KR101214812B1 - Multi-purpose conversion coating solution for metal surface treatment and method thereof - Google Patents

Abstract

The present invention is a surface treatment method for the unpainted surface, shorten 10 processes of zinc phosphate coating, which is a typical representative surface treatment method, to 5 processes or less, and in particular, as shown in the representative diagrams [2, 3, 4 degrees]. It is one of silicon, magnesium, vanadium, silver, zirconium, hafnium, and titanium in an alkaline solution mixed with a surfactant. Or surface treatment composition and anodizing film (anodizing) that provide a metal surface suitable for coating by treating the base metal with a solution containing silane coupling hydrolyzate and silicon compound that contains two or more metals and promotes adhesion between fluorine and silicon. The present invention relates to a surface treatment composition capable of sealing a surface thereof and a surface treatment method of a base metal using the same.

Description

Multipurpose coating composition for metal surface treatment and surface treatment method {MULTI-PURPOSE CONVERSION COATING SOLUTION FOR METAL SURFACE TREATMENT AND METHOD THEREOF}

The present invention relates to a surface treatment composition and a surface treatment method for providing a metal surface for coating and sealing an anodized surface.

More specifically, one or two or more metal salts, silane hydrolysates, fluorine of silicon, silver, magnesium, vanadium, zirconium, titanium, and hafnium in a solution containing sodium hydroxide or potassium hydroxide solution or two mixed solutions and a surfactant The surface treatment composition and anodizing (anodizing) which can provide the proper metal surface for coating by simultaneously degreasing or coating by depositing or spraying a base metal with a solution of a certain condition with a mixed solution is sealed. It relates to a surface treatment composition that can be treated and a surface treatment method of a base metal using the same.

A typical pretreatment method for the conventional metal surface treatment for unpainted coating is a zinc phosphate coating process, which is divided into ten processes such as degreasing, washing with water, surface adjustment, chemical coating, and washing with water to treat base metals.

Such zinc phosphate coating is widely known as parkerizing and is prepared by dissolving zinc, nickel and manganese in phosphoric acid, nitric acid and fluorine compounds. Conventional surface treatment solution is coated with zinc phosphate coating on the metal surface through alkaline degreasing and washing, surface adjustment and acidic coating and washing and purifying process to provide proper metal surface for painting. It is formed and provided to the painting process.

In the details of the zinc phosphate coating process, FIG. 1 shows ten consecutive processes for zinc phosphate coating. First, hot water (1) is performed with hot water of about 40-50 ° C. to increase the temperature of the base metal to make it easy to degrease the oil and various foreign substances on the metal surface. Degreasing steps (2, 3) to remove the oil on the metal surface using a degreasing agent are carried out twice at 45 to 50 ° C. By washing the alkaline residues cleanly through two washing processes (4, 5) at room temperature, and performing the surface adjustment process (6) at room temperature to form an active point on the metal surface so that fine crystals of zinc phosphate coating can be formed. Complete the pretreatment for zinc phosphate coating. Thereafter, the solution is treated once with a zinc phosphate coating solution (7) maintaining a temperature of 45 to 50 ° C, and washed with water (8) and pure water (9, 10) to remove acidic coating solution and residual ions remaining on the metal surface. In order to provide a coating process with zinc phosphate crystal coating which the base metal can improve the corrosion resistance and paint adhesion.

The conventional zinc phosphate surface treatment process requires the following environmental problems and process operational improvements.

That is, the conventional zinc phosphate coating process (7) requires several washings (8, 9, 10) to remove the strongly acidic coating solution remaining on the base metal surface, and the phosphoric acid contained in the washed solution. Causes eutrophication of rivers and rivers. In addition, manganese and zinc as heavy metals and nickel as toxic substances continuously generate large amounts of heavy metal sludge in the process, causing environmental problems.

In addition, the inorganic accelerators (NaNO2, NaClO3, etc.) used during the process are decomposed in the zinc phosphate coating process, which is an acidic solution, to generate corrosive gas, and cause fine rust on the metal surface in contact with it. The controlling and removing system must be operational.

Recently, the use of nonferrous metals is increasing in the automobile and home appliance fields to improve durability and light weight of products. Accordingly, in the existing zinc phosphate coating, various materials such as zinc plating, zinc alloy, zinc iron alloy, aluminum alloy, and magnesium are being worked in one pretreatment process. However, non-ferrous metal ions etched in the coating solution, in particular aluminum ions accumulated during operation, accelerate the aging rate of the surface treatment solution and prevent the formation of zinc phosphate coating of appropriate quality in the iron material. Therefore, in order to control this, a certain amount of fluorine is added to the surface treatment solution in order to partially work, but a large amount of nonferrous metal cannot be continuously operated, and efforts to improve it have been continued.

Due to this problem, a separate chromate treatment process is applied to secure corrosion resistance of certain materials such as aluminum alloy and zinc alloy. Chromate treatment is a method of coating a rust-preventive coating by dipping nonferrous metal materials in a solution mainly containing chromic acid or dichromate, and the trivalent and hexavalent chromium used here have the limitation that they are subject to environmental regulation. I rarely use it.

As described above, the conventional surface treatment process operation exposes workers to harmful heavy metals, and the generated wastewater contains substances that cause rivers and environmental pollution, thereby simplifying the application of new surface treatment compositions and streamlining the treatment process. Needed.

In order to solve this problem, the multi-purpose coating solution composition for treating the metal surface of the present invention is an environment-friendly metal salt having high corrosion resistance and heat resistance such as silicon, silver, magnesium, vanadium, zirconium, titanium, hafnium, and sodium hydroxide or potassium hydroxide or a mixture of two. Dissolve and alkalize with a mixture of surfactants in the solution, so that the temperature, pH, and concentration (metal content) of the solution are adjusted under certain conditions. Precipitation on the surface takes place simultaneously. That is, the surface of the base metal is attached with various contaminants (processing, metal powder, etc.) during the process of pressing, cutting, etc., and it is calcified by saponification reaction with alkaline solution, and emulsified and dispersed. Of contaminants, etc. are removed, and at the same time, the local metal ion surface index (pH) of the contact interface is increased by etching with fluorine in the material metal surface, so that one or two or more of the environmentally friendly metals are removed. A coating material of an insoluble compound in the form of a fluorine compound, a hydroxide, or an oxide is formed and precipitated on the metal surface, and the precipitate is a chemical which improves adhesion and corrosion resistance by silane coupling hydrolyzate, and the metal composition in the solution precipitates on the surface of the steel sheet. The reaction is thought to be as follows.

o. In alkaline solution

H ₂ SiF ₆ + ₂ NaOH → Na ₂ SiF ₆ + H ₂ O

Na ₂ SiF ₆ + 4 NaOH → 6NaF + SiO ₂ + 2H ₂ O

H ₂ ZrF ₆ + ₂ NaOH → Na ₂ ZrF ₆ + H ₂ O

Na ₂ ZrF ₆ + 4 NaOH → 6NaF + ZrO ₂ + 2H ₂ O

o. In acidic solution

_{H 2 ZrF 6 + M + H} 2 O → ZrO 2 + M ++ + 6F - + H 2 ↑

The metal salt coating as described above may be deposited and adhered to the metal surface of the metal in the form of a fine thin film, and a small amount of cationic metal, metal salt, and organic metal salt may be additionally used as a reaction accelerator to increase the coating weight depending on the intended use.

The composition of the solution of the present invention increases not only the metal surface treatment agent in the pretreatment process for unpainting, but also the treatment time of the invention solution when used as a sealing agent for preventing surface corrosion and preventing contamination after anodizing of aluminum (increasing the film weight). ) Equivalent results could be obtained compared to conventional sealants.

The typical sealing mechanism of the anodized film is made of nickel, cobalt, cadmium, etc. in an aqueous metal salt solution with appropriate conditions, and when anodized aluminum is deposited, the metal salt in the aqueous solution enters the micropores of the anodized film and precipitates (precipitates). Sealing method, pressurized steam method is excellent in corrosion resistance, but it is not possible to use large building materials or continuous processing process because high pressure sealed cylinder is required. Boiling water treatment method is cheaper in processing cost and can be processed continuously but corrosion resistance weak.

Currently, the sealant generally used in Korea contains nickel, which is harmful to human body, and thus has a disadvantage that cannot be used in tableware-related products.

Conventional painting equipment pretreatment line has excessive initial capital investment cost and the number of processes is complicated, so the operation of the line is complicated. In order to protect workers and workplaces from such harmful environment, additional facilities should be operated.

The present invention provides an environmentally friendly surface treatment composition and its surface treatment method capable of shortening the pretreatment process by simultaneously degreasing and coating the contaminated coatings in the same solution as a method for improving the problems of the pretreatment process. In addition, the sealing treatment of the anodized film does not use a metal, such as nickel, which is harmful to the existing human body, it is intended to apply the surface treatment composition having the same performance as the existing product in the industrial field.

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The surface treatment composition of the present invention for solving the above problems is a surface treatment solution for the uncoated paint containing a surfactant so that the degreasing and coating can be made at the same time, sodium hydroxide or potassium hydroxide solution or a mixture of two solutions are formed in an appropriate ratio Excellent corrosion resistance on the surface of metals with a composition containing surfactants to increase the degreasing power in the alkaline solution and at least one metal salt selected from silicon, silver, magnesium, vanadium, zirconium, titanium and hafnium and silane coupling hydrolyzate A mixed composition in which fluorine and a silicon compound are appropriately reacted to form an insoluble metal salt having adhesion, and is used by diluting it in water at a predetermined ratio.
In the surface treatment method according to the present invention, the solution temperature of the composition is 20 ~ 70 ℃, the hydrogen ion concentration index (pH) 4 ~ 13.5, can be used in the treatment time 5 ~ 1,000 seconds, the degree of contamination of the metal surface and the base metal According to the characteristics and condition of the acid solution to the alkaline solution using both ranges are configured to enable the surface treatment for painting.

In addition, in case of aluminum anodized film, sealing effect was achieved when the solution temperature was 20 ~ 70 ℃, hydrogen ion concentration index (pH) 4 ~ 13.5, and the treatment time was 10 ~ 30 minutes. Although it is effective, it has a disadvantage of longer processing time (more than 30 minutes), and high solution temperature shortens sealing time (less than 10 minutes), but excessive etching of aluminum surface occurs. Conditions must be selected.

When using the metal surface treatment composition for the uncoated coating according to the invention compared with the process using a conventional zinc phosphate coating agent,
Conventionally, hot water washing (1), degreasing (2), degreasing (3), washing (4), washing (5), surface adjustment (6), coating (7), washing (8), pure water (9) and pure water In the case of using the composition of the present invention, the degreasing and coating process are performed simultaneously when the composition of the present invention is used. And since the process such as the pure tax (10) can be shortened the pretreatment process is less expensive than the existing pretreatment line, do not use heavy metal harmful to the human body, hardly generated heavy metal sludge. These advantages are significant energy savings and can reduce CO2 emissions.

In addition, since it does not generate harmful gases such as nitrous acid gas generated in the existing zinc phosphate coating process, it is not only environmentally friendly, but also there is no fear of rust on the surface of the base metal due to harmful oxidizing gas, thereby obtaining an excellent film. The treated metal surface can secure excellent corrosion resistance and adhesion after painting without a separate post processing or chrome sealing process.

When used as a surface sealant after aluminum anodization, if the pH of the composition is properly adjusted and the treatment time is increased, it can be used as a surface sealant after anodization without using nickel metal, which is harmful to a conventional human body.

1 is a schematic view showing a conventional zinc phosphate surface treatment process.
2 is a schematic view showing a metal surface treatment process according to the present invention.
3 is a schematic view showing a metal surface treatment process application according to the present invention.
Figure 4 is a schematic diagram showing a shortened metal surface treatment process according to the present invention.
5 is a SEM (× 1000 times) photographed picture of a general cold rolled steel (SPCC).
Figure 6 is a SEM (× 1000 times) photographed after the zinc phosphate coating on a cold rolled steel (SPCC).
7 is a SEM (× 1000 times) photographed after the invention solution treatment on a cold rolled steel (SPCC).
8 is a SEM (× 1000 times) photograph of an aluminum (AL) steel sheet.
Figure 9 is a SEM (x 1000 times) photographed after the zinc phosphate coating treatment on an aluminum (AL) steel sheet.
10 is a SEM (× 1000 times) photographed after the invention solution treatment on an aluminum (AL) steel sheet.
FIG. 11 is a SEM (× 1000 times) photograph of a galvanized zinc steel (GA). FIG.
12 is a SEM (× 1000 times) photograph taken after zinc phosphate coating treatment on an alloyed zinc steel sheet (GA).
Figure 13 is a SEM (x 1000 times) photographed after the invention solution treatment on an alloyed zinc steel sheet (GA).
Figure 14 is a SEM (x 1000 times) photographed after the nickel sealant treatment on an aluminum (AL) steel sheet.
Fig. 15 is a SEM (× 1000 times) photographed after sealing of the present invention on an aluminum (AL) steel sheet.

Hereinafter, with reference to the accompanying drawings will be described in detail the specific technical configuration of the present invention.

The coating surface treatment composition of the present invention is a mixed solution of alkali metal salt and acid metal salt, which removes the processing oil and rust preventive oil applied to the metal surface and removes and separates the surfactant mixture which is an auxiliary agent, and the fluorine and precipitated insoluble substance. A composition consisting of a silane coupling hydrolyzate and a metal compound having good heat resistance and corrosion resistance, which is used to dilute it with a certain ratio of pure water, and the proper use range of the treatment solution is hydrogen ion concentration index (pH). ) 4 ~ 13.5, solution temperature 20 ~ 70 ℃, treatment time 5-1,000 sec.

The composition of the present invention is applicable to various kinds of metal products such as cold rolled steel (SPCC), alloyed zinc steel (GA), aluminum (AL) or aluminum alloy, die castings, anodized film sealing, casting products, etc. Hydrogen Ion Concentration Index (pH) 4 to 13.5 and 0.001 to 150 g / L surfactant mixture of a composition containing sodium hydroxide or potassium hydroxide or a mixed solution of sodium hydroxide and potassium hydroxide, silicon, magnesium, vanadium, silver, zirconium, titanium, It is prepared from a composition containing 10 to 10,000 ppm of the metal content of any one of the hafnium metals, or the sum of the total amounts of two or more metals is 10 to 10,000 ppm.

The alkali metal salt source is not particularly limited, but an alkali metal or an alkaline earth metal of the periodic table of the elements is representative of sodium hydroxide or potassium hydroxide.

Surfactants as degreasing aids include anionic, cationic, or non-ionic surfactants. Anions that are subject to environmental regulation are excluded and nonionics are used. The source of the nonionic surfactant is not particularly limited, but contaminants on the surface of the metal may be easily dispersed in the alkali metal salt solution after the saponification reaction, emulsification, and calcification. It should be selected and formulated so as not to cause break phenomena.

The hydrolyzate of the silane is not particularly limited, but a metal salt deposited on the surface of the steel sheet without being precipitated or decomposed in an alkaline or acidic solution should be selected and manufactured to increase adhesion with paint.

The surface treatment solution may be used in the metal content of silicon, magnesium, silver, vanadium, zirconium, titanium, hafnium up to 10ppm-10,000ppm, the source is not particularly limited, but inorganic salts such as carbonate, fluorine salt, ammonium salt, nitrate, etc. Or a mixture or compound of organic salts. The reason why the metal is used as a main component of the film is that the metal can be selectively used for excellent corrosion resistance, abrasion resistance and heat resistance, and is environmentally friendly compared to conventional surface treatment solutions containing harmful heavy metals (chromium, nickel, etc.). It is because it is a phosphorus metal.

Fluorine, which is used as an etchant on the base metal surface, dissolves the base metal surface and makes direct contact with the surface treatment solution composition. At this time, the base metal surface contact surface has a local hydrogen ion index (pH), so that the metal salt is insoluble fluorine compound or hydroxide. , To be precipitated in oxide form. Although the supply source of fluorine is not specifically limited, Metal salt, ammonium salt, hydrofluoric acid, etc. can be mixed and used suitably.

The surface treatment method using the above-described invention solution composition will be described in more detail.

As shown in FIG. 2, the pretreatment process for painting is composed of five processes, namely, hot water (once) → inventions (2, 3) → pure water (4, 5). Compared with the conventional zinc phosphate coating treatment shown in FIG. 1 consisting of 10 steps, the number of steps is greatly reduced. According to the pretreatment method of the present invention, it is possible to omit from the surface adjustment process 6 to the pure water washing step 10 in the pretreatment chemical conversion process shown in FIG. 1.

First, it is preferable to perform the composition of this invention within the temperature range of 20-70 degreeC. In order to provide a metal surface suitable for the painting process, the lower the composition solution temperature is, the longer the treatment time is, and the surface of the steel sheet is stained. On the contrary, the higher the solution temperature is, the shorter the treatment time is. Since the solution becomes unstable due to excessive etching on the surface and water evaporation in the solution, an appropriate operating temperature should be selected. Steel plate without surface of base metal contaminated with rust preventive oil can be processed from room temperature (20 ℃) to high temperature (70 ℃), but steel plate with surface of base metal contaminated with rust preventive oil can be quenched by alkali mixture in invention solution within a certain time. Appropriate temperature is required to be removed, and preferred treatment temperature is 50-55 ° C.
The metal content of silicon, silver, magnesium, vanadium, zirconium, titanium, and hafnium, which is a metal which improves the corrosion resistance and adhesion of the coating material in the solution composition of the invention, can be used from 10 to 10,000ppm, but if the metal content is less than 10ppm, Productivity decreases due to metal salt precipitation time taken for a long time on the surface of steel plate, metal salt precipitation time is shortened if metal content is more than 10,000ppm, but aging of solution is accelerated and composition solution loss is increased due to process loss of process in the production line. As a result, the proper metal content in the composition solution is appropriately 400 to 2500 ppm.

It is preferable to adjust and use the hydrogen ion concentration index (pH) within the range of 4 to 13.5 when surface treatment of the base metal. In detail, it is used at the hydrogen ion concentration index (pH) 4 to 13.5 when there is no contamination on the surface of the base metal. When the surface of the base metal to be treated has oil or other contaminants such as processed oil, the hydrogen ion concentration index (pH) is preferably in the range of 12 to 13.5, and the hydrogen ion concentration index (pH) is higher than 13.5. Higher surface etching is rapidly increased and dissolved metal ions (nonferrous metals) accelerate the rate of aging of the solution, thereby increasing the consumption of chemicals. The hydrogen ion index (pH) can be adjusted by using an inorganic acid, an organic acid and its salt, and used to adjust the hydrogen ion index (pH) when preparing the initial solution composition.

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The surface treatment time is preferably 5-1,000 seconds. If the treatment time is less than 5 seconds, the reactivity on the surface of the base metal is inferior, the adhesion of metal salt does not occur sufficiently, and the normal surface is not degreased, and the metal surface becomes rough and stains occur. If the treatment time is treated for more than 1,000 seconds, the increase of ions in the solution and the speed of aging increase. Considering this point, it is appropriate that the treatment time of the invention solution is 200 to 300 seconds for the steel plate coated with rust preventive oil, and 40 to 240 seconds for the steel plate whose surface is not contaminated with rust preventive oil.

Since the working conditions (temperature, hydrogen ion concentration index, treatment time, metal content) of the four surface treatment processes described above affect the film quality and characteristics, the working solution should always be adjusted to the appropriate conditions. In consideration of various evaluation test procedures such as embodiments of the present invention, the optimum treatment conditions for the surface treatment solution are the most suitable for the steel plate contaminated with the rust-prevented oil, the treatment temperature of 40 to 50 ° C., the pH of 12 to 13.5, and the treatment time of 3 to 5 minutes. The uncontaminated steel sheet was treated with a treatment temperature of 30-50 ℃, a pH of 4-13.5, and a treatment time of 40-240 seconds.

Inventive solution treatment for sealing after aluminum anodization was good at surface pH of 20% and treatment time of 20 min, temperature below 20 ℃ At the treatment time of 30 minutes or more and the temperature of 40-70 degreeC, the sealing effect was favorable but surface gloss fell. The sealing time and gloss were affected by treatment time, temperature, and pH of the treatment solution. The treatment conditions were most appropriate when the treatment conditions were pH5-9, 25 ℃ and 20 minutes.

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The SEM (x1000) photograph of Figs. 7, 10 or 13 and the SEM (x1000) photograph of the aluminum anodized film and the sealing process after the zinc phosphate coating and the surface treatment of the present invention after the surface treatment of the present invention are shown in Figs. See for more information.

5 to 13 are SEM (× 1000 times) photographs taken before and after the surface treatment of zinc phosphate coating and invention on general cold rolled steel (SPCC), fused alloyed zinc steel (GA), and aluminum steel (AL). .

In FIG. 6, the zinc phosphate coating crystal has a micro size meta (μm) unit size, so that many pores exist between the crystals. Same (see FIG. 5).

For the metal surface treatment solution composition and the surface treatment method of the present invention described above, the following tests were carried out to find the effect of the metal surface treatment for uncoated coating and the sealing after anodization.

{Comparative example: for not painting}

The following test used a conventional zinc phosphate coating as a comparative example with the inventive solution.

First, as a comparative example of the present invention, three types of representative steel sheets used in coating lines such as general cold rolled steel sheet (SPCC), alloyed zinc steel sheet (GA), and aluminum steel sheet (AL) were selected, and the corresponding specimens were used as shown in Table 1 below. Anodized according to the zinc phosphate coating standard process of automobile coating line.

The quality level and evaluation of each coating specimen were applied to the following test items and methods and quality evaluation criteria.

1. Apply paint

. Electrodeposition paint: Black electrodeposition paint (NV 18%) used in domestic automotive parts coating line was used.

2. Conventional Surface Treatment Agents: Comparative Examples

.Use of zinc phosphate coating products used in pretreatment process of domestic automobile coating line

3. Test condition of invention solution: Application of Examples

. {Table 3} Process according to the invention solution surface treatment process

. Invented the surface treatment solution 3,000ppm rust preventive oil to make the solution most similar to the working conditions of the degreasing process in the surface treatment process used in industrial sites to process the specimen.

4. Applied antirust oil: Bumwoo Chemical's water-insoluble antirust oil P-DBH (A)

. Anticorrosive oil coating amount of each test steel: 2.0 ± 0.2gr / m ²

. Coating method: After degreasing and drying the solvent, the specimen was cooled to room temperature, immersed in an antirust oil solution for 10 seconds, left at room temperature for 4 days, and prepared as a test steel sheet.

5. Test method

The specimen size of AL, SPCC, and GA used in this test was 150 × 75 × 0.8 (mm), and the zinc phosphate coating chemicals in the pretreatment process used in the test of the comparative example were used in the domestic automobile line. Specimens were processed according to the TSDS.

6. Sludge visual observation

For comparative comparison with the comparative examples and examples, sludge generation was compared after 10 specimen treatments per 1 L of test solution.

{Table 1} Zinc Phosphate Coating Process

{Comparative Example: Anodized Sealing}

Nickel-type sealant, which is typically used in the domestic industry, was treated according to the process as shown in Table 2 and used as a comparative example.

. Nickel type: 0.3% dry bath, 25 ℃, 20 minutes treatment

{Table 2} Anodizing and Sealing Process

Example 1 for painting

In the same manner as the comparative example, the solution of the present invention was subjected to the surface treatment according to the process shown in Table 3 for three specimens, such as general cold rolled steel (SPCC), alloyed zinc steel (GA), and aluminum steel (AL). The relevant standards, test items and methods were applied in the same way as the comparative example.

EXAMPLES Before each test, the specimens were cleaned and dried with organic solvents in the same manner as in Comparative Examples, and then dipped in Bumwoo Chemical's water-insoluble rust preventive oil P-DBH (A) for 10 seconds, taken out, and left to stand at room temperature for 4 days. It was used as a test steel sheet.

In addition, 0.3% (3,000ppm) of non-aqueous rust-prevented oil P-DBH (A) of Bumwoo Chemical was added to the surface treatment solution of the present invention before each test specimen treatment, and stirred at 50 to 55 ° C for 10 minutes to use as an example test solution.

{Table 3} Invention solution surface treatment process

The surface treatment solution in which 3,000 ppm of rust-preventive oil was added was 240 seconds using the surface treatment process of {Table 3} the invention while maintaining an alkali solution containing fluorine, a surfactant, a silane hydrolyzate, a silicon metal content of 1,000 ppm and a titanium metal content of 350 ppm at 50 ° C. Specimens were deposited during the process.

Example 2

The specimens were treated in the same manner as in Example 1 except that the silicon metal content was changed to 350 ppm and the titanium metal content was changed to 1,000 ppm.

Example 3

The specimens were treated in the same manner as in Example 2 except that the silicon metal content was changed to 350 ppm and the titanium metal content was changed to 50 ppm.

Example 4

The specimens were treated in the same manner as in Example 1 except that the potassium alkaline solution of Example 1 was changed to sodium alkaline solution.

Example 5

The specimens were treated in the same manner as in Example 1, except that the potassium alkali solution of Example 1 was changed to a ratio of metal potassium content and metal sodium content by 1: 1.

Example 6

The specimens were treated in the same manner as in Example 1, except that the potassium alkali solution of Example 1 was changed to a 2: 1 ratio of metal potassium content and metal sodium content.

Example 7

The specimen was treated in the same manner as in Example 1 except that the time was changed to 60 seconds.

Example 8

The specimen was treated in the same manner as in Example 1 except that the time was changed to 120 seconds.

Example 9

The specimen was treated in the same manner as in Example 2 except that the time was changed to 60 seconds.

Example 10

The specimen was treated in the same manner as in Example 2 except that the time was changed to 120 seconds.

Example 11

The specimen was treated in the same manner as in Example 3 except that the time was changed to 60 seconds.

Example 12

The specimen was treated in the same manner as in Example 3 except that the time was changed to 120 seconds.

Example 13

The specimen was treated in the same manner as in Example 4 except that the time was changed to 60 seconds.

Example 14

The specimen was treated in the same manner as in Example 4 except that the time was changed to 120 seconds.

Example 15

The specimen was treated in the same manner as in Example 1 except that the temperature was changed to 30 ° C.

Example 16

The specimens were treated in the same manner as in Example 2 except that the temperature was changed to 30 ° C.

Example 17

The specimens were treated in the same manner as in Example 3 except that the temperature was changed to 30 ° C.

Example 18

The specimens were treated in the same manner as in Example 4 except that the temperature was changed to 30 ° C.

Example 19

The specimens were treated in the same manner as in Example 5 except that the temperature was changed to 30 ° C.

Example 20

The specimens were treated in the same manner as in Example 1 except that the temperature was changed to 40 ° C.

Example 21

The specimen was treated in the same manner as in Example 2 except that the temperature was changed to 40 ° C.

Example 22

The specimens were treated in the same manner as in Example 3 except that the temperature was changed to 40 ° C.

Example 23

The specimens were treated in the same manner as in Example 4 except that the temperature was changed to 40 ° C.

Example 24

The specimen was treated in the same manner as in Example 1 except that the pH was changed to 9.

Example 25

The specimen was treated in the same manner as in Example 2 except that the pH was changed to 9.

Example 26

The specimen was treated in the same manner as in Example 3 except that the pH was changed to 9.

Example 27

The specimens were treated in the same manner as in Example 4 except that the pH was changed to 9.

Example 28

The specimen was treated in the same manner as in Example 5 except that the pH was changed to 9.

Example 29

The specimen was treated in the same manner as in Example 6 except that the pH was changed to 9.

Example 30

The specimen was treated in the same manner as in Example 1 except that the pH was changed to 12.

Example 31

The specimen was treated in the same manner as in Example 2 except that the pH was changed to 12.

Example 32

The specimens were treated in the same manner as in Example 3 except that the pH was changed to 12.

Example 33

The specimen was treated in the same manner as in Example 4 except that the pH was changed to 12.

Example 34

The specimen was treated in the same manner as in Example 5 except that the pH was changed to 12.

Example 35

The specimens were treated in the same manner as in Example 6 except that the pH was changed to 12.

Example 36

The specimens were treated in the same manner as in Example 1 except that the pH was changed to 4 without applying or adding antirust oil to the test specimens and the inventive solution.

Example 37

The specimens were treated in the same manner as in Example 2 except that the pH was changed to 4 without applying or adding antirust oil to the test specimen and the inventive solution.

Example 38

The specimens were treated in the same manner as in Example 3 except that the pH was changed to 4 without applying or adding antirust oil to the test specimens and the inventive solution.

Example 39

The specimens were treated in the same manner as in Example 4 except that the pH was changed to 4 without applying or adding antirust oil to the test specimens and the inventive solution.

Example 40

The specimens were treated in the same manner as in Example 5 except that the pH was changed to 4 without applying or adding antirust oil to the test specimens and the inventive solution.

Example 41

The specimens were treated in the same manner as in Example 6 except that the pH was changed to 4 without applying or adding antirust oil to the test specimens and the inventive solution.

Example 42

The specimens were surface treated in the same manner as in Example 1 except that the zirconium metal content was 300 ppm, the silicon metal content was 1,000 ppm, the titanium metal content was 150 ppm, and the treatment time was changed to 120 seconds.

Example 43

The specimens were treated in the same manner as in Example 1 except that the zirconium content was 100 ppm, the silicon metal content was 500 ppm, the titanium metal content was 150 ppm, and the treatment time was 120 seconds.

Example 44

The specimen was treated in the same manner as in Example 1 except that the content of zirconium was 50 ppm, the silicon metal content was 350 ppm, the titanium metal content was 50 ppm, and the treatment time was 120 seconds.

Example 45

The specimen was treated in the same manner as in Example 36 except that the time was changed to 180 seconds.

Example 46

The specimen was treated in the same manner as in Example 36 except that the time was changed to 120 seconds.

Example 47

The specimen was treated in the same manner as in Example 36 except that the time was changed to 90 seconds.

Example 48

The specimen was treated in the same manner as in Example 36 except that the time was changed to 60 seconds.

Example 49

The specimen was treated in the same manner as in Example 36 except that the time was changed to 40 seconds.

Example 50

The specimen was treated in the same manner as in Example 37 except that the time was changed to 60 seconds.

Example 51

The specimen was treated in the same manner as in Example 37 except that the time was changed to 120 seconds.

Example 52

The specimen was treated in the same manner as in Example 38 except that the time was changed to 60 seconds.

Example 53

The specimen was treated in the same manner as in Example 38 except that the time was changed to 120 seconds.

Example 54

The specimen was treated in the same manner as in Example 39 except that the time was changed to 60 seconds.

Example 55

The specimen was treated in the same manner as in Example 39 except that the time was changed to 120 seconds.

Example 56

The specimen was treated in the same manner as in Example 40 except that the time was changed to 120 seconds.

Example 57

The specimen was treated in the same manner as in Example 36 except that the temperature was changed to 30 ° C. and the treatment time was changed to 120 seconds.

Example 58

The specimen was treated in the same manner as in Example 37 except that the treatment temperature was changed to 30 ° C. and the treatment time was changed to 120 seconds.

Example 59

The specimen was treated in the same manner as in Example 38 except that the temperature was changed to 30 ° C. and the treatment time was changed to 120 seconds.

Example 60

The specimen was treated in the same manner as in Example 36 except that the temperature was changed to 40 ° C. and the treatment time was changed to 120 seconds.

Example 61

The specimen was treated in the same manner as in Example 37 except that the temperature was changed to 40 ° C. and the treatment time was changed to 120 seconds.

Example 62

The specimen was treated in the same manner as in Example 38 except that the temperature was changed to 40 ° C. and the treatment time was changed to 120 seconds.

Example 63

The specimen was treated in the same manner as in Example 39 except that the temperature was changed to 40 ° C. and the treatment time was changed to 120 seconds.

Example 64

The specimens were treated in the same manner as in Example 36 except that the pH was changed to 9 and the treatment time was changed to 120 seconds.

Example 65

The specimen was treated in the same manner as in Example 37 except that the pH was changed to 9 and the treatment time was changed to 120 seconds.

Example 66

The specimen was treated in the same manner as in Example 38 except that the pH was changed to 9 and the treatment time was changed to 120 seconds.

Example 67

The specimen was treated in the same manner as in Example 39 except that the pH was changed to 9 and the treatment time was changed to 120 seconds.

Example 68

The specimens were treated in the same manner as in Example 40 except that the pH was changed to 9 and the treatment time was changed to 120 seconds.

Example 69

The specimen was treated in the same manner as in Example 41 except that the pH was changed to 9 and the treatment time was changed to 120 seconds.

Example 70

The specimens were treated in the same manner as in Example 36 except that the pH was changed to 12 and the treatment time was changed to 120 seconds.

Example 71

The specimen was treated in the same manner as in Example 37 except that the pH was changed to 12 and the treatment time was changed to 120 seconds.

Example 72

The specimens were treated in the same manner as in Example 38 except that the pH was changed to 12 and the treatment time was changed to 120 seconds.

Example 73

The specimens were treated in the same manner as in Example 39 except that the pH was changed to 12 and the treatment time was changed to 120 seconds.

Example 74

The specimen was treated in the same manner as in Example 40 except that the pH was changed to 12 and the treatment time was changed to 120 seconds.

Example 75

The specimen was treated in the same manner as in Example 41 except that the pH was changed to 12 and the treatment time was changed to 120 seconds.

Example 76

The specimen was treated in the same manner as in Example 1 except that no silane hydrolyzate was added.

Example 77

Specimens were treated in the same manner as in Example 1 except that no fluorine compound was added.

Example 78

Specimens were treated in the same manner as in Example 1 except that potassium and sodium metal were not added.

Example 79

The specimen was treated in the same manner as in Example 1 except that no surfactant was added.

Example 80

The specimen was treated in the same manner as in Example 1 except that the vanadium metal content was changed to 1,500 ppm and the titanium metal content was 500 ppm.

[Anodized and Sealed Nickel Type]

Comparative Example 81

0.3% of nickel-type sealant was dissolved in pure water, and treated according to “Table 2] Anodizing Film and Sealing Process”, and used as a comparative example.

Example 82 Invention Solution Composition

The specimen was surface-treated in the same manner as in Example 1 except that the specimen treatment time was changed to 20 minutes and the temperature was 25 ° C. without applying or adding antirust oil to the test specimen and the inventive solution.

Example 83

The specimen was surface-treated in the same manner as in Example 2 except that the specimen treatment time was changed to 20 minutes and the temperature was changed to 25 ° C. without applying or adding antirust oil to the test specimen and the inventive solution.

Example 84

The same treatment as in Example 82 was carried out except that the pH was changed to 11.

Example 85

The specimen was treated in the same manner as in Example 82 except that the pH was changed to 9.

Example 86

The specimen was treated in the same manner as in Example 82 except that the pH was changed to 7.

Example 87

The specimen was treated in the same manner as in Example 82 except that the pH was changed to 5.

Example 88

The specimen was treated in the same manner as in Example 82 except that the pH was changed to 4.

Example 89

The specimen was treated in the same manner as in Example 83 except that the pH was changed to 11.

Example 90

The specimen was treated in the same manner as in Example 83 except that the pH was changed to 9.

Example 91

The specimen was treated in the same manner as in Example 83 except that the pH was changed to 7.

Example 92

The specimen was treated in the same manner as in Example 83 except that the pH was changed to 5.

Example 93

The specimen was treated in the same manner as in Example 83 except that the pH was changed to 4.

Example 94

The specimen was treated in the same manner as in Example 82 except that the solution temperature was changed to 15 ° C.

{Table 4} Test Items and Methods, Quality Criteria

{Table 5} Measurement of Coating Amount of Invention Solution Treated Specimen

→ The metal adhesion amount of the above solution was measured by FRX, and the zinc phosphate coating amount was measured by wet method.

{Table 6} Anodizing and sealing test method, evaluation standard

{Table 7} Sealing test results of anodized film

{Table 8} Comparison of paint property test results after surface treatment-Cationic electrodeposition coating

As shown in the {Table 1}, Comparative Example 1 treated with zinc phosphate coating satisfies most test items required by the domestic coating industry. However, in Comparative Example 1 of the salt-resistant hot water secondary adhesion test of 240 hours, the unidirectional peeling of 3-4 mm or more in the "×" cut side of the galvanized zinc steel (GA) occurred, but the "Example 1-Example" treated with the solution of the present invention. 6, Examples 30 to 75, and 80 "in one side peeling was less than 3mm, in the salt spray test conducted for 500 hours, Comparative Example 1 has a unilateral peeling of 4mm or more on the surface of the galvanized zinc steel sheet (GA) Although the molten alloy plated steel (GA) treated with the inventive solution, the unilateral peeling showed good results of 3 mm or less.
According to the test results using the rust-preventive oil in the composition solution and the treated specimen in the test, the degreasing of the surface of the steel sheet as in the "Examples 7 to 14" which tested that the treatment time of the invention solution was 120 seconds or less. Although staining, corrosion resistance, and adhesiveness were poor due to defects, “Example 20 to Example 23” treated at a solution temperature of 40 ° C., pH 13.5, and a treatment time of 240 seconds and a solution temperature of 50 ° C., pH 12, and a treatment time of 240 Good results were obtained in "Examples 30 to 35" which were first tested.

The test time and hydrogen ion concentration index (pH) were not used in the test steel plates and the inventive solution without the use of rust-preventive oil, and tested after changing the metal content in the composition solution. ), Good results were obtained in "Examples 45 to 75" in which the temperature was changed. That is, in the process without using rust preventive oil, its use range is 40 seconds or more, pH 4 ~ 13.5, 30 ~ 50 ℃. Therefore, depending on the product characteristics of the object to be treated in the pretreatment line, When the surface of the workpiece is subjected to shot blasting, solvent degreasing or degreasing and washing, the invention solution can be used by extending the operating conditions from acidic to alkaline range.

In the sealing test after anodization, the proper treatment condition for aluminum surface gloss and sealing effect was pH 5-9, 25 ℃, and 20 minutes.

Zinc Phosphate Coating Process
1: degreasing 2: degreasing 3: degreasing
4: Washing 5: Washing 6: Surface adjustment
7: Zinc phosphate coating 8, 9: Water washing 10: Pure tax
Invention solution process
DESCRIPTION OF REFERENCE NUMERALS 1 Hot Dishes 2 Invention Solution 3 Invention Solution
4: Pure Tax 5: Pure Tax

Claims (8)

In the surface treatment agent treated on the surface of a metal or nonferrous metal steel plate,
Sodium hydroxide or potassium hydroxide mixed solution containing one or two or more metal salts selected from silicon, silver, magnesium, vanadium, zirconium, titanium and hafnium and added with a surfactant, silane hydrolyzate and fluorine Metallic surface treatment solution composition for coating.
The method of claim 1,
The metal surface treatment solution composition for coating coating, characterized in that the metal content of one or two or more metal salts selected from silicon, magnesium, vanadium, silver, zirconium, titanium and hafnium is 10 to 10,000 ppm.
The method of claim 1,
A non-painting metal surface treatment solution composition comprising adding a surfactant to a mixture of sodium hydroxide and potassium hydroxide.
delete delete In the metal surface treatment method using the metal surface treatment solution composition for coating the base of claim 1,
The solution temperature of the composition is maintained at 20 ~ 70 ℃, the hydrogen ion concentration index is (pH) 4 ~ 13.5, the surface treatment for coating metal, characterized in that the surface treatment for 5 to 1000 seconds.
In the metal surface pretreatment method using the metal surface treatment composition for coating the base of claim 1,
A coating pretreatment method for a metal surface for painting base, comprising: hot water washing, degreasing and coating, washing with water, and pure water washing.
8. The method of claim 7,
A method for pre-painting a metal surface for coating, characterized in that degreasing and coating are simultaneously processed in one process.

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