KR20160102586A - Nonphosphorus zirconium coating agent capable of using industrial water - Google Patents

Abstract

The present invention provides a zirconium cladding material for industrial water or tap water to be used in a zirconium coating treatment process or in a water washing process just before zirconium coating treatment, wherein calcium ion [Ca ²⁺ ] contained in industrial water and existing zirconium cladding containing fluoride [F ^-] a nor not bind free ions in the zirconium chemical conversion of organic functional liquid to be present in, and to assist in the film (organic functional Group; OFG) is presented, and calcium ions in addition to the anti-corrosive function contains [Ca ²⁺ ] and phosphorus (P) free. The use of the zirconium encapsulant of the present invention satisfies the coating quality required in the automobile industry and enables the zirconium coating to be performed in a short time (15 seconds to 2 minutes) Various metals (iron, zinc, aluminum) can be processed simultaneously.

Description

TECHNICAL FIELD [0001] The present invention relates to a zirconium-based zirconium cladding agent for industrial use,

The present invention relates to a coating agent for metal coating, and more particularly, to an environmentally friendly zirconium coating agent free from phosphorus (P), which is an environmental pollutant, and which can be used for industrial water, and a method of using the same.

In general, when rust-preventive oil is applied on a natural metal surface, it is possible to improve the corrosion resistance of the metal, but it is not possible to apply an advanced coating. This is because various contaminants such as rust and dust oil are on the surface of the metal, so that if the metal surface is painted, the paint quality is degraded.

Recently, it is common to coat metal phosphates on various metal surfaces and to coat them to improve coating properties such as corrosion resistance.

1915 American C.W. Since Parker produced a drug that uses phosphate coating on metal surfaces, development has been continuing until now to improve coating quality, save energy, save resources, and save manpower. In particular, the coating quality of a vehicle such as an automobile is remarkably improved by the application of the developed phosphate coating chemicals, so that the paint can not be peeled off even in the event of a vehicle collision or a contact accident. Even if the vehicle is exposed to rain in the open air or in cold regions where snow often occurs, or if there is a vehicle in the hot desert, paint paint will be firmly attached to the metal surface so that the painted vehicle will not rust for more than 10 years, Colorful) color as much as possible.

Examples of related patents using phosphate coating chemicals include the following patent documents.

In the case of Japanese paper making, Japanese Patent Application Laid-Open No. 63-223186 (1988.9.16) discloses a conventional coating solution (also referred to as a chemical conversion solution) used in a phosphate coating process. ) ion: 1500 ~ 3000mg / l, manganese (Mn) ions: 500 ~ 5000mg / l, nickel (Ni) ions: 500 ~ 5000mg / l, phosphate (PO ₄₎ ion: 5000 ~ 30000mg / l, nitrate (NO ₃ (2000) to 20000 mg / l of zinc (Zn) ions and 5000 to 40000 mg / l of phosphoric acid (PO ₄ ) ions in Japanese Patent Application Laid-open No. 3-20476 l, nickel (Ni) ions: 420 mg / l, and nitric acid (NO ₃ ) ions: 7500 to 13500 mg / l.

However, recent global trends are focused on eco-friendly development. Accordingly, the use of the lead [Pb] component, which is an environmental pollutant, was prohibited in the composition of the electrodeposition paint, and chromium [Cr ^{+ 6} ], which has been widely used as an aluminum metal surface treatment agent, was also not usable.

And, it has become inevitable to improve the metal phosphate coating agent, which has been widely used so far. This is because the metal phosphate coating agent contains a large amount of phosphoric acid [H ₃ PO ₄ ], zinc [Zn], manganese [Mn], nickel [Ni], nitric acid [HNO ₃ ]

Currently, research and development of environmentally friendly surface treatment agents are actively underway in Japan. According to the August 2008 issue of the Japan Coating Technology Magazine, as a project to upgrade the strategic base technology from the Osaka Municipal Industrial Research Institute and the Ministry of Economy, Trade and Industry (METI), Gifu Chemical Industries Co., Ltd. And developed a zirconium encapsulant as a substitute.

However, existing zirconium cladding chemicals developed by Naturalized Chemical Co., Ltd. are only 120 hours (based on cold rolled steel) in the salt spray test after coating, which is insufficient to apply to the automobile industry. In cold rolled steel sheet standards in the automotive industry, brine spray tests must be satisfied for more than 800 hours.

Japanese Patent Application Laid-Open No. 10-1359967 entitled " Japanese Patent Application Laid-Open No. 10-0317680 "Surface treatment agent for non-coating treatment capable of simultaneously treating aluminum alloy and steel sheet" JP-A-63-223186 (September 16, 1988) Japanese Unexamined Patent Application Publication No. 3-20476 (Jan. 29, 1991)

Accordingly, an object of the present invention is to provide an eco-friendly zirconium encapsulant which can satisfy the quality required in the automobile industry, and a method of using the same.

Another object of the present invention is to provide an eco-friendly zirconium encapsulant which can reduce the environmental pollution degree by 1/100 or more as compared with a phosphate encapsulant, and can provide excellent corrosion resistance (salt spray test for 1000 hours or more) and short time treatment (15 seconds to 2 minutes) and its use method. .

It is another object of the present invention to provide a lean environment-friendly zirconium encapsulant which can simultaneously treat various metals such as iron, zinc and aluminum, has an anticorrosive function and can use industrial water, and a method of using the same.

The present invention according to the above object is to provide an industrial water or tap water having a calcium ion [Ca ²⁺ ] of at most 75 mg / l and an electric conductivity of 100 to 300 μs / cm for use in a zirconium coating treatment process or a water washing process before a zirconium coating treatment in order to allow, calcium fluoride [CaF] further having a great bonding force the material to prevent the material or combination of calcium fluoride [CaF] in a dissolved state in water, fluoride [F ^-] than the conventional zirconium-containing as essential Friendly zirconium zirconium encapsulant which is capable of using industrial water further added to the encapsulant.

The above materials are organic functional groups (OFG)

And the organic functional group (OFG) is preferably an anion carboxyl group.

Further, the present invention is further characterized in that a calcium ion [Ca ²⁺ ] is further added for imparting rustproofing property, corrosion resistance after painting and coating adhesion, and the content (X) of the organic functional group is obtained by using the following calculation formula.

[Content (X) calculation formula]

Here, f is a factor of 0.1N-KMnO ₄ ,

         5: Sampling ml,

        C: iron (Fe) ion amount

Further, as another aspect of the present invention, the zirconium encapsulant can be used in industrial water or tap water during the zirconium coating treatment process or before the zirconium coating process, and also for the corrosion resistance and coating adhesion after the coating, Wherein the organic zirconium zirconium compound is at least one compound selected from the group consisting of zirconium ions, zirconium ions, zirconium ions and zirconium ions.

As another aspect of the present invention, there is provided a zirconium encapsulant, which has a greater binding force than calcium fluoride [CaF] and which can be used in a zirconium coating process or in a water washing process before a zirconium coating process, Organic Functional Group (OFG) to prevent the binding of dissolved substances or calcium fluoride [CaF]

Wherein the zirconium film is formed by a film action according to the following chemical reaction formula using a zirconium film-forming agent.

[Chemical reaction formula]

As another aspect of the present invention, the structure of a functional group in which a zirconium film layer is formed by coating a steel, zinc [Zn], or aluminum [Al] with the zirconium film of the present invention is represented by the following chemical formula The present invention relates to an environmentally friendly zirconium zirconium cladding system capable of using industrial water.

[Chemical Formula]

As a method of using the present invention, a liquid zirconium encapsulant containing 20 to 150 mg / l of calcium ions, 30 to 500 mg / l of zirconium ions and 25 to 300 mg / l of an organic functional group (OFG) Water used in the bath process of the zirconium film-forming process or the water-washing process prior to the zirconium film-forming process is subjected to ion exchange or RO water having an electric conductivity of not more than 50 / / cm for industrial water or tap water (electric conductivity 100 ~ 300 s / cm)

The coating treatment in the zirconium coating treatment step is carried out at 20 to 35 ° C for 15 to 120 seconds.

The present invention implements an environmentally friendly zirconium cladding material which is free of phosphorus [P] component which is an environmental pollutant, can contain calcium ion for rust prevention function and can use industrial water, and can satisfy the coating quality required in the automobile industry , And the environmental pollution level can be reduced to more than 1/100 of that of existing phosphate coating agents. In addition, there is an advantage that excellent corrosion resistance (salt spray test for 1000 hours or more) and short time film treatment (15 seconds to 2 minutes) are possible and various metals (iron, zinc, aluminum)

Figs. 1A and 1B are comparative photographs showing the natural dry state after 20 minutes of immersion of the phosphate coating and the zirconium coating in accordance with the prior art,
FIG. 2 is a photograph showing a naturally dried state after 20 minutes of water immersion after coating with a zirconium film agent containing calcium ions [Ca ²⁺ ] according to an embodiment of the present invention,
FIGS. 3A to 3C are conceptual diagrams showing a coating film layer formed of a zirconium film agent according to an embodiment of the present invention on iron, zinc,
4A to 4C are graphs showing the relationship between the composition of the zirconium coating layer of the present invention formed on the surfaces of the steel, zinc [Zn] and aluminum [Al] materials shown in Figs. 3A to 3C by energy dispersive X-ray spectroscopy (EDS) Fig.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

As a eco-friendly metal surface treatment agent (coating agent) mentioned in the above [Background of the Invention] section, a zirconium conversion agent is used as a substitute for a conventional phosphoric acid conversion agent. The advantages of the zirconium conversion agent include iron and zinc The alloy and the aluminum metal can be processed at the same time and can be used at a low temperature (room temperature ~ 35 ° C).

The mechanism is as follows.

H ₂ ZrF 6 + M + 2H ₂ O → MZrO ₂ (coating) + 4H ⁺ + 6F ^- + H ₂

Here, M: steel, zinc [Zn], aluminum [Al] Substance,

Table 1 below shows the previous and subsequent processes related to the known zirconium film treatment.

Process Name One.
Degreasing 2.
Suesse 3.
Suesse 4.
Mars (coating) processing 5.
Suesse 6.
Suesse 7.
Pure three 8.
dry 9.
Electrodeposition coating Temperature 45 ° C Room temperature Room temperature 15 ~ 35 ℃ Room temperature Room temperature Room temperature time 2 minutes 1 minute 1 minute 2 minutes 1 minute 1 minute 1 minute use
water industry
water industry
water Ion-exchanged water or
RO number Ion-exchange water
Or RO number industry
water Ion-exchange water
Or RO number Ion-exchange water
Or RO number

Here, it is possible to use industrial water or tap water (electric conductivity of 100 to 300 / / cm) in the processes 2 and 5, but as a conventional zirconium cladding, (Rinse) should be ionized water (Deionized Water) or RO (Reverse Osmosis Water, electric conductivity: 50 μs / cm or less).

The use of ion exchange water in the water washing requires the use of calcium ions [Ca ²⁺ ] or other dissolved ions (Mg, Fe, etc.) in the industrial water to deteriorate the zirconium film, (CaF) precipitate is formed and the coating or the electrodeposition is disturbed.

The zirconium conversion treatment agent (hereinafter referred to as "zirconium coating agent"), which is a zirconium coating agent, is environmentally friendly, and thus it is surely a substitute for the conventional phosphate coating treatment agent. However, it is very hesitant to apply it in the field of use such as automobile manufacturing company.

The reasons are as follows.

First, ion-exchanged water (DI Water) or RO water (electric conductivity of 50 / / cm or less) should be used as rinse water at the time of flushing before the zirconium film treatment process, and the zirconium film- It is necessary to use ion exchanged water (DI water) or RO water even when humidification is necessary. In order to apply this process to the process, it is necessary to additionally provide an apparatus for producing ion exchange water (D.I Water) or R.O water.

When DI water is used ^{, an} ion exchange resin is used to remove cations (Ca ²⁺ , Fe ^+, Mn ⁺ , etc.) and anions (Cl ^- , SO ₄ ^- etc.) A large-capacity device is required. In addition, after about one week of use, the exchange capacity of the ion exchange resin is lowered. At this time, it is troublesome to regenerate with hydrochloric acid [HCl] and caustic soda [NaOH], and secondary environmental pollution such as pH change may occur .

Also, when R.O. water is used, the same troublesome and difficulty as the ion exchange water (D.I.

Second, the zirconium film is very thin compared to the phosphate film, which is likely to cause rust during the process. As for the amount of the coating, the zinc phosphate coating is 2000 to 3000 mg / m ² , and the zirconium coating is 50 to 200 mg / m ^2, which is about 1/10 to 1/20 of the zinc phosphate coating. In the automobile coating (Hwaseong) treatment process in the field, after about 20 minutes after the coating (chemical conversion) treatment, the subsequent process is carried out. Water is buried in a metal material such as iron and the metal material is exposed to the air for about 20 minutes before being put into a subsequent process, Lt; / RTI >

The inventors of the present invention actually rusted the zirconium film in a laboratory under the most similar condition to the site, and then rusted the steel material as shown in FIG. 1 (b).

1A and 1B are comparative photographs of a natural drying state after 20 minutes of immersion of a phosphate coating and a zirconium coating after water deposition according to the prior art, 1B is a naturally dried state after 20 minutes from the immersion in water after the zirconium coating.

The rust generated as shown in FIG. 1B causes paint unevenness and poor adhesion.

Accordingly, in the present invention, an eco-friendly zirconium encapsulant is implemented, and first, a method of using Industrial Water (electric conductivity of 300 μs / cm or less) is sought.

The reason why Rinse is used as DI water or RO water in the zirconium film coating process or the previous water washing process is that the evaporation residue or the calcium ion [Ca ²⁺ ] Etc. react with the fluorine ion [F ^- ] contained in the zirconium encapsulant to generate fluoride such as calcium fluoride [CaF], which not only interferes with the chemical conversion coating but also causes the coating failure due to micro sludge . This is because the calcium salt (fluoride or sulfate) is deposited on the circulation pipe installed for the zirconium film treatment process and the pipe is clogged.

Therefore, the water used for the zirconium encapsulant is ion exchanged water (DI Water) or RO Water (water) containing less than 25 mg / l of calcium ion [Ca ²⁺ ] and chlorine ion [Cl ^- ] and sulfate ion [SO ₄ ^- (Pure water) is recommended. Industrial water is generally unsuitable for use as water in a zirconium cladding because it contains up to 300 mg / l of evaporation residues and less than 75 mg / l of calcium ions [Ca ²⁺ ].

The water quality standards of conventional industrial water, i.e., water, are shown in Table 2 below.

Item Industrial water quality standard Metal product manufacturing cleaning Turbidity 20 (Max) 16 (Max) pH 6.5 to 8.0 7.0 CaCO3 (mg / l) 75 (Max) 40 (Max) Total Hardness (mg / l) 120 (Max) 50 (Max) Evaporation residue (mg / l) 250 (Max) 300 (Max) Cl ^- ion (mg / l) 80 (Max) 10 (Max) Fe ion (mg / l) 0.3 (Max) 0.1 (Max) Mn ion (mg / l) 0.2 (Max) 0.1 (Max) Data Japan Industrial Water Association Handbook on Water and Wastewater (International Conference on p.25)

However, the use of ion exchange water (DI water) or RO water in the treatment of zirconium film requires the addition of a manufacturing facility as described above, so that its operation and operation cost are also inconvenient.

The present inventors have studied how industrial water can be used in a zirconium film treatment process and as a result, it has been confirmed that industrial water can be used if fluoride such as calcium fluoride (CaF 2) is produced and precipitates are not formed.

That is, calcium ions [Ca ²⁺ ] contained in industrial water and fluorine ions [F ^- ] contained in conventional zirconium encapsulants should not be bound and exist in zirconium-laden liquid in a free ion state. In other words, if a material that has a greater binding force than calcium fluoride [CaF] and is dissolved in water or uses a substance that interferes with calcium fluoride [CaF] bonding is used, tap water or industrial water Can be used.

The inventors of the present invention have found that when calcium ions [Ca ²⁺ ] contained in industrial water are converted into fluorine ions [F ^- ] contained in a zirconium coating agent as a result of using an organic functional group (hereinafter referred to as "OFG" And it was also in the state of being dissolved, and it was also able to help formation of a zirconium conversion film.

The working principle is as follows.

① Action of O.F.G with Calcium

② Coating action (chemical reaction formula)

Here, M is steel, zinc [Zn], and aluminum [Al] Substance.

In addition, the present invention implements an eco-friendly zirconium encapsulant, and secondly implements a method of imparting anti-rust properties so that rust does not occur during the process.

As described above, the zirconium film has a very thin film and is very fragile. Therefore, when the material is steel, the conventional zirconium encapsulant was rusted during the process of about 20 minutes until the coating after the chemical conversion coating.

In the automobile industry, it is very likely that rust will occur in iron materials because three types of composites such as steel, galvanized steel, and aluminum steel are put in the process together. It is necessary to strengthen the rust prevention because it causes paint failure. Generally, zinc and manganese ions may be included in the zirconium coating liquid either alone or in combination in order to impart anticorrosive properties to the coating agent. However, since all of these metal ions are environmentally regulated substances, they can not be used in large quantities.

In the present invention, calcium [Ca ²⁺ ], which is not a substance to be environmentally controlled, is used for imparting anticorrosive properties.

The OFG (Organic Functional Group)

Is dissolved in a solution (Solution) by binding with calcium ions [Ca ²⁺ ]

As shown in Fig.

In the present invention, 20 to 150 mg / l of calcium ions [Ca ²⁺ ] required for imparting rust inhibition and OFG of 25 to 300 mg / l were added to prevent fluoride formation. As a result, Despite this, very satisfactory results were obtained with no rust in the iron material.

3A to 3C show a conceptual diagram in which a zirconium coating layer according to an embodiment of the present invention is formed on a zinc or aluminum material.

FIG. 3A is a conceptual diagram illustrating a zirconium coating layer formed on a steel material, FIG. 3B is a conceptual diagram illustrating a zirconium coating layer formed on a zinc [Zn] material, and FIG. 3C is a conceptual diagram illustrating a zirconium coating layer on an aluminum [Al] .

The concept of illustration shown in Figs. 3A to 3C can be expressed as a functional group as shown below.

In order to confirm the reality of the concept of FIGS. 3A to 3C, the present inventor has developed a method of measuring energy by using energy dispersive x-ray spectroscopy (EDS) The results of measurement of the components of the zirconium coating layer of the present invention formed on the surface of the specimen of FIGS. 4A to 4C were obtained.

4A is an EDS qualitative analysis result table and spectrum graph for a zirconium coating layer on a steel specimen surface, FIG. 4B is an EDS qualitative analysis result table and a spectrum graph for a zirconium coating layer on the surface of a zinc [Zn] [Al] EDS qualitative analysis result table and spectral graph of the zirconium coating layer on the surface of the specimen.

As can be seen from FIGS. 4A to 4C, it can be seen that calcium ion [Ca ²⁺ ] is contained in the zirconium coating layer.

In the present invention, OFG is used to use industrial water for zirconium encapsulant treatment, and another calcium ion is added to the existing zirconium encapsulant to impart rust inhibition to the rust during the zirconium coating process.

Calcium ions and the separately added to the corrosion protection given calcium ions in the industrial water a fluoride [F ^-] containing the required zirconium pimakje hayeoseo combined with haejuneunde not to create a precipitate of calcium fluoride [CaF], zirconium pimakje of the invention This is accomplished by incorporating OFG (Organic Functional Group) with calcium ion before fluoride ion [F ^- ]. The OFG (Organic Functional Group) of the present invention preferably uses an anion carboxyl group (Anion Carboxy Group).

Composition ions of the environmentally friendly zirconium film agent according to the embodiment of the present invention and their ion concentrations are summarized in Table 3 in the following table.

Ion name Ion content (mg / l) Ion name Ion content (mg / l) ① O.F.G 20-300 ( ²⁾ Zr ²⁺ 30 to 500 ③ Ca ²⁺ 20-150 ④Zn ²⁺ 50 to 300 ⑤ F ^- 20-150 ⑥Mn ²⁺ 30 to 200 ⑦ Ag ⁺ 0 to 20 ⑧Fe ²⁺ 0 to 50 ⑨ NO ₃ ^- 0 to 50 ⑩B ^-3 0 to 150

The composition of the zirconium encapsulant of the present invention shown in Table 3 will be described in more detail below.

(1) O.F.G (Organic Functional Group) used an anionic carboxyl group and was adjusted to 20 to 300 mg / l when measured by the method of Measurement Method 1 described later.

(2) The zirconium ion-containing compound [Zr ²⁺ ] used in the composition of the zirconium cladding agent is selected from the group consisting of Hexafluoro Zirconic Acid [H ₂ ZrF ₆ ], Zirconium Tetrafluoride [ZrF ₄ ], Zirconium Sulfate Sulfate [ZrSO ₄ ], Zirconium Nitrate [Zr (NO ₃ ) ₂ .nH ₂ O] and the like were used. In order to function as a coating agent, Zr ²⁺ ions were diluted with industrial water and made up to 30 to 500 mg / l when made up.

( ₃ ) Calcium nitrate [Ca (NO ₃ ) ₂ ] and calcium sulfate [CaSO ₄ ] were used as the calcium ion [Ca ²⁺ ] compound of the present invention and diluted with industrial water for functioning as a coating agent Make up to 20 ~ 150 mg / l.

④ Zinc Nitrate [Zn (NO ₃ ) ₂ · nH ₂ O] and Zinc Sulfate [ZnSO ₄ ] were used as the zinc ion [Zn ²⁺ ] compound and diluted with industrial water And 50 ~ 300 mg / l as Zn ^{2 +} ions when humidified. This is equivalent to 1/100 of the conventional chemical conversion agent (encapsulating agent).

(5) Hydrogen fluoride [HF] and boroboric acid [HBF ₄ ] are used as the fluorine ion [F ^- ] compound, and fluorosilicic acid may sometimes be used. For the function, it was diluted to 20 ~ 150 mg / l when it was diluted with industrial water and made up.

⑥ Mn manganese [Mn (NO ₃ ) ₂ ] was used as a manganese ion [Mn ²⁺ ] compound, and when it was diluted with industrial water for function, it was 30-200 mg / l as Mn ²⁺ ion.

⑦ silver nitrate [AgNO ₃ ] was used as the [Ag] compound, and when it was diluted with industrial water for functioning, it was 0 ~ 20 mg / l when made up.

⑧ Iron (Ferric Nitrate) [Fe (NO ₃ ) ₂ ] was used as the iron [Fe] compound and it was 0 ~ 50 mg / l when it was boiled with industrial water for its function.

⑨ Nitrate ion [NO ₃ ] is not used separately except the metal compounds of ② ~ ⑧ above.

⑩ Boron ion [B- ³ ] exists when fluoroboric acid is used and is not used separately.

Table 4 below shows the front and back processes related to the zirconium film treatment using the zirconium film of the present invention having the above composition.

Process Name One.
Degreasing 2.
Suesse 3.
Suesse 4.
Coating (Mars) treatment 5.
Suesse 6.
Suesse 7.
Pure three 8.
dry 9.
Electrodeposition coating Temperature 45 ° C Room temperature Room temperature 20 ~ 35 ℃ Room temperature Room temperature Room temperature time 2 minutes 1 minute 1 minute 15 to 120 seconds 1 minute 1 minute 1 minute use
water industry
water industry
water industry
water
or
Water supply Industrial water or
Water supply industry
water industry
water
Or water Ion-exchange water
Or R.O

In the process of the present invention, the liquid zirconium coating agent contains calcium ion [Ca ²⁺ ] in an amount of 20 to 150 mg / l and zirconium ion in an amount of 30 to 500 mg / l in four steps of coating the liquid zirconium film agent, Industrial water (electric conductivity of 100 to 300 占 퐏 / cm) or water can be used as water used for bathing at the time of coating treatment.

Industrial water (electric conductivity of 100 to 300 占 / / cm) or tap water can be used as the water washing water in the immediately preceding process of the zirconium film treatment process, that is, the water washing process of the third and sixth times.

This is largely different from the use of water used in the bathing process of the conventional zirconium film-forming process or the water-washing process prior to the zirconium film-forming process mentioned in Table 1 as ion exchanged water or RO water having an electric conductivity of 50 μs / cm or less .

In the present invention, the zirconium film treatment is carried out at a temperature of 20 to 35 ° C. for 15 to 120 seconds. This permits a relatively low energy use compared to the case of coating at around 45 ° C. in the conventional phosphate coating treatment.

A number of specific embodiments according to the present invention are summarized in Table 5 below.

NO Example
ION One 2 3 4 5 How to measure One O.F.G mg / l 25 102 158 216 304 See Measuring Method 1 2 Zr ²⁺ mg / l 31 85 149 334 485 I.C.P 3 Ca ²⁺ mg / l 20 62 96 115 150 I.C.P 4 Zn ²⁺ mg / l 52 123 163 215 301 I.C.P 5 F ^- mg / l 151 98 70 53 23 See Measuring Method 2 6 Mn ²⁺ mg / l 32 74 104 156 202 I.C.P 7 Ag ⁺ mg / l 0 5 10 16 27 I.C.P 8 Fe ²⁺ mg / l 0 6 25 12 51 I.C.P 9 NO ₃ ^- mg / l 3 11 25 5 58 Ion meter,
See Measuring Method 2 10 B ^-3 mg / l 0 17 0 82 150 See Measuring Method 3 11 PO ₄ ^-3 mg / l none none none none none I.C.P 12 Electrical conductivity
(ms / cm) 1.8 2.3 2.8 3.9 7.2 Conductivity meter 13 Computational chart
(0.01 M NaOH) 35 22 14 12 10 See Measuring Method 4 14 PH 2.8 3.5 4.3 4.8 5.6 Using Ph meter 15 Adhesion test Good Good Good Good Good See Measuring Method 5 16 Impact resistance test Good Good Good Good Good See Measuring Method 6 17 5% salt water immersion test
(50%, 240HR) Good Good Good Good Good See Measuring Method 7 18 5% salt water spray test 1000HR Within 2m / m on one side Within 1m / m on one side Within 1m / m on one side Within 1m / m on one side Within 1m / m on one side See Measuring Method 8 19 Flexibility test Good Good Good Good Good See Measuring Method 9
20
Zr content in the coating (mg / m 2) CR 35 62 95 130 165 See Measuring Method 10 GA 22 38 54 61 80 " Al 43 65 82 109 146 "

As a characteristic constitution of the present invention, the water for use, that is, water is Tap water or Industrial water having an electric conductivity of 100 to 300 / / cm. The measured values in Table 5 were obtained by measuring by Inductively Coupled Plasma (ICP).

The measurement methods mentioned in Table 5 will be described in more detail as follows.

※ Measurement method 1: Measurement method of O.F.G

1) Take 5 ml of sample solution or Make up soln in the process accurately with a mass hole pipette, take in a 300 ml round bottom flask, and add about 100 ml of distilled water.

_{2) 1: 1 H 2 SO} 4 solution into 10ml,

3) 10 ml of 0.1N-KMnO ₄ standard solution is accurately taken with a mass hole pipette,

4) Install a Lviv chiller in the opening of a round bottom flask and allow to boil for 30 minutes while allowing the vapor to evaporate to condense and fall into a round bottom flask, then separate it from the cooler. If the color of the liquid after the boiling is transparent, add 10 ml of 0.1N-KMnO ₄ and boil again for 30 minutes. (Check for red or sword-red color)

5) Take exactly 10 ml of 0.1 N Na ₂ C ₂ O ₄ standard solution with a mass hole pipette. At this time, red (0.1N-KMnO ₄ ) or dark red color disappears and becomes colorless. (If 0.1N-KMnO ₄ is added, you must add as much as you add.)

6) Temperature 80 ± while maintaining 10 ℃ 0.1N-KMnO ₄ content of the calculation to the end point (END point) and the titration (Titration) that are standard pink solution is kept for 20 seconds or more as to the number of consumed ml " A ".

7) Blank Test Take 5ml of Industrial Water or Tap Water between the processes and add about 100ml of distilled water. Then, the above steps 2) to 6) are carried out and 0.1N-KMnO ₄ Consumption ml is referred to as "B" in the formula of content below.

8) Calculation of content of O.F.G (X)

Here, f is a factor of 0.1N-KMnO ₄ ,

         5: Sampling ml,

C: Iron [Fe] ion amount (measure iron ion that has increased between processes (if it is fresh solution), (take 5 ml of sample in process, add 10 ml of 1: 1 H ₂ SO ₄ and 100 ml of distilled water, add 0.1N-KMnO ₄ The solution is titrated at room temperature. The point at which the pink color is maintained for more than 30 seconds is the end point, and the number of ml of 0.1N-KMnO ₄ is called "C".)

※ Measurement method 2: F ^- ion content measurement and NO ₃ ion content measurement method

Measure the F ^- ion content and NO ₃ ion content (mg / l), respectively, using a well - calibrated ion meter.

※ Measurement method 3: Measurement method of boron (B ^2- ) ion

Use a boron (B) ion test kit. The use model name in the present invention is PACKTEST WAK-B (SEKANG INS (02-6292-1000)) product inspection kit.

※ Measurement method 4: Measurement method of Total Acid

10 ml of the sample is accurately sampled by a measuring pipette and placed in a 100 ml Erlenmeyer flask. 3 ~ 5 drops of phenolphthalein (ph.pht) indicator are added dropwise and then titrated with 0.01 M NaOH. The point converted from colorless to pink is regarded as the end point, and the number of the consumed ml is referred to as a computation degree (TA).

※ Measurement method 5: Adhesion test method

When the zirconium coating is applied and the painted specimen is cross-cut at 1 mm intervals (Cross cut), there should be no peel off of the checkerboard 50% or more.

※ Measurement method 6: Impact resistance test method

Using a Dupont impact tester, weigh 1 kg of weight at 50 cm height to check for damage to the coating. At this time, there should be no breakage of the coating.

※ Measurement method 7: Test method of salt water immersion test at 5%

Using a thermostat, the specimen, which had been scratched with a cross (+), was immersed for 240 hours in a 5% salt solution [NaCl] maintained at 50 ° C., washed well and rubbed with a cellophane tape. The loss of the coating should not exceed 3 mm on one side when the tape is removed.

※ Measurement method 8: 5% salt spray test method

A 5% salt solution [NaCl] is sprayed at 35 ° C for 1000 hours using a salt spray tester and the film loss of the positive (+) side should not exceed 3 mm on one side.

※ Measurement method 9: Flexibility test method

Place the specimen on a round bar Φ10mm using a Flexibility Tester, and remove the coating by 360 ° at a time.

※ Measurement method 10: Measurement method of Zr content in film

Measure three times using XRF (X-ray fluorence) analyzer and take the average value in mg / m ² .

Table 6 below shows the results of the coating film performance test after the environmental zirconium film treatment according to the embodiment of the present invention is performed.

Iron (SPC) GA (galvanized steel plate) Al (aluminum
And alloys thereof) How to measure One.
Attachment

1mm Go Scale

See Section 5 2.
Impact resistance test

Using Dupont Impact TEST

See Section 6 3.
5% salt water immersion test


After demineralizing 240Hr in 5% salt water (50 ℃), the peel width should not exceed 3mm on one side by using tape.

See Section 7 4.
5% salt spray test


After 800Hr, the peel width should not exceed 3mm on one side by using tape.

See Section 8 5.
Flexibility test

Using a Ø10 m / m round bar, break it 360 ° at a stroke.

See Section 9

As shown in Table 6, the present inventors confirmed that the zirconium coating of the present invention satisfied the performance required in each test.

Effects according to the embodiment of the present invention can be summarized as follows.

First, the present invention realizes an environmentally friendly metal surface treatment agent which minimizes environmental polluting substances. Conventional phosphate surface treatment agents contain a large amount of environmental pollutants as described above in the Background of the Invention, but the environmentally friendly zirconium coating agent of the present invention has reduced environmental pollution by less than about 1/100 as compared with the prior art.

Table 7 shows the results of comparison of the environmental pollution between the conventional phosphate surface treatment agent and the zirconium coating agent of the present invention.

division
Item Emission Standards Conventional phosphating agent
(5 ~ 6% bathing suit) Invention
(2 ~ 3% bathing suit) Remarks Total nitrogen (mg / l) 60 500 ~ 2000 3 to 50 Total (mg / l) 8 5000 ~ 30000 None Zn (mg / l) 5 1500 ~ 3000 50 to 300 Mn (mg / l) 10 500 ~ 5000 30 to 200 Cu (mg / l) 2 5 to 10 1-5 Ni (mg / l) 500 ~ 5000 None Law amendment Ca (mg / l) None None 20-150

The items in Table 7 above and emission limits are based on the Korea Environmental Preservation Act, and the bath concentration is the concentration at which the conversion film is run.

Secondly, the present invention can use industrial water, so that the process using the conventional phosphate coating agent can be changed or used without any additional equipment such as an ion exchange apparatus. As described in the first problem of the present invention described above, in countries such as Europe, the water used for the zirconium film treatment process is recommended as the ion exchange water (D.I Water) or the R.O water. However, since the zirconium cladding system of the present invention can use industrial water, it is not necessary to install additional ion-exchanged water or pure water production equipment, and its operation and operation costs are not included.

Thirdly, since the calcium ion [Ca ²⁺ ] is contained in the present invention, corrosion resistance and paint adhesion (adhesion) after painting are greatly improved. It is believed that this is due to the unique denseness of the calcium ion and the affinity of the zirconium film. However, when the calcium ion content is more than 200 mg / l, the coating film may be deteriorated, so that the content is most preferably 20 to 150 mg / l.

Fourth, the present invention significantly reduces the amount of industrial waste (sludge) generated. When the conventional phosphate coating agent is contacted with a metal material (steel, Zn, Al), a large amount of chemical precipitates such as phosphoric acid, iron and zinc are formed in the coating tank while being etched. This precipitate is collected in the filtration process and treated as industrial waste. In the zirconium encapsulant according to the present invention, the sludge generated during the coating process is reduced to about 1/10 or less as compared with the previous one.

Fifth, the present invention is capable of energy saving by coating film low temperature. Normally, the phosphate coating should be treated at 45 ℃ for 2 minutes. However, since the present invention is carried out at 20 to 35 ° C for 15 to 120 seconds, not only energy saving but also convenience of working time is provided.

Sixth, the present invention can simultaneously treat many metal materials such as steel, zinc [Zn] and aluminum [Al]. Due to the influence of fluorine ion [F ^- ] contained in the zirconium film, it becomes possible to simultaneously treat many metal materials.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the scope of claims and equivalents thereof.

INDUSTRIAL APPLICABILITY The present invention can be used as a pretreatment agent for vehicle and metal coating, and can be used for metal surface treatment for improving coating quality.

Claims (11)

In order to enable industrial water or tap water having a calcium ion [Ca ²⁺ ] of up to 75 mg / l and an electric conductivity of 100 to 300 μs / cm to be used in a zirconium coating treatment process or a water washing process before zirconium coating treatment, calcium fluoride [CaF ] more has a large binding force the material to prevent the binding of substances or calcium fluoride [CaF] in a dissolved state in water, fluoride [F ^-] a a conventional hayeoseo further added to be the composition in zirconium pimakje containing industrial required Environment-friendly zirconium zirconium coating available with water.
The organic electroluminescent device of claim 1, wherein the material comprises an organic functional group (OFG)

Wherein the water-soluble zirconium-based zirconium-based zirconium-based zirconium-based zirconium-based zirconium-based zirconium-based zirconium zirconium-based zirconium-
[Claim 3] The environmentally friendly zirconium zirconium coating composition according to claim 2, wherein the organofunctional group (OFG) is an anion carboxyl group.
The eco-friendly zirconium clay coating agent according to claim 1, wherein calcium ions [Ca ²⁺ ] are further added for imparting rust resistance, corrosion resistance after painting, and coating adhesion.
4. The environmental friendly zirconium clathrate system according to claim 2 or 3, wherein the content (X) of organic functional groups is obtained by using the following formula.
[Content (X) calculation formula]

Here, f is a factor of 0.1N-KMnO ₄ ,
5: Sampling ml,
C: iron (Fe) ion amount In the zirconium encapsulant,
It is preferable to use 20 to 150 mg / l of calcium ion and 30 to 500 mg / l of zirconium ion for industrial use water or tap water for use in the zirconium coating treatment process or water washing process before zirconium coating treatment and for imparting rust resistance, l and an organofunctional group (OFG) of 25 to 300 mg / l, based on the total weight of the organic zirconium compound.
The environmentally friendly zirconium zirconium coating composition according to claim 6, wherein the organofunctional group (OFG) is an anion carboxyl group.
In the zirconium encapsulant,
In order to enable industrial water or tap water to be used in a zirconium coating treatment process or in a water washing process before a zirconium coating treatment, a substance having a binding force larger than that of calcium fluoride [CaF] and having a substance dissolved in water or a combination of calcium fluoride [CaF] Organic Functional Group (OFG)

Wherein the zirconium film is formed by the action of a film according to the following chemical reaction formula using the zirconium film-forming agent containing the organic zirconium film-forming agent.
[Chemical reaction formula]

Characterized in that the structure of a functional group in which a zirconium coating layer is formed by coating a steel, zinc [Zn] or aluminum [Al] with a zirconium coating agent is expressed by the following chemical formula: This environmentally friendly zirconium cladding system is possible.
[Chemical Formula]

A liquid zirconium encapsulant containing 20 to 150 mg / l of calcium ions, 30 to 500 mg / l of zirconium ions and 25 to 300 mg / l of an organic functional group (OFG) is used in the zirconium coating treatment process, (Water conductivity of 100 to 300 / / cm), which is an ion exchange water or an RO water having an electric conductivity of 50 / / cm or less, is employed in the water treatment process or the water washing process of the zirconium film treatment process A method of using an environmentally friendly zirconium cladding agent capable of using industrial water as a feature.
11. The method according to claim 10, wherein the zirconium coating treatment is performed at 20 to 35 DEG C for 15 to 120 seconds.

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