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WO1993016813A1 - Procede d'amelioration d'un revetement du type a autodeposition - Google Patents

Procede d'amelioration d'un revetement du type a autodeposition Download PDF

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Publication number
WO1993016813A1
WO1993016813A1 PCT/US1993/001184 US9301184W WO9316813A1 WO 1993016813 A1 WO1993016813 A1 WO 1993016813A1 US 9301184 W US9301184 W US 9301184W WO 9316813 A1 WO9316813 A1 WO 9316813A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
coating
concentration
oxidation
titration
Prior art date
Application number
PCT/US1993/001184
Other languages
English (en)
Inventor
Motoo Nakano
Takaomi Nakayama
Takumi Honda
Original Assignee
Henkel Corporation
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 Corporation filed Critical Henkel Corporation
Publication of WO1993016813A1 publication Critical patent/WO1993016813A1/fr

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Classifications

    • 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
    • C09D5/088—Autophoretic paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings

Definitions

  • This invention relates to a method for improving the secondary adhesion of a deposited resin film obtained by immersing a substrate metal in an autodeposition type coating composition, so that a resin film is formed on the metal surface from the dispersed resin particles contained in the autodeposition composition.
  • compositions which can form a resinous coating on a substrate metal surface by immersion of the substrate metal surface in the composition are known as autodeposition type coating compositions.
  • Patents, such as JP Provisional Pub ⁇ lication No. Sho 47-17630 and 52-21006 have described coat ⁇ ing compositions which contain resin dispersed in water, oxidants such as H 2 ⁇ 2 , and acids such as HF, wherein the pH level is less than about 3.8.
  • the characteristic feature of an autodepositing composition is that when a metal sur ⁇ face is submerged in the composition, a coating film is formed due to the chemical reaction of the composition with the metal surface (in other words, resin particles associ ⁇ ate with the metal ions which eluted from the metal surface due to the etching action and deposit on the metal sur ⁇ face) .
  • resin particles associ ⁇ ate with the metal ions which eluted from the metal surface due to the etching action and deposit on the metal sur ⁇ face without applying electricity from an outside source such as needed for electrodeposition, a resin film is formed evenly on the metal surface.
  • the deposited resin film obtained by the above men ⁇ tioned autodeposition type coating composition has to be adherent to the metal surface.
  • the require ⁇ ment for the adhesion between the deposited resin film and the metal surface is not only the adhesion with the metal surface immediately to shortly after the resin is dried (hereafter called the primary adhesion) , but also the adhe ⁇ sion achieved after a long period of time in an environment where such coated substrates are practically used, or in a laboratory simulation of such an environment, (hereafter called the secondary adhesion) .
  • the secondary adhesion of the coating film to the metal surface is an important prop ⁇ erty that determines the quality of the processed material. Disclosure of the Invention
  • the invention aims to solve the problems in the above mentioned conventional technology and to improve the secon ⁇ dary adhesion of the deposited film formed by the autodepo- sition type composition.
  • the method according to the invention uses H 2 0 2 as an oxidant and its concentratio is not more than 2.0 grams per liter (hereinafter usually abbreviated "g/L") , and the secondary adhesion is improved by controlling the H 2 0 2 con ⁇ centration with an oxidation-reduction titration.
  • the autodeposition type coating composition is fil ⁇ tered.
  • Figure 1 is a correlation diagram between oxidation- reduction potential method values and hydrogen peroxide concentration values.
  • Description of Preferred Embodiments The method according to the invention is characterized in that commonly known materials are used for the autodepo ⁇ sition type coating composition, but the concentration of oxidants, especially the concentration of H 2 0 2 , is kept with ⁇ in a fixed range.
  • the range of the H 2 0 2 concentration according to the invention is equal to or less than 2.0 g/L. It preferable if the range exceeds 0.04 g/L, and more preferable if it is not greater than 1.0 g/L.
  • the H 2 0 2 concentration is equal to or less than 0.04 g/L, the quality, especially the secondary adhesion, of the film formed often shows incon ⁇ sistent results.
  • the concentration exceeds 2.0 g/L, the film obtained becomes too thin and has an undesirably rough surface. Thus the value of the product is signifi ⁇ cantly decreased.
  • An actual example of the auto deposition type coating composition that can be used for this invention is, for ex ⁇ ample, a composition consisting of dispersed resin, acids (for example HF) , ferric fluoride, and pigment as needed (for example, carbon black), with a pH level between 1.6 and 5.0. (Cf. JP Patent Publication ⁇ Kokoku ⁇ No. Sho 52- 35692) .
  • the content of each constituent is: from about 5 to 550 g/L of dispersed resin solids; from about 0.4 to 5 g/L of HF; from about 1 to 50 g/L of ferric fluoride (tri- hydrate salt) ; from 0.04 to 2.0 g/L of the oxidant H 2 0 2 ; and the appropriate amount of a pigment of preferred color.
  • an oxi- dation-reduction titration is used as the method to measure the H 2 0 2 concentration in the composition. Any known oxida ⁇ tion-reduction titration can be used, and there is no re ⁇ striction on these methods and titration solutions.
  • JP Patent Publication ⁇ Kokoku ⁇ Nos. Sho 52-35692 and 53-28461 propose a continuous stabilization method (hereinafter called continuous use) in which ferric ions (from FeF3) are added to the above mentioned composition from the beginning. Also, as a method to control these problems, JP Patent Publication ⁇ Kokoku ⁇ No. Sho 59-275 can be referred to as the prior technology.
  • This reference proposes a control method in which a known amount of H 2 0 2 is added to the autodeposition type coating composition con- taining known amounts of organic resin particles, hydro ⁇ fluoric acid, and ferric fluoride (FeF 3 ) , and the concen ⁇ tration of the ferrous ions in the composition is monitored by the oxidation-reduction electric potential between a reference electrode and a platinum electrode immersed- in the autodeposition composition.
  • the oxidation-reduc ⁇ tion electric potential measurement control method is not advantageous for improving the secondary adhesion of the deposited resin film obtained by the auto deposition type coating composition according to this invention, because of the reasons given below, and it is better to measure the H 2 0 2 concentration by oxidation-reduction titration of a sample of the autodeposition composition.
  • the oxidation-reduction electric potential (ORP) method in a conventional autodeposition composition as described above, cannot measure the concentration of indi ⁇ vidual oxidants directly. For example, if the metal object to be coated is iron, so that the composition after even a few minutes of use contains both ferric and ferrous ions, the ORP is expressed by the following equation (the Nernst equation) :
  • ORP value E 0 + 0.059 log ([Fe 3+ ]/[Fe 2+ ])
  • E Q the Standard ORP for this particular oxidation-reduction couple, is 0.4 volt versus the normal hydrogen electrode.
  • the. concentration of the oxidant H 2 0 2 is measured by the ox ⁇ idation-reduction titration method, with the H 2 0 2 concen- tration calculated as stoichiometrically equivalent to the amount of KMn04 consumed in the titration, and the ORP val ⁇ ues according to the prior art ORP method are measured for each H 2 0 2 concentration, so that the correlation is ob ⁇ tained.
  • the results are shown in Figure 1. As seen in Figure l, beyond the area where the H 2 0 2 concentration exceeds 0.1 g/L, the ORP value shows less and less change, and at the high concentration range, the curve becomes horizontal and approaches to a fixed value. That is, at the high concentration range, correlation between the ORP values and the H 2 0 2 concentrations almost disap ⁇ pears.
  • the ORP method is less than optimal to control the measure ⁇ ment of the H 2 0 2 concentration in this invention.
  • the ORP method can have a destabilizing effect on the coating composition.
  • the ORP values often drop rapidly as a result of the accumulation of fer ⁇ rous ions by dissolution from the large total area of sub ⁇ strates coated during the continuous use, and if one tries to maintain the ferrous ion at a lower level, by maintain- ing higher concentrations of H 2 0 2 , the accuracy of control drops rapidly.
  • control by ORP becomes a cause of de ⁇ stabilizing the coating composition, even when control by ORP was adequate at earlier stages of using the bath, when there was less accumulated iron and the ORP value was in its relatively high accuracy of control range.
  • controlling by ORP has the drawbacks of not being able to measure the oxidant concentration di- rectly, inability to control as accurately as desired when the oxidant concentration is relatively high, and destabi ⁇ lizing the coating composition.
  • the oxidant H 2 0 2 concentration can be directly measured, and it can also handle the high concentration area of H 2 0 2 , and its use does not destabilize the coating composition.
  • the adhesion between the metal surface and the deposited resin film can be controlled, and as a result, the secondary adhesion of the deposited resin film is im ⁇ proved.
  • An important feature in one embodiment of the inven ⁇ tion is that, for the continuous use of coating composi ⁇ tion, a portion of the composition is filtered through a filter that excludes materials with a high molecular weight and/or large particle size, and the H 2 0 2 concentration is measured by the oxidation-reduction titration using the filtrate.
  • H 2 0 2 with the oxidation-reduction titration, if the coating composition is directly titrated, it has been found to be difficult to judge the end point of the titration, because of the presence of resins and pig ⁇ ments in the composition.
  • resins and pigments, etc. are removed. Thus, the judgment of the end point becomes easier when the filtered solution is used for the oxidation reduction titration.
  • dis ⁇ persed resins including pigments
  • acid ingredients such as HF are added as needed.
  • the dispersed resins are controlled by the periodic measurement of the solids con ⁇ tent in the composition.
  • control by measurement with the LineguardTM 101 meter proposed in US Patent 3,329, 585 can be used satisfactorily.
  • the acid concentration of the coating composition can be easily measured by a neutralization titration of the fil ⁇ tered composition.
  • the base coating composition i.e., the composition exclusive of the hydrogen peroxide content, used in these examples and comparison examples had the characteristics shown in Table 1.
  • Newcol® 261A emulsifier (45 % solids) 0.30 Aquablack® 255 (carbon black dispersion) 3.87
  • the balance of the composition was demineralized water.
  • Cold-rolled steel sheets 7 x 15 centimeters in size were used for the metal substrate coated.
  • the sheets were cleaned by an alkali degreasing and washed with water be ⁇ fore coating. After being coated, they were washed with water, then dried in an oven at 110° C for 25 minutes be ⁇ fore tests were performed.
  • the H 2 0 2 concentration in the coating com ⁇ position a portion of the coating composition was filtered through a high molecular film with a mean pore diameter of less than 1.0 micrometer (" ⁇ m") , and the filtered solution was used for an oxidation-reduction titration.
  • the oxida ⁇ tion-reduction titration was performed by the following operation. A 10 milliliter ("mL") volume was collected from the filtered solution and 5 mL of 50 % sulfuric acid was added; this mixture was then titrated with 0.025 N KMn0 4 solution. When the collected filtered solution shows a light red color, it has reached the end point. From the volume of 0.025 N KMn0 4 solution, the H 2 0 2 concentration in the coating composition can be calculated.
  • the HF concentration was measured by neutralization titration on a 10 mL sample from the filtered solution. Bromophenol blue indicator was added. Then, the sample was titrated with 0.1 N NaOH solution. When the collected filtered so ⁇ lution turns pink, it has reached the end point. From the volume of 0.1 N NaOH solution which was required to reach the end point, the HF concentration in the coating compo ⁇ sition is obtained.
  • the oxidation-reduction electric potential in the coat ⁇ ing composition was measured using a Pt electrode versus an Ag/AgCl (saturated) electrode at a temperature of 20° C.
  • the external appearance of the film was judged by vis ⁇ ual observation after the substrate was coated and dried.
  • Table 2 below, "0" indicates no abnormality; "X” indi ⁇ cates pin holes and roughness were observed.
  • Example 1 A composition which consisted of 1 liter of the above- mentioned water soluble base coating composition plus 0.10 g of H 2 0 2 was used for coating.
  • This invention can improve the adhesion of the depos ⁇ ited resin film to the metal surface, particularly the sec ⁇ ondary adhesion, and can stabilize the composition by keep ⁇ ing the concentration of the oxidant H 2 0 2 , as measured by an oxidation-reduction titration method, within a fixed range.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

On a amélioré l'adhérence secondaire d'une couche mince en résine autodéposée par l'utilisation de peroxyde d'hydrogène comme oxydant primaire en une concentration non supérieure à 2,0 g/L, mesurée par titrage à oxydoréduction d'un ou de plusieurs échantillons de la composition d'autodéposition.
PCT/US1993/001184 1992-02-24 1993-02-24 Procede d'amelioration d'un revetement du type a autodeposition WO1993016813A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP07215592A JP3164874B2 (ja) 1992-02-24 1992-02-24 自己析出型被膜の改良方法
JP4/072155 1992-02-24

Publications (1)

Publication Number Publication Date
WO1993016813A1 true WO1993016813A1 (fr) 1993-09-02

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Application Number Title Priority Date Filing Date
PCT/US1993/001184 WO1993016813A1 (fr) 1992-02-24 1993-02-24 Procede d'amelioration d'un revetement du type a autodeposition

Country Status (4)

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JP (1) JP3164874B2 (fr)
AU (1) AU3661693A (fr)
MX (1) MX9300985A (fr)
WO (1) WO1993016813A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6379752B1 (en) 1997-12-13 2002-04-30 Henkel Kommanditgesellschaft Auf Aktien Rubber-metal composite
EP2126156A1 (fr) * 2006-12-01 2009-12-02 Henkel Kommanditgesellschaft Auf Aktien Bain d'auto-dépôt à teneur élevée en peroxyde
US12180384B2 (en) 2019-07-12 2024-12-31 Henkel Ag & Co. Kgaa Single layer autodepositable coating formulation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6060945B2 (ja) 2014-07-28 2017-01-18 株式会社村田製作所 セラミック電子部品およびその製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4191676A (en) * 1976-03-08 1980-03-04 Union Carbide Corporation Autodeposition process and composition
US4310450A (en) * 1980-09-29 1982-01-12 Union Carbide Corporation Crosslinkable autodeposition coating compositions containing a glycoluril derivative
US4313983A (en) * 1979-05-04 1982-02-02 Mouhanad Chaker Process for depositing latex films on metal surfaces

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4191676A (en) * 1976-03-08 1980-03-04 Union Carbide Corporation Autodeposition process and composition
US4313983A (en) * 1979-05-04 1982-02-02 Mouhanad Chaker Process for depositing latex films on metal surfaces
US4310450A (en) * 1980-09-29 1982-01-12 Union Carbide Corporation Crosslinkable autodeposition coating compositions containing a glycoluril derivative

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6379752B1 (en) 1997-12-13 2002-04-30 Henkel Kommanditgesellschaft Auf Aktien Rubber-metal composite
EP2126156A1 (fr) * 2006-12-01 2009-12-02 Henkel Kommanditgesellschaft Auf Aktien Bain d'auto-dépôt à teneur élevée en peroxyde
EP2126156A4 (fr) * 2006-12-01 2012-03-07 Henkel Kgaa Bain d'auto-dépôt à teneur élevée en peroxyde
KR101272170B1 (ko) 2006-12-01 2013-06-10 니혼 파커라이징 가부시키가이샤 고 과산화물 자가석출 바스
US12180384B2 (en) 2019-07-12 2024-12-31 Henkel Ag & Co. Kgaa Single layer autodepositable coating formulation

Also Published As

Publication number Publication date
MX9300985A (es) 1995-01-31
JP3164874B2 (ja) 2001-05-14
JPH05237457A (ja) 1993-09-17
AU3661693A (en) 1993-09-13

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