TW524884B - Zinc phosphate conversion coating and process - Google Patents

Abstract

Concentrates containing (a) an hydroxylamine sulfate accelerator, and (b) zinc, nickel, manganese, and phosphate ions are formulated into aqueous coating solutions for treating metal surfaces, such as ferrous, zinc, and aluminum surfaces. In the process of using this solution, hydroxylamine ions become depleted or reduced in concentration in the applied solution. A replenishing solution is added for reusing the solution until the replenished coating solution reaches a sulfate level of no more than 14 g/l.

Description

524884 Printed by A7 B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of Invention () & [Reference to Related Invention Application] This application is under review US Application Serial No. 08/663, 374 (application date is June 13, 1996), a follow-up invention; it is a follow-up invention No. 08/440, 044 (application date: May 12, 1995, has now been abandoned); it is the United States Application Series No. 08/123, Subsequent invention of No. 500 (application date: September 17, 1993, which has been abandoned); it is a US application, application series No. 736, 835 (application date: July 29, 1991, which has been abandoned) Re-invent. These applications are incorporated herein by reference. [Background of the Invention] The present invention relates to a zinc phosphate coating for a metal surface, and a treatment method for phosphorizing a metal surface with an acidic phosphate aqueous solution. The present invention can be applied to various materials including cold rolled steel sheets (,, CRS ,,), alloys and aluminum. σ [Statement of related skills] Today's dish salt coating solution is generally a dilute aqueous solution containing acids and other chemicals. When applied to an active metal surface, it will interact with the metal surface and form on the metal surface. It is essentially an invisible layer or coating. -Generally, a crystalline coating is preferred. He Zhizheng. Ionic generation: These solutions include phosphate ions, zinc and other metal ions (especially fierce, nickel and other divalent gold, the special properties desired in the coating. Other representative nitrate, nitrite, gas The ions in the brewing process can be representative of the salt of the dish or the salt of the gaseous oxalate. And trimming; ⑵Ziwei / 3 sequence of the following processing steps: ⑴cleaning⑷ ⑷Zing treatment; and post-processing ——As usual in each of the above steps, the paper size is toward the towel (please read the precautions on the back before filling this page)-(210 X 297 mm) 524884 A7 B7 V. Description of the invention () Wash between steps. Prevent or at least reduce excess material from being taken to the next step. Despite advances in phosphate coating solution compositions and phosphating methods, there is a continuing need to further improve these compositions and processing methods to make it easier Regulate treatment methods, ensure proper coating weight, reduce rust or white spot formation, and reduce harmful environmental impacts and dangers. [Explanation of the Invention] In the description of this article (except for the scope of patent application and operation In the examples or otherwise specified by exceptions), all numbers representing the total amount of ingredients or reaction or conditions of use should be understood to be modified by the word "about" to describe the broadest scope of the present invention. Generally speaking, it is indicated Implementation within the limits of the numbers is preferred. Also, unless specifically indicated to the contrary: Percentages, "parts" and ratios are by weight; the term "polymer" includes oligomers; A description of a substance that is preferably used for purposes related to the present invention means that a mixture of any two or more members of the group or class is equally suitable or better; the description of the composition in chemical terms means that, in A component added to any combination specified in the narrative, without the need to exclude in advance the interactions that occur between the various compositions in the mixture once mixed; the definition of a substance in the ionic form means that there are sufficient equilibrium ions to Causing the composition to be electrically neutral as a whole (any counter ion specified by this suggestion should preferably be selected from the balance of other suggestive ionic forms Off 4-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -----

ϋ I n ^ OJ n —.1 n ϋ -1 ϋ I Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 524884 A7 B7 V. Description of the invention () t-child 'to the extent possible, you can also choose other such counter ions at will ; And in addition to avoiding counter-ions that have a detrimental effect on the targets indicated in the present invention): and the term "Morr, and its variations can be applied to elements, ions, and other chemical species defined by numbers and the type of atom present, And applied to compounds with well-defined molecules. [Summary of the Invention] 'Certain specific phosphate compositions containing nickel and manganese and hydroxylamine sulfate ("HAS") as a dye accelerator have been discovered Can provide polycrystalline coatings, and still maintain the application and performance of HAS dye accelerant, without changing its flaky or needle-like crystal morphology (as described in US Patent 4,865, 653). The present invention The HAS-promoted dyeing and scaling treatment composition can be used in various temperatures including iron alloys, zinc alloys, and aluminum in the desired temperature range from 6 to 6 C (at 46 to 54 ° C). And its alloys Produces a desirable uniform gray, fierce, and modified linoleic acid coating, and can be performed by spraying and / or dipping, and by any other method that does bring the composition into contact with the substrate Coating. If necessary, the hydroxylamine sulfate dye accelerant can be incorporated into the manufacturing and replenishment mixture without the need for traditional supplemental dye accelerants (such as nitrite) 'because of their chemical instability, and Subsequent application is not suitable for single package concentrates from which a fully functional composition can be prepared by dilution with only water. The composition according to the invention also has a high degree of sulfate ions which may be introduced into the composition when in use. In addition to providing the overall desirable advantages without the disadvantages faced by the previous technique, the present invention also provides improved operational uniformity at low temperatures and reduces the harmful environment associated with nitrite Impact and danger. This degree applies to China National Standard (CNS) A4 specification (210 X 297 public love) (Please read the precautions on the back before filling this page) «— — — — — I — Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 524884 A7 V. Description of the Invention (Polycrystalline coating contains Zη, Mn, and Ni stored in the coating, and Fe exists in the coating on the iron surface. The invention also includes a preparation or concentrated composition As a specific example, it can be subsequently diluted with water to form an aqueous, acidic coating solution for spray or dip coating treatment methods. [Description of Specific Embodiments] " Generally, the composition according to the present invention ( Used to form a phosphate-converting coating that does come into contact with a metal substrate) It will preferably contain (more preferably substantially, or more preferably) water and:, (Please read the precautions on the back before (Fill in this page) P Composition P04_ ^ Zn ion Ni ion Μη ion HAS _3 ion ILate ion sulfate ion concentration (WT%) ^ 5 ^ 2. 5% 0. 05 to 0.2% 〇 02 to 0 15 % 0 · 02 to 0 · 15 ° / 〇〇 · 1 to 0 · 25% 0 to 0.2% 0 to 0.15% 0 to 1.4% Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and any misaligned fluorine Compound ions such as fluorosilicate, fluorotitanate, fluoroborate, etc. Stoichiometric equivalents of the compound, the solution should be tied around its fe between the fluoride ion content in the range of the above-described preferred concentration range listed. The coating solution can be obtained by diluting the concentrate containing the composition of the aforementioned concentration when the concentrate is diluted with water at 48 g / liter of concentrated s. Specifications ⑽χ 297 public love 524884 A7 B7 i. Description of the invention () Formed by dilution with water. Therefore, the concentrate is formulated to provide a coating solution that preferably contains (better substantially, or even more preferably) water and the following composition: (G) 0.5 to 2 g / L, More preferably 0.8 to 1 g / L of zinc ions; (ii) 5 to 25 g / L, more preferably 10 to 15 g / L of phosphate ions; (I) 0.2 to 2 1.5 g / L, more preferably 0.5 to 1 g / L of manganese ions; (J) 0.2 to 1.5 g / L, more preferably 0.5 to 1 g / L of nickel ions; ( (K) 1 to 2.5 g / L, more preferably 1 to 2.5 g / L of hydroxylamine dye accelerator; and (optionally) (L) at most 1.5 g / L of total fluoride, which (more (Better) free-state fluoride content of 400-600 parts per million; and (optionally) (M) up to 2 g / l of nitrate ion; and (optionally) (N) up to 14 g / Liters (more preferably not more than 90 g / l, and more preferably not more than 6_0 g / l) of sulfate ion. 0: 0.5 至 1.0 In the scale treatment solution, preferably the weight ratio range of the ion to the dishate ion is 1.0: 10 to 1.0: 25, and the weight ratio range of the total to the sum of manganese and nickel is 1.0: 0.5 to 1.0 : 2. 5 (of which the ratio of manganese to nickel is the best printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) = 1. 0: 1. 0), and 1. The ratio range of 〇: 0.05 to 1.0: 1.5 is satisfactory. The above-mentioned "fluoride content" is clearly defined and can be conveniently referred to in US Patent No. 3,431,182. And is commercially available from Orion Instruments for a fluoride-sensitive electrode in a two-form measurement. The term "free-state fluoride content, 'as used herein is relative to commercially available from Hank Corporation. (Madison, Michigan) Pyco + Echem, -7-This paper size applies to China National Standard (CNS) A4 (21G X 297 public love) " -------- 524884

£ 120 in the Printing & Consumer Cooperatives Department of the Intellectual Property Bureau of the Ministry of Economic Affairs: Who is active, who is 6, 6, ^ The process liquid θ 'T detailed in the report 9 _ P in ＋+ Α technology The method will be: in a quasi-solution, and if two counts are needed, the instrument on the instrument will be accurate & 彳, Tegu k 10-round > A fork to Q. Then the electrode is removed: water or _ water Core, wipe dry, and adjust the desired temperature to the same temperature as the specified standard. The millivolt directly from the instrument (hereinafter written as " V " or ",) Read the infiltration and «convert to parts per million (_) by comparing with a solution obtained from a solution containing a known free state gaseous content: milliseconds. In the dishing composition of the present invention, Desirably, the total acidity of the solution is IS to 25 (more preferably 17-22, most preferably 19-20), and the free acidity is G.3-1.0 (more desirably 4_G8, and most preferably 0.5 ^ 7). The acidity is expressed in terms of points in the text, where "points," as used herein, means 0.1 N NaOH to titrate a 10 ml aliquot to a pH of 8.2 (to a miscellaneous indicator Number 8 ml (to bromophenol blue indicator for free acid) of the desired (,, ,, 1); in general the acid), and is titrated to Chiu & amp. Suitable and preferred sources of the components of the phosphating solution of the present invention include the following: For zinc ions: zinc oxide, carbonate, nitrate, etc .; for dish ions: phosphoric acid, zinc phosphate, zinc hydrogen phosphate 'phosphate Dihydrogen zinc, manganese phosphate, manganese phosphate, manganese dihydrogen phosphate, etc .; For manganese ions: manganese oxide, manganese carbonate, manganese nitrate, the above-mentioned manganese phosphate compounds; for nickel ions: nickel oxide, nitric acid Nickel, nickel carbonate, etc .; For fluoride ion * 8------------- f 丨 丨 丨 丨 丨 丨 Order _________P (Please read the precautions on the back before filling this page) This paper Dimensions apply to China National Standard (CNS) A4 (210 x 297 mm) 524884

V. Description of the Invention (3) Hydrogenic acid, fluoric acid, fluorinated oxalic acid, fluorinated oxalic acid, digasification: and ^ metal salts (for example, zinc salts, nickel, salts, etc.) ; For salt ions: nitric acid, zinc nitrate, etc. Daconyl fe is the basic dye-promoting agent in the composition according to the invention and can be added to the concentrate before the feed solution. Subtractive amines can be added in any form (including any known source). The term "xylamine-promoting dye" is used herein to mean any compound, such as a light amine salt or complex, that is generally present in the group via dissociation via dissociation, and a relatively small amount of amine reduction is in equilibrium. The free hydroxylamine is consumed by the chemical reaction that produces the desired phosphate coating on the treated metal substrate t. Examples of suitable L-based amine-promoted swordfish include hydroxylamine scale salt, nitrate, or sulfate, Its w compound. More preferably, the source of the base amine is a stable form of μ base amine. As noted above, the metal surface treated according to the present invention includes an iron-based surface, a zinc-based surface, aluminum -Base surfaces and surfaces based on their individual alloys. These metal surfaces can be treated separately or in combination. When this treatment is applied to iron-based surfaces and words-based surfaces (for example) car bodies In the above process, some advantages of the present invention can be most prominently displayed. It is known that other steps can be performed before or after the improved phosphating step of the present invention. Therefore, it is advantageous to make other steps to inspect the portion to be coated. , Craftsmanship, or Other items are essentially free of greasy, dusty or other foreign materials. This is preferably accomplished by using suitable cleaning procedures and materials known to those skilled in the art. These include, for example, mild or intense cleaning Detergents, acidic cleaners, etc. This type of cleaner-generally after it, or ..., ^-This paper is in accordance with China National Standard (CNS) A4 specification (21〇X 297 public love) (Please read the note on the back first ? Matters then fill out this page)

H ϋ ϋ I H ϋ ϋ ^ 口 V · n I n! Ϋ n I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

V. Description of the invention (previously washed with water. Highly preferred as part of the cleaning step. After this item, use a conditioning step, or become this: use a titanium phosphate compound, and the known conditioning The representative solution of the solution is to be coated by the present invention, including the condensed acid salts. The coated article is washed with water and dried, and after the coating is formed, the air drying is preferably completed. The drying step can be carried out by a simple package [compressed air drying method. In the coating step ^; used at elevated temperature ^ T :, and sometimes also using up to 糸 to maintain the temperature at 46. It takes a long time to 5 Achieve uniform coating: degree. At lower temperature, change within one generation, depending on the coating temperature and processing time can be 30-1803. This = Ming is special and better. , Which violates the following steps: 1 ... " is used to limit the invention. (Please read the precautions on the back before filling out this page) 1 order -------- Intellectual Property Bureau Staff, Ministry of Economic Affairs Printed by Consumer Cooperatives

524884

Han shrinkage Example 1 In this example, '' is derived from the following substances. Namely, a substance H3PO4 (75% in water) was prepared from HN03 (42. Bailie). Hydroxylamine sulfate MnO ZnO Ni (N03) 2 (30% aqueous solution) H2SiF6 (25% in water) HF (70 % Stored in water) Total parts of water (by weight), 390 · 〇5.0 parts (by weight) 35.0 13 · 5 26. 〇75.0 80. 〇7. 0 368. 5 ~~ ^ 〇〇〇7 〇c Please read the notes on the back before filling out this page) Order ---------

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (At first, 331 parts of water were used to dissolve the other ingredients; then another 37.5 parts were finally added to prepare a concentrated solution containing a total of 1,000 parts.) Then the concentrated solution was diluted with water and An effective composition is obtained, which contains grams of concentrated composition per liter of the effective composition (this dilution is hereinafter referred to as "w / vn"), has a free acid (uFAn) value of 15 points, and an overall acid ("ΤΑΠ) value of 42 points. . The ratio of Mn to Ni ions is 1: 1, the ratio of Zn to Mn and Ni ions is 1: 1, and the ratio of Zn to phosphate ions is 对: ι3β7. 11-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 524884 A7 V. Description of the invention (Example 2 Concentration = In the example, the following substances are used to make injuries according to the amount of shirts H3P〇4 (75%) HN〇3 (42 ° Βί) sulfuric acid via amine substance MηΟ ZηΟ Ni (N03) 2 (30%) HF (70%) H2SiF6 (25%) water content (by weight) 390. 〇5. 0 35.0 parts (by weight 21. 5 26 · 0 120 · 0 7.0 80. 0 315. 5 (Please read the precautions on the back before filling this page)

n H ϋ n H ϋ ϋ 1: mouth, · ϋ ϋ 1 nn. ^ 1 I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and then dilute the concentrated solution with water to 6% w / v, with a FA value of 13. 5 points and a TA value of 40 points. The ratio of Mn to Ni ions is i: i, the ratio of Zn ions to the sum of Mn and Ni ions is 1: 1.6, and the ratio of Zn ions to phosphate ions is 1: 13 · 7. Example group 3 This example will be used to exemplify a coating method for phosphating treatment according to the present invention, which uses the spraying technique and the concentrated solution of Example 1. Dilute the concentrated solution with water to a concentration of 48 grams of concentrated solution per liter of coating solution. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 524884 A7 _B7_ V. Description of the invention () and NaOH Added to reduce the free acid concentration of the coating solution to 0.7 points and an overall acid value of 20. After the 4-inch by 6-inch metal plate is degreased and cleaned with a commercially available alkaline cleaner (P + A Parco ™ Cleaning Solution 1500C), it is washed with water, and the plate is suspended with a commercially available titanium salt. Solution (P + A Fixodine ™ Z8). The plate was then treated with the phosphate coating solution formed from the concentrate of Example 1 as described above. After the phosphating treatment, the plate was washed with water at a surrounding temperature with 30 seconds of water spray cleaning and then 30 seconds of deionized water spray cleaning and washing. The plate was then dried at ambient temperature with pressurized air. The results obtained at a temperature of 115 ° F and a spraying time of 120 seconds for the phosphate coating are shown in Table 1 below, in which several examples are applied to cold-rolled steel sheet (CRS) and hot-dip galvanized iron sheet HDG). (Please read the precautions on the back before filling out this page) Xia—1 — — — — — — Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 524884 A7 B7 V. Description of the invention () Sample coating weight (MG / FT2) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs CRS HDG A 168 189 B '150 180 C 159 180 D 120 153 E 120 147 F 156 159 G 120 138 Η 129 162 I 120 168 J 156 168 K 129 159 L 156 141 Μ 156 168 N 126 159 0 162 171 P 149 148 Q 121 156 R 117 153 S 121 151 T 136 156 U 120 145 Μ-(Please read first Note on the back then fill out this page) Order ---------

A This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 524884 A7 B7 V. Description of the invention () The coatings of i) are crystalline, open-flap or needle-shaped), and the size of M is 3-15 microns (for CRS) and 2-10 microns (for HDG). 1 Other examples were carried out at different spraying times and temperatures, and visual observations of the same coating ^ indicate that a sound coating can be obtained at least as low as 105 ° F, but at higher levels The temperature is better. 1 Example group 4 A series of 2036 and 5052 aluminum flat plates 4 inches wide and 6 inches long were treated in the same way as CRS and HDG as described in Example 3, except that potassium fluoride additives were used. (8.6% free F ions, and 8.99% κ ions) to achieve a free-state fluoride concentration of 500-600 ppm. A temperature range of 115-130 ° f is acceptable, while it takes 120 seconds at lower temperatures. These flats exhibit coating weights ranging from 122 to 173 mg / ft2 (for aluminum 2036 alloy) and 150 to 195 mg / ft2 (for aluminum 5052 alloy 5). For this alloy, the crystal size varies between 5 and 30 microns. Example Group 5 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs In this example, several different substrates were sprayed for 60 seconds in accordance with the private sequence of Example Group 3. In addition to Ming alloy and cold-rolled sheet steel (, '), the substrates of two different electroplated alloys ("EG ,,), and Ci-nickel alloy and ΔΟΓ' (which is a Ci-iron alloy) are also processed. The results are listed in the following Table 2. This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (21 × 297 mm) 524884 A7 V. Description of the invention (Table 2 Matrix CRS 127 90EG 180 NAT. 70/70 EG 280 Coating weight Crystal size Visual appearance Thermal bath temperature 01G / FT2) (microns) (〇F) ~ M2 ~ 2-8

Zn-Ni A01 164 183 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Good Good Good Good Good Good 120 120 120 2-8 3-10 3-10 5- 20 5-18 120 120 130 130 2036 Aluminum 5052 Aluminum 1. In this case, the concentrated solution of Example 2 is used to make the working solution, and it replaces the spray coating method in Example Group 3. The metal plate was immersed in the coating bath liquid, and it was made again by diluting the concentrated liquid to gram / liter (as performed in Example 3). The results of the treatment of various substrate plates (4 in. X 6 in ·) at a temperature of 2 minutes infiltration time m115cF are shown in Table 3 below, which also illustrates the analysis of the coating composition. Table 3 Matrix coating weight composition of the formed salt coatings,%: (MG / FT2) CRS EG HDG A1 2036 177 185.] 168. (168 · (179 195

Zn

Ni 27 1.3 37. 5 1. 3 37 1.8 29. 9 2.2

Mn17Ϊ 4.3 4.5 6.7 ^ 38 ~ 38 38.9 42. 5

Fe T5 0. 16 0. 14 0.32 ------- t -------- This paper size applies to China National Standard (CNS) A4 (21〇χ 297 mm) Bureau of Intellectual Property, Ministry of Economic Affairs Printed by Employee Consumer Cooperative 524884 A7 B7

5. Description of the invention () L In general, the crystal size of all the substrates in this group is 1-5 microns. As mentioned in Example Group 3, a temperature higher than 105 ° F (for example, 115. to 135 ° F) is preferred, and a time higher than 60 seconds (and most preferably higher than 80 seconds) is also preferred. In all cases, the presence of hydroxylamine sulfate did not change the morphology from needles or agglomerates, but still remained relevant to the coating method and substrate, as well as a quantity and other components in the coating solution (such as zinc and Phosphate ion) ratio in the presence of manganese, and the morphology related to the amount of hydroxylamine used. Therefore, the coating in the present invention is a flaky or agglomerated (the latter is a case of CRS infiltration coating) crystal structure, which Can provide excellent coating weight under low temperature coating by spray or wetting technology. Hydroxylamine dye accelerant can be added to the concentrate itself to avoid the need to formulate the coating solution from the concentrate later Add it. This coating solution does not require (and preferably does not contain) nitrite ions as dye accelerators, thereby reducing the harmful environmental impacts that are often associated with nitrites (or at least some consumers believe they are). And danger. 7 The best composition according to the present invention will generally provide a coating solution with the following ingredients (the contents of which are listed below) for spraying or soaking methods: n-This paper size applies to Chinese National Standard (CNS) A4 specifications ( 210 X 297 mm) (Please read the notes on the back before filling this page)

524884 A7 V. Description of the invention (Table 4 Ingredients Hydroxylamine sulfate Zinc ion Nickel ion Imon ion Phosphate ion Nitrate ion Complex image Free fluoride

WT 0. 168 0. 10 0. 05 0. 05 1. 37 0. 12 0. 074 0. 022 (Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs In the previous composition, the ratio of the sum of the zinc and phosphate pairs and nickel was. Such compositions can be full = with a desired coating weight 'not only in the mineral substrate' and high-quality examples formed on the substrate 8 In terms of practical coating operation examples, the coating solution It may be necessary to replenish to maintain the proper concentration of each of the coating money towels and maintain the acidity. The replenishment composition will contain various substances (when added to the coating solution) of different substances and ions that can effectively maintain the ions at the appropriate concentration for coating, and will normally contain their amounts (added in the replenishment solution) (To the coating solution) ammonium carbonate or ammonium bicarbonate which can effectively maintain the desired acidity of the coating solution, and ammonium hydroxide is preferred. -This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 524884 A7 V. Description of the invention () The better replenishing composition of the paint solution is actually wounded (the following are the following) Number by weight) / / Table 5 Ingredients WT% Water ^ 70: H3P〇4 (75%) 378. Sulfonyl sulfate 100. MnO 12. ZnO 68. Ni (1403) 2 solution (30%) 60 HF (70%) 2 · H2SiF6 (25%) 50. Hydroxide (26. BaumC) 58. 0 0 5 (Please read the note on the reverse side first, then fill in this page) Employees of Intellectual Property Bureau, Ministry of Economic Affairs Consumption Cooperative Printed Example Group 9 As indicated above, the preferred base amine for the composition according to the invention is HAS. The use of this substance results in the accumulation of sulfates in the coating composition, as it does not appear to be consumed by any of the reactions that are part of the coating conversion forming process. Therefore, experiments were performed to determine whether this accumulation would adversely affect the formation of the phosphate coating or its compliance value as a paint primer. The conversion type coating composition including a sulfate used has a composition shown in Table 6 below. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

I 1 * an n ϋ MBmMm n 0 0, _ n · ϋ n 11 n la — · ϋ I A- 524884 A7 B7 V. Description of the invention (Table 6 TAA ZN MN NI P04 N03 F S04 batch (PTS · (G / L) (G / L) (G / L) (G / L) (G / L) (G / L) (G / L) 1 23 · 0 1 · 0 0. 75 0 · 88 14. 6 2 9 1. 1 0.84 2 23. 0 1. 0 0 · 75 0 · 88 14. 7 2. 9 1. 1 3.2 3 23. 2 1. 0 0 · 74 0 · 89 14. 3 2. 8 1. 1 5.3 4 23. 5 1 '/ 〇0 · 73 0 · 88 14. 5 2. 8 1 · 1 9. 1 5 24. 0 1 · 0 0 · 73 0 · 87 13. 8 2 · 7 0 · 93 14.0 Note to Table 6 These batches have a free acid value between 0.6 and 0.7 points, a concentration between 0.15 and 175, and sulfuric acid via amine (please read the precautions on the back first) (Fill in this page again.) The production of the batches with the composition shown in Table 6 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs was prepared by using the same general method as in Examples 1 and 2 above. Concentrate, then dilute it and add the appropriate amount to provide the sulfates shown in Batches 2-5 (the sulfate content in Batch 1 is from the HAS used in the concentrate from which all batches were prepared) concentration The sodium sulfate was used to prepare a working coating composition, which was used in the same method as described in Example Group 6, and the conversion coating was formed by immersion at 11 ° F for 12G seconds instead of spray contact. To be converted as Lai, the conversion-coated sample was spray-washed with water to have a Qi value of 6.3 and contain 1% 仏 of 1 ^ (: 〇1Cazhu 8〇 (is a kind of commercially available from P + A After-treatment of the concentrated solution). The samples thus treated were washed in deionized water, and then dried in an oven at 225 ° F for 5 minutes. 、, 20-This paper size applies Chinese National Standard (CNS) A4 Specifications ⑵ G χ 297 male Eding 'pack -------- order ---

524884 A7 V. Description of the invention (These treatments produce uniform coatings on all substrates without being affected by sulfates / saturation. Observed on cold-rolled sheet steel, electro-galvanized, and hot-dip galvanized substrates, respectively. Available with coatings of 193 to 281 mg / ft2 (including 2 to 6 micron crystals), 2 to 262¾ g / ft2 (including 2 to 6 micron crystals), and 229 to mg (feet 2 (2 to 12 micron crystals)) The weight of the coating on the cold-rolled steel sheet decreases with the increase of the sulfate concentration, but it is equal to the coating weight on the electroplated zinc and hot-dip galvanized coating. After the first addition of sulfate, the weight of the coating decreases significantly, and thereafter Keep relatively constant. ^ Then the samples prepared as described above are coated with conventional commercially available paints or paint system coatings (PPG, ED-4 and general automotive base coating / clean coating systems), and The coated samples were subjected to conventional accelerated corrosion resistance tests (APGE (20 cycles), GM 9540P-B (40 cycles); Chrysler chipping (25 GM 9511 P cycles with short-range impact)); And six months of Florida exposure. All four accelerated tests are It is (statistically) that the effect of cold-rolled sheet steel does not deteriorate with the accumulation of sulfates (up to 14 g / l) in the linate conversion coating of the present invention. In fact, at higher sulfate concentrations ( More than 0.8 g / l), the effectiveness of cold rolled steel sheet at 9540 pb, Chrysler breakout day line), and Florida exposure test appears to be statistically lower than that of the control group (batch 1 in Table 6). The performance is good. The performance of the galvanized steel sheet may become worse as the sulfate concentration increases. The average slip observed across the day line in millimeters was observed for all two items under 14 g / l sulfur Ssc salt In terms of testing, it is usually larger than that performed under q 8 g / L sulfate. For the 9540P-B test system mm (please read the note on the back before filling out this page)

1 l_i Ι ϋ n * 1 n Van in 口 · 11 11 1 I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 21-524884 A7 B7 V. Description of the invention (for 0.9, for Chrysler chipping test system 2 test · The millimeter is 3.3. However, only for 14 grams; liquefaction = results in, significantly different from the control group 0.8 g / liter = Florida exposure_ The test implies that according to the sulfate in the hair is 5 Qingsheng, resulting in statistics; the effectiveness of Zhong Zinc, which is an average slip of 3. _.9 mm ^ Off: G · 3 or 1 ^ paint loss, 77 ^ and discontinuity concentration: academic (vision Depending on the accelerated test), the effectiveness of hot-dip ore zinc is improved, remains the same, or diminishes when sulfur is improved. Apge and Fro == indicates that the performance is reduced, 954㈣ indicates that the performance remains the same. ) The effectiveness of replenishing is enhanced. If the test is performed, Hot Dip Lin will suffer from Chrysler chipping test and will not lose more than 0.3% paint.

AfGE and the six-month Florida exposure test (which generally produces greater day-to-day slippage than the GM 9540P-B or Chrysler chipping tests) seem to emphasize that the sulfate concentration has any potential negative effects on the performance of hot-dip galvanized steel influences. According to the conclusion of this study, the high sulfate concentration of 14 g / l will not reduce the effectiveness of the conversion coating produced on the substrate of the cold rolled steel sheet according to the present invention. Sulfate concentrations of at least 6 g / l do not have a deleterious effect on the performance of galvanized steel. Sulfate concentration of 9 g / l or higher may hinder the performance produced on hot-dip galvanized steel and cause a small amount of slip measurement (please read the precautions on the back before filling this page)

., 22-524884 A7 B7 V. Description of the invention () The test results show that there is no decrease in performance due to the increase in sulfate concentration, and the test results that caused a large amount of slip indicate its performance degradation. The former tests may be more directly related to most practical use cases. (Please read the note on the back? Matters before filling out this page) Order ---------

Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 23-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

524882Γ Scope of application for patents The employee of the Intellectual Property Bureau of the Ministry of Economic Affairs, a cooperative prints a processing method for forming a crystalline coating on a metal surface, which is achieved by a processing method including the following steps: (a) apply The metal surface is in contact with an acid conversion coating solution containing phosphonium ions, ion ions, and hydroxylamine sulfate for a period of time sufficient to form a crystalline zinc linoleate conversion coating. (B) The coating solution is re-applied. Replenishing a replenishing composition containing hydroxylamine sulfate to form a replenishing coating solution; and (c) contacting the replenishing coating solution with a metal substrate and replenishing the coating solution until the sulfate present in the replenishing coating solution appears The concentration does not exceed 14 g / L; wherein the acidic aqueous solution essentially comprises water and: 0.8 to 1.2 g / L of zinc ions; 5 to 25 g / L of phosphate ions; 0.2 to 1.5 g / L of ions 0 · 2 to 1.5 g / L of nickel ions; 0.1 to 0.25% of the base (is an amine dye accelerator, which is determined by the stoichiometric equivalent of the base amine), the acidic aqueous solution is ： The weight ratio range of zinc ion to phosphate ion ranges from 1.0 to 1:25, and the weight ratio range of zinc to manganese and nickel total range is from 1.0 to 0.5 to 1.0: 2.5. The ratio of manganese to nickel ranges from 1. 〇 ·· 0.5 to 1. 0 ·· 1.5, and _______ large paper size is applicable to China National Standard (CNS) A4 specification (2) 0 χ 297 mm ) ------------ Installation -------- Order --------- (Please read the precautions on the back before filling this page) 524884 A8 B8 C8 D8 Six applications for patent scope string please amend the scope of patents-^ ηπ〇 / ^ / 1Π 2. 3. 4. 5. 6. The Intellectual Property Bureau of the Ministry of Economic Affairs employee consumer cooperative printed a free acidity of 0.3 to 1.0 points. According to the treatment method of the scope of application of patent No. 1, wherein the metal substrate is a cold rolled steel sheet. According to the processing method of the first patent application scope, wherein the metal base is hot-dip galvanized steel, and its contact with the resupply coating solution is from weight I to the sulfate concentration exhibited by the resupply coating solution does not exceed 9 g / l. ^ The treatment method according to item 1 of the scope of the patent application, wherein the metal substrate is electroplated steel, and its contact with the resupply coating solution is repeated until the sulfate concentration exhibited by the resupply coating solution does not exceed 6 g / l. until. The treatment method according to item 1 of the scope of patent application / Valley fluid has 21 points of sulfate ions not exceeding 6 g / liter, and the free acidity is 0.4 to 4 points. The treatment method according to item 5 of the patent application scope. The solution has a total acidity of 19 to 20 points and a free acidity of 0.05 to 0. A method as used in step (c) of the treatment method of item 1 of the patent application scope. The coating solution was replenished, wherein the sulfate solution presenting a sulphate> 14 ° C was 14 g / L. A method for replenishing coatings, such as used in step (c) of the treatment method item 1 in the scope of the patent application, is the valley solution, wherein the coating solution exhibits a sulfate concentration of 6 g / l after contact with electroplated zinc. Wherein the acidic water has a total acidity of 17 to which the acidic water -------------------- Order --------- (Please read the note on the back first Please fill in this page for more details) Towel Guan Family (cns) A4 Specification ⑵Qx 297 Male Stone-