr)
BR (1) BR9105932A (fr)
CA (1) CA2072258A1 (fr)
DE (1) DE69104825T2 (fr)
ES (1) ES2063494T3 (fr)
WO (1) WO1991010756A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991019828A1 (fr) * 1990-06-19 1991-12-26 Henkel Corporation Composition liquide et procede de traitement de boites en aluminium ou en fer blanc destines a ameliorer la resistance a la corrosion et a reduire le coefficient de friction
JPH04187782A (ja) * 1990-11-21 1992-07-06 Nippon Parkerizing Co Ltd ぶりきｄｉ缶用表面処理液
JP2771110B2 (ja) * 1994-04-15 1998-07-02 日本パーカライジング株式会社 アルミニウム含有金属材料用表面処理組成物および表面処理方法
EP0838537B1 (fr) * 1995-07-10 2001-10-17 Nippon Paint Co., Ltd. Traitements de surface de metaux, procede de traitement de surface de metaux et materiau metallique ayant subi un traitement de surface
JP3544761B2 (ja) * 1995-10-13 2004-07-21 日本パーカライジング株式会社 アルミニウム含有金属材料用表面処理組成物および表面処理方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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 (fr) * 1983-08-29

Also Published As

Publication number Publication date
CA2072258A1 (fr) 1991-07-11
DE69104825T2 (de) 1995-05-24
EP0510105A1 (fr) 1992-10-28
AU642468B2 (en) 1993-10-21
BR9105932A (pt) 1992-11-24
DE69104825D1 (de) 1994-12-01
WO1991010756A1 (fr) 1991-07-25
ES2063494T3 (es) 1995-01-01
JPH03207766A (ja) 1991-09-11
AU7224391A (en) 1991-08-05

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