CS179582A2 - Zpusob fosfatovani kovoveho povrchu ze zeleza nebo zinku - Google Patents

Abstract

Iron- or zinc-based metal surfaces, especially on a component having both and iron-based surface and a zinc-based surface, for example car bodies, are phosphated by dipping them into an acidic aqueous solution containing: (a) from 0.5 to 1.5 g/l of zinc ion; (b) from 5 to 30 g/l of phosphate ion; (c) from 0.6 to 3 g/l of manganese ion; and (d) a conversion coating accelerator. The phosphated metal surfaces are then suitable especially for electrocoating.

Description

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The invention relates to the use of phosphate coating compositions suitable for use in this process.

Japanese Patent Buffering refers to a process for phosphating iron surfaces of iron (R) which is particularly useful in the treatment of products having complex surfaces such as aotomebilum in such a way that it is commercially used in eutomobell. , [0010] (a) pre-treatment of automobile bodies prior to the ion-active electrostatic (R) coating coating, which is now widely used in Japan by the coating method, is phosphated by firstly immersing the metal surface in acidic solutions containing 0.5 to 0.5% by weight. 1.5 g of ionzine, 5 to 10 g of phosphate ions and 0.01 to 0.2 g of dye ions, and / or rotate to 2 &amp; α-O-bromobenzene sulphonate, at a bath temperature of 40 ° C to 70 ° C for at least 15 ° C, followed by spraying with the aforementioned ň 2-sec. not solving the fast drying coating of the automotive industry to use on automobile bodywork parts which are coated with zinc or zinc alloys only on the surface · If the method according to the aforementioned Japanese patent is applied - 1 - ns Such materials (ie, rs of metal parts having both metal surfaces and metal surfaces with zinc) are applied to the surface of the coating with an adhesive coating having an alum and a uniform and dense surface. as well as excellent adftoai and versatility against such a film coating of the surface and the column is suitable. However, in the case of a coating film formed on the surface of a vapor, the spraying resistance of the coating is not sufficient to cause electrostatic corrosion, sufficient secondary adhesion (i.e., by dipping the surface and deposited on the surface). Coating © and transverse scratching into warm water The last electrostatic coating - the intermediate coating - The topcoat is easily worse than the surface behind Melose.

In addition to the aforementioned Japanese patent specification, the metal surface foafatisael compositions are described in U.S. Patent Application Serial No. 03161565, which discloses a method for phosphatizing metal surfaces using a phosphatizing agent comprising a spherical essential aliphatic, engene, phosphate, nitrate and nitrite. in the above clogs * i

DESCRIPTION OF THE PREFERRED EMBODIMENTS The description of the phosphating method using a solution comprising the tons of drag, manganese, siloxane, tungsten, and chloxes in awoistvioh, shown in gresee tores.

The inventions of etchings are based on the nature of the plastic surface, which is particularly suitable for the treatment of metal surfaces, such as automobile body surfaces, which absorb surfaces as both the body and the locus. The electrophoresis is advantageous for the development of novel new solids suitable for electrostatic coating, namely electrostatic coating. : 'i. Thus, in the context of the invention, there is a surface of the surface of the molasses and swelling, in the case of a metal surface of the seal of acidic rostokw, which is more suitable for use in a 1 liter test, 0.5 e 1, 1 g, and preferably (B) &gt; 30 g, preferably 10 and 20 g of sodium bisulfate, c) 0.1 g of preferably 0.8 to 2 g of manganese ions and &lt; 1 &gt; ujchXevaé keaversoihe.povleku. .yřeéséten vyáélesu is the same acidic scientific tool for. phosphating the surface and © Melose or - 5 - «lato. vyanadujicl ee ti », to tete proetředke» 4 © listed 4? rettek.

Coating Coatings Ury * 4 is at least one% tatotni. 1) 0, CX oB 0.2 g / Xltr, and preferably 0.04 el 0, 1 g / l ltr j d i n e l l l l, l. 1 II) 0.05 µM 2 µl / ltr, preferably 0.1 and 1.5 g / ltr

α-nitrile ions of xyloate ions, and Λ III) 0.5 to 5 «/ liter, and preferably 1 B B 4 / / liter of hydrogen peroxide (v« pulled to 10Λ Boi) j

AND

Lead acidic faulty matte car if it falls j td * contain aXeupee One kind of lonts and tichtos | (e) 10 10 gzlitre, preferably 2 g / cm3 / cm3 / cm3, and f) 0.0 g / l and 11 g / l, preferably 0.2 g / l and 1.5 g / ltr of bread lontones.

After the metal coating is then applied, the coating is coated, for example, by the electrophoretic coating, and preferably by the cationic coating, of the elastomeric coating.

The term "zinc surface" refers to iron surfaces, surfaces of 20 iron alloys, zinc surfaces and zinc alloys and surfaces. Zinc and zinc alloys include, for example, zinc-coated steel, dip-coated and hot-dipped steel surfaces coated with elite, hot dipping, hot-dip galvanized steel »galvanized zinc-coated» , and a steel sheet coated with a coating of alloys, a galvanic process, according to the present invention, that the surfaces of metal parts, such as car bodies, having both iron surfaces and surfaces are The locus can be processed according to the invention and an excellent flock. According to the process according to the invention, it is indeed possible to bond the conversion coatings, such as those obtained by immersing the treated surface in an adhering bath, with only a quantity of etch and a metal surface of the process according to the invention. The etching of the chemicals used in the process according to the invention as well as the fat produced by the process are only 2/3 and 4/5, respectively, for the use of the conventional methods. A method according to the invention which is equally applicable to the treatment of the surface formed by a single embodiment of the described type of preferred embodiment of the present invention is to look at the metal surface to be phosphatized, for example, by spraying with / or immersing the pellet drills the alkaline, scorched, heat-cured heat at 50 to 60 ° C for 1 minute, then rinsing it with ordinary water and tap water, spraying r / or. immersing at room temperature in the fabric of the surface repair agent for a period of at least 1 second, then immersing at a temperature of 40 to 70 ° C into the acidic aqueous plant by means of the invention for at least 15 seconds, and finally rinsing it with the preferred water ». water supply and water supply.

The acidic aqueous growth of the composition according to the invention has a oleic acid ions content of 0.5% to 1.5 g / liter. Is-13 ff.noisiví. zinc ions than flour than about 0.5 g / liter, the colored surface of the vanilla layer does not form on the surface. If the mass of the ions of the ions is greater than 1.5 g / liter, if the ions of the erythrocyte layer form a heat-forming surface on the surface, the crystal of the leaf crystals is formed, some of which are formed by the process of formation. they are not suitable as a backing for a catioactive and electrostatic coating of the dog

If the phosphorus content of phosphorus compounds is 5 g / liter, a non-irreversible coating is formed. - B -

Phosphorous ion ions are over 30 j / lltr, there is no improvement in the orthorane a and the use of more X X g g / l orthophosphorous ions and ions is not harmful ·

If the permissible release of manganese ions is about 0.6 g / ltr, the manganese content of the layer formed on the zinc surface is non-diminishing, which has a poor adhesion to the coating. the cephalic acid-cationic electrostatic coating layer. If manganese ions exceed about 3 g / ltr, it does not and does not further improve the deposition of the phosphorus layer. It is therefore uneconomical to use more than about 3 g / l.

With respect to the preferred accelerated coating, as described above, if less than the lower limit is present, the iron surface coating is insufficient, causing the formation of yellow rust, etc. If the amount of accelerator is greater than that said upper limit, is formed on the surface of a vein-obscure, blue-colored invert.

As an example of a zinc ion source for use in the process of the present invention, mention may be made of nitric oxide, carbonate carbonate and nitrous nitrate, of which the wax is used alternatively.

An example of a source of phosphorphthalene and phosphorous sodium phosphate, zinc phosphate, and phospho-phenylalanine, may be at least one example of an ion source, such as manganese nitrate, manganese nitrate, chlorine msnene and ftaforeSneo tsennnllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll sllllllllllllllllllll one.

As an example of the source of uryclovadd cooveroxide and la®, sodium nitrite, ammonium nitrite, m- nitrousbaseaaoxfosose and hydrogen peroxide *

With regard to the additional ingredients mentioned above, the addition of nickel ions to the composition containing the resin and the resultant function of the phosphorus-free coating, tskl® adhesion &amp; the corrosion resistance of the coating formed by the electrostatic coating is furthermore known as an example of a possible additive for nickel ions to include nickel carbonate, nickel chloride, nickel chloride, or nickel phosphate, and to at least one example of dual ion ionization. nitric acid, nitrate nitrate, nitrate, or nickel nitrate, and, for example, ebloroanic ions Xa®, include ehleric acid, sodium hypochlorite, or ammonium nitrate * -

Typically, the process according to the invention provides a temperature of 40 [deg.] C [theta] C, about a temperature of 45 [deg.] C. &amp; When the lower leg of the aai 40® 6 heats up, fcenverani commanded &amp; and the need for further refinement of the metal surface to obtain a satisfactory coating, the temperature will emerge in the form of an unacceptable speed, diad, and / or coating. The back bath and the bath result in an unsuitable conversion coating. In the bath with the equilibrium it forms shining liquors. While the metal surface in the peatttftt is usually in contact with the &quot; melt &quot; 15 seconds, preferably ≥ 140 seconds. it is puzzling for a period of about 15 seconds, a suitable layer is not formed, three processing of metal workshops, and alodite pwfll surfaces, such as for example in car bodywork, the finer of the workpiece is firstly preferred WMt immersion © o o o 15 e ek ek výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou pak pak výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou výhodou In order to produce a screen that adheres to the surface while it is being matured, the benefits of the invention are transferred for a long time if the speed of the production line is imported, the spraeavdtfpeaeareed in the case of the sucker. with subsequent spraying ». - 11 les X n X X X WXii explained below! examples. ? Examples 1 1 Ι 8 ají 8 ají · 8 · ají 8 el působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ působ. Examples 14 and 14 are comparative examples, and the calories and known satayes are compared in otelia.

The actual process, which is suitable in the examples, should be added to the aqueous coating compositions, the examples of which are given in Table T, the metal to be treated and the results obtained after phosphating are shown in Table II.

All the four metal coatings listed in Table II are modified by the following procedure. * A) First, and degreased, and used in the bleaching composition (Nlppea Faint Co »» SlihlO ® f · SB 200 * by weight »· yes 2 is added to the metal surfaces for 1 minute, followed by "immersion" in the coil to the blanket for 2 minutes - fc) the metal surfaces are then rinsed with 15 min. allowing the metal surfaces to be immersed at room temperature for 1 second in a surface treatment composition (Wtppof Palot Co., Co., Ltd., 5% by weight of 0, 1 S) | d) above the surface of the surface immersed in the temperature of # 52 ° <3 for about 10 seconds into the acidic aqueous plant mentioned above, the surface of the surface is then rinsed at room temperature and water for 15 seconds. room temperature to deionized water, not less than 15 minutes later, are then dried at 100 ° C in hot air for 10 minutes, at which point the coating weight on the treated metal surface (results are shown in Table Π), and Also, the treated metal surface is a ketone active electrostatically coated with the material. Wippon faint CoM WO W 0-3 »» a ý V V V V / / / / / / / / / / V V V V V V V V V V V 0 0 0 0 0 The sheets and the sheets provided with the thus formed coating are then subjected to three and three heads of the headband. .

W® second cauldron and sheet metal, epaquainted with a coating and coated with a coating, and its coating material Wlppon ralpha, TO WS gray in the M / U®, which is then fired by the IMS ® S p e th e th e th e th e th e th e th e mppoatFalat 0 © «» * <5β &amp; $ 8 fiý (MargareWa bél) "v tišila · 40yU®, which a®-burns out how TiCa» e «glazedplated sheets and 3 coatings and triple burns ·

Yieehmy is then placed on the stiffened surfaces and then subjected to an adhesive test, while the rolled-up steel sheet is soaked in such coatings as it is described in the following. thy® amine tests »· perform tektei A) feet atříkáalm m lanky (aiS-2 * 2871) íe vaeike area e alektm the prints andrelatedthattheytheytheytheythesurethaandtheareaand thentheprefect 500 intends (pesiakevaa steel) or © looo intends (aa cold-rolled steel sheet) sprays 5 May roatecsolants. B) Adofee tea-fc »

Fe immersion of the sheet to be coated in water * 14 water ® Wlot * | 0® $ ** for 10 days ee with a sharp tool to make 1 a; 2 mm from your groove to make 100 sheets <on each of the surfaces s® pile adheres the adhesive tape and sets the number of coating squares that cling to the sheet after the adhesive tape is torn off # 0) Rust test:

The coated portion is tilted at an angle of &lt; &apos; &gt; with respect to the horizontal plane and is capable of being repeatedly triggered by an arrow and a 90 [deg.] Tapered head, produced and alloyed with steel (grade I-G-4404, Hv hardness at least). 700), a weight of 1.00 g and a total length of 14.0 mm, except for the coated surface, 2 $ scratches are formed. Thereafter, the coated wreath is subjected to four test cycles, each consisting of brine spray (JIS-2-2871, 24 hours), moisture exposure (40 ° C, relative humidity, 120 hours) and faded from left at room temperature (24 hours). The end of the test is determined by the mean values (in mm) of the largest diameter of the rust stains and the mere results shown in Table IX.

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Table XX · Continued Metal eskou®® Rigidity Example 8 Example 19 Example 1® Example 11 Layer The sample appearance is good Equal good Good Equilibrium and aesthetics Aroma and Eifite , metallurgy and metallurgy, and metallurgy metallurgical »a® herk, steel teotnoai. 2 layers (§ / g &amp;) '2.7 43 4.5 4.0 plesM brine spraying (prdsir in »«} 1.5 33 33 • 4.0 grooves to be fed in. 2 »« IWIOO 15/100 58/100 «8/100 1 raii 100/10 © 0/100 0/300 0/100 • electric * bed linen • Thorn barrel view vsork good good * good * sareness and - sherry of dense and compact hutnota dobré rove · »aernoat ahutnot · hrotneot avrstvy Ca /») 2,3 3,7 33 3,3 peetřlk sele tórou Chopper v »©) M 10,5 ^ 3 M ridge '*« · 100 / 100,15 / 100 0/100 '0/100 24/100' 0/100 33/100 0/10 © 22 fa b alka II - kev investigated property example / 8 example F example U0 example n sample layer good equals good equality and iU · morality and estheticity immutability measure and ha tne and metallurgy -i metallurgy applied electron- weight -> layers (a / ®) 2 »9 4.3 4.0 for oeel spraying brine (diameter in m) 2.0 5.0 1.0 3.0 Adjacent grooves in distance, 2 mat 1 »» 100/100 100/100 20/100 0/100 64/100 8/100 52/100 12/100 aa stu-: dated rolled non-wrought pattern look good good straightness and solidity good uniformity metallurgy good equorašrnos ta hutnota hmknost. ·> Layers <g / ® ~) 2.0 0.8 3.1 23 brine spraying (average in »») 1 4 1.5 1.5 grooves, among others, in the range of 100 100/100 100/100 100/100 100/100 IffiB 100/100? 80/100 10O / 100 100/100 stains (diameter in am.) 0, S8 3,10 1,10 1,30 * o - .f ft I and 1 I and XX * jMk * a $ a «metal examined property example 1 &amp; Example Π Example 14 Layer · Alloy Sample appearance Good Equal * Good Equilibrium Equal * Asěroest Moderate Measure. <;. dipped weight 9 4.2 3.0 4.6 • and crumb layer (g / s) 5µ.srw spraying selaskon. (diameter in mm) 3,5 3,0 4,0 shifts prll- Ivenavést <dist # 12 sm y ,. mm> 2 / xoe 0/100 appearance vsserkta aXoktre * lytlka peainko-safa and the next pXaah adheres the weight of the layer (g / sT) by the spray (diameter in mm)

frýhyVO 2 ffiffi1 mm good uniformity good uniformity good equilibrium 3,5 2,2 3,8 T, 0 73 8,0 t> / 100 34/100 0/100 0/100, - O / lOO 0/100 faal * · Π * betraying metal skcwttwtóá property.example-, 12: example 13 example 2 $ 'layer vAM vor good revon- good. equals good equilibrium alloys extruded metallurgical veneer, subdivided lectra biotropy layers << § / »3.6. a, 8; 4.5 Xytical steel plate brine spray (primer va®} 3.5 3.9 3.0 grooves sawdust "vsdax.MVcSt 2 ffil 48 / 1C0 68/100 0 / 10C 1 ®fa 6/100 9/100 0 / 100 ss cold-rolled steel plates insight sample good equals -mut twr "good flat-layer weight (g / ti) density density --wmvnkst mi mos t 3,0 1,2 3,4 saline spray (va®) 1,5 3 , 5 3.0 * grooves in left side 1 100/100 60/100 0/100 1 n® 100/100 45/100 0/100 resistive f stains (average in ®m) 1.30 4.51 2 , 52

Claims (4)

Α | · - * - - 25 - / - ø · δ atvyn * xeaui ·, 2půs b feoíaMvdní fcevovdhc pewrehtt> eSeXeaa and © b © a-into, -r nbaS ae metal surface <4 © Kyse- ku at at ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku ku 0,6 0,6 0,6 0,6 ku ku 1 &amp;nbsp; &lt; tb &gt; &lt; tb >, &lt; tb &gt; &lt; tb &gt; &lt; tb &gt; &lt; tb &gt; &lt; tb &gt; / Xiir · 3, the method of clauses X is disclosed, and as at least one group of substances is accelerated, the amount of the compound is at least 0.01 µM 0.2. g / liters, e ř ř * * ee ee ee £ £ £ £ £ ová X X X X X X y y y S S g g g g g g g g g g g g g g g g g g g g g , 1 <rostok contains jetelt ever ury ever ever ever íh po ever ever ever vla vla vla vla vla vla »» t t t t t t t t t t t t t t t t t t t t g g g The method according to clauses 1 to 4, wherein the solution additionally contains the ionic ions in an amount of 1 g / g / ltr. 6. A method according to items 1 to 5 ', dispensing a sieve ®, &amp; The plant contains chloronium lions in a quantity of 0.05 µg / liter. 7. The process of clauses 1 to 6, wherein the metal coating is immersed in the rococo for a period of time. at least 15 seconds, after which the surface is injected with this roatoke for 2 seconds · The method according to FIGS. 1 to 7 shows that the metal surface to be treated is both leless and slot. $. The method according to clauses 1 to 8, which is known from the art, contains a layer length of 0.7 to 1.2 g / liter, phosphorothenone ion to 10 to 20 g / liter with mengene ions. 0.8 g 2 g / lltr. Characterized in that the phosphated metal surface is rinsed and provided with a coating applied by the coating. 11. An acidic aqueous composition for iron or zinc phosphatizing surfaces, characterized in that the composition is a rosette according to points 6 to 9. JIJDr.