KR102027984B1 - Ultraviolet Cured Organic-Inorganic Hybrid Coating Composition - Google Patents
Ultraviolet Cured Organic-Inorganic Hybrid Coating Composition Download PDFInfo
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Abstract
The present invention is to provide a zirconium inorganic-based UV-curable organic-inorganic composite coating solution excellent in corrosion resistance and adhesion to the upper coating, excellent storage stability, the UV-curable organic-inorganic composite coating solution of the present invention is a zirconium precursor, a silane coupling agent Zirconium sol comprising methacrylic acid as a solvent and a catalyst; Ultraviolet curable acrylic resins; And a photoinitiator, and includes 15 to 30 wt% of the ultraviolet curable acrylic resin, 0.5 to 2 wt% of the photoinitiator, and the balance zirconium sol based on the total solution weight.
Description
The present invention is to provide a UV-curable organic-inorganic composite coating solution excellent in corrosion resistance and adhesion to the top coating.
Alloy-plated surface-treated steel sheet is increasing in demand for the purpose of improving the corrosion resistance in the automotive, home appliances and building materials industry. In particular, among the surface-treated steel sheet, zinc plated steel sheet has been recently commercialized by zinc-based binary and ternary alloy plated steel sheets at home and abroad for the purpose of improving corrosion resistance.
Zinc alloy coated steel sheet is widely known and used as a typical anti-corrosive steel sheet for protecting the base metal (carbon steel) from corrosion. However, as the use and storage environment becomes more severe, there is a demand for post-treatment techniques such as surface treatment for better corrosion resistance, temporary rust resistance, and discoloration during storage.
Currently, the steel plate coating is treated with a lower chromate film to improve corrosion resistance and an upper resin film to prevent chromium elution and improve paintability. However, hexavalent chromium is a representative carcinogen and has a strong toxicity to humans and causes environmental pollution. As it is classified as an environmental regulation substance, its use is restricted.
Therefore, in order to prepare for this, each steel company has been actively researching chromium-free coating and applying it to some products. However, as chromium has not yet been fully regulated and is considered to be less than chromate in terms of quality and cost, studies for improving quality performance and reducing costs of chromium-free coatings are ongoing.
In order to secure the same degree of corrosion resistance as the chromate coating through the chromium-free coating, it is necessary to add a harmless inorganic material, and in particular, the inorganic material is nano-structured to form an organic compound and a nanocomposite structure.
The organic-inorganic nanocomposite structure may be formed using a sol-gel process, thereby forming an organic-inorganic composite film. In general, the inorganic sol-gel coating provides excellent adhesion between the metal and the organic resin coating, but does not provide adequate anticorrosive ability because of the high possibility of cracking. However, by adding an organic element to form an organic-inorganic composite coating, the adhesion to the top coating can be improved, and a thick coating can be formed, thereby providing an effective anticorrosion ability against the corrosive medium.
The organic-inorganic composite sol-gel coating is an environmentally friendly way to replace chromate-based pretreatment because of its excellent anticorrosive performance and effective self-healing performance. Much research is being done.
However, when the organic-inorganic composite coating is applied to the surface of the alloy-plated steel sheet in the steel manufacturing process in the steel company, the coating is heated and cured at a PMT (peak metal temperature) of 250 ° C. or higher in a hot air drying furnace to secure predetermined corrosion resistance. Could. In addition, volatile organic compounds (VOCs) from coating solutions that occur during such thermal curing can cause problems of environmental pollution. These shortcomings may put a burden on production costs as well as a slowdown in steel manufacturing.
On the other hand, in the case of curing the coating layer by ultraviolet curing, it is more environmentally friendly than the thermal drying curing method because it does not discharge the volatile organic solvent generated by the thermal curing as described above, and thus the productivity can be improved because the curing speed is faster. Of course, it can be cured even at low temperatures, and energy can be added only to necessary parts, resulting in energy savings.
The present invention is to provide a zirconium inorganic-based UV-curable organic-inorganic composite coating solution excellent in corrosion resistance and adhesion to the upper coating, excellent storage stability.
The present invention relates to a zirconium inorganic-based UV-curable organic-inorganic composite coating solution, wherein the UV-curable organic-inorganic composite coating solution comprises a zirconium sol comprising methacrylic acid as a zirconium precursor, a silane coupling agent, a solvent and a catalyst; Ultraviolet curable acrylic resins; And a photoinitiator, and includes 15 to 30 wt% of the ultraviolet curable acrylic resin, 0.5 to 2 wt% of the photoinitiator, and the balance zirconium sol based on the total solution weight.
The zirconium sol comprises 50 to 60% by weight of the zirconium precursor, 20 to 35% by weight of the silane coupling agent, 10 to 20% by weight of the solvent and 0.05 to 0.5% by weight of the catalyst.
The zirconium precursor may be zirconium tetrapropoxide, zirconium ethoxide or mixtures thereof.
In addition, the silane coupling agent may be selected from the group consisting of methacryloxypropyltrimethoxysilane, glycidoxypropyl trimethoxysilane, methyltrimethoxysilane and aminopropyltriethoxysilane.
In addition, the solvent may be selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
And, the catalyst may be selected from the group consisting of methacrylic acid, acrylic acid, nitric acid and hydrochloric acid.
The ultraviolet curable acrylic monomer is one, two or more difunctional selected from the group consisting of 1,6-hexanediol diacrylate, 2-ethylhexyl acetate, 1,3-butanediol diacrylate and diethylene glycol diacrylate Monomer and a mixture of one or two or more trifunctional monomers selected from the group consisting of trimethylolpropane triacrylate, pentaaryltritoltriacrylate, and dipentaaryltritolhexaacrylate. At this time, the bifunctional monomer and the trifunctional monomer is preferably mixed in a weight ratio of 1: 1 to 1: 3.
In addition, the photoinitiator may be selected from the group consisting of 1-hydroxycyclohexylphenyl ketone, benzyldimethylcatal, 1,1-dichloroacetophenone and benzophenone.
According to the present invention, an ultraviolet curable organic-inorganic composite coating solution excellent in storage stability can be obtained.
By using the UV-curable organic-inorganic composite coating solution of the present invention, cracking of the inorganic film can be prevented, and the corrosion resistance of the steel sheet can be improved, and excellent adhesion with the upper resin film can be obtained.
In addition, by coating the surface of the steel sheet using the UV-curable organic-inorganic composite coating solution provided in the present invention can be cured coating layer by ultraviolet irradiation can improve the steel sheet production rate, it is possible to reduce the energy consumption.
Furthermore, by curing the coating layer by UV curing, it is possible to prevent the discharge of the volatile organic solvent to be environmentally friendly.
1 is a UV absorption peak measured by UV-Vis Sepctroscopy the degree of ultraviolet absorption of the zirconium-based organic-inorganic composite coating solution according to the present invention.
FIG. 2 is a graph showing evaluation results of corrosion performance obtained by performing a bipolarization test on a steel sheet having a coating layer formed using the coating solution of Example 1 and a steel sheet of Comparative Example 7. FIG.
3 is a photograph of the degree of corrosion after the salt spray test for the steel sheet having a coating layer formed using the coating solution of Example 1 and the steel sheet of Comparative Example 7.
Figure 4 is a photograph of the degree of corrosion of the processing unit on the surface of the steel sheet having a salt spray test after processing the steel sheet having a coating layer formed using the coating solution of Example 1 and Comparative Example 7.
FIG. 5 is a photograph showing the degree of peeling of the coating on the surface of the steel sheet, which was subjected to a peeling test after powder coating on a steel sheet having a coating layer formed using the coating solution of Example 1. FIG.
The present invention is to provide an organic-inorganic composite coating solution containing a UV-curable zirconium-based inorganic material, the coating solution of the present invention comprises a zirconium-based inorganic sol and UV-curable resin as a main component.
The ultraviolet curable organic-inorganic composite coating solution of the present invention uses zirconium as a main component as an inorganic substance, and is obtained by mixing an inorganic sol containing zirconium with an ultraviolet curable resin. The inorganic sol containing zirconium includes a zirconium precursor, a silane coupling agent, a solvent and a catalyst.
In this invention, it is preferable to use the said zirconium precursor as a zirconium supply source which is an inorganic substance. A zirconium inorganic sol prepared using a zirconium precursor reacts with the metal surface of Zn to form an insoluble metal zirconate salt, thereby forming an insoluble film of zirconium oxide and zirconium hydroxide. The film thus obtained has excellent adhesion to metals and slows the transmission of moisture, hydrogen, corrosive ions, and the like from the outside, thereby exhibiting excellent corrosion resistance. In addition, since the reaction density is relatively lower than that of the silicon-based inorganic coating, it is possible to form a better corrosion resistant coating due to the lower generation of cracks in forming the coating. The zirconium precursor may be used in the present invention without particular limitation as long as it includes zirconium. Preferably, zirconium tetrapropoxide or zirconium ethoxide may be used, and these may be used alone, as well as in combination. It may be.
The zirconium precursor is preferably included in the range of 50 to 60% by weight in the total weight of the inorganic sol. When the content is less than 50% by weight, the content of the inorganic material is relatively low, so that the content of the silane coupling agent may be relatively increased, which may worsen the storage stability of the solution by gelling the solution during the solution storage by reaction with the organic material. On the other hand, when the content of the zirconium precursor exceeds 60% by weight, the inorganic content is too high, and the inorganic material that does not form an organic-inorganic complex by coupling with the organic material remains, which is sufficient to increase the corrosion resistance of the film You can't.
The inorganic sol of this invention contains a silane coupling agent in order to form the network of the said zirconium which is an inorganic substance, and the photocurable resin which is an organic substance. The silane coupling agent combines the zirconium precursor and the ultraviolet curable resin to form a network of an inorganic material and an organic material, and a coupling agent generally used for bonding an organic material and an inorganic material may be used. For example, methacryloxypropyl trimethoxysilane, methacryloxypropyl trimethoxysilane, glycidoxy propyl trimethoxysilane, methyl trimethoxysilane, and aminopropyl triethoxysilane are mentioned. These silane coupling agents can be used individually or in mixture of 2 or more.
The silane coupling agent is preferably included in an amount of 20 to 35% by weight in the total weight of the inorganic sol. If the content of the silane coupling agent is less than 20% by weight, it may be insufficient to form a network between the inorganic zirconium precursor and the organic material, which may not provide sufficient corrosion resistance. On the other hand, when the content of the silane coupling agent exceeds 35% by weight, as described above, the solution during the storage may be gelled by the reaction with the ultraviolet curable resin, which is an organic material, thereby lowering the solution stability.
In addition, the said inorganic sol contains a solvent. It is preferable that the said solvent uses a nonpolar solvent. The coating solution of the present invention is preferably an ultraviolet curable solution, and by using a nonpolar solvent in this way, the burden on the environment due to the volatile organic compound can be reduced. Conventional hybrid solutions using zirconium, etc., were generally prepared using alcohol solvents for stability of dispersion. However, this hybrid solution has a risk of fire due to solvent evaporation in continuous processes such as steel manufacturing processes. It is difficult to apply, and in order to solve this problem, non-polar solvents of ketones can be applied to free the physical properties of the solution and the risk of fire. In addition, the curing process by ultraviolet irradiation is very environmentally friendly because the amount of evaporation of the solvent contained in the film is very small compared to the general thermosetting process can reduce the amount of VOC generation. Although it does not specifically limit as said nonpolar solvent, Acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone can be used.
Such a solvent is preferably included in an amount of 10 to 20% by weight in the total weight of the inorganic sol. If the content of the solvent is less than 10% by weight, there is a problem that the inorganic content of the solid content is too high to disperse the inorganic material and the solution production, if the content is more than 20% by weight, the corrosion resistance when forming the film due to the too low solid content ratio There is a problem of deterioration.
Furthermore, the inorganic sol includes a catalyst. The catalyst serves to promote a hydrolysis reaction for converting the zirconium precursor into a sol, and may use an acid catalyst, and examples thereof include acrylic acid, methacrylic acid, nitric acid and hydrochloric acid. The catalyst content is not particularly limited, but may include 0.05 to 0.5% by weight.
Inorganic sol can be obtained by mixing the above components. Specifically, a zirconium sol containing zirconium as a main inorganic component can be produced by mixing and stirring the zirconium precursor, silane coupling agent, solvent, and acid. The stirring is not particularly limited, but may be performed at a temperature in the range of 20 to 30 ° C. for 1 to 4 hours, and a stirring device that is commonly used may be used, and the present invention is not particularly limited.
The ultraviolet curable zirconium-based organic-inorganic composite coating solution of the present invention may be obtained by mixing the ultraviolet curable organic material and the photoinitiator with the obtained zirconium sol.
An acrylate may be used as the ultraviolet curable organic material. The acrylate may be an acrylate monomer or oligomer. In the present invention, the acrylate may be used bi- and tri-functional acrylate. Although it does not specifically limit as said bifunctional acrylate, For example, 1, 6- hexanediol diacrylate, 2-ethylhexyl acetate, 1, 3- butanediol diacrylate, diethylene glycol diacrylate, etc. are mentioned. These bifunctional acrylates can be used, Of course, these can also be mixed and used. As the trifunctional acrylate, and trimethylolpropane triacrylate, pentaaryltritoltriacrylate, dipentaaryltritolhexaacrylate, and the like can be used, and any one or a mixture thereof can be used. It may be.
The bifunctional acrylate and the trifunctional acrylate are preferably used by mixing, and the mixing ratio thereof is preferably mixed in a weight ratio of 1: 1 to 1: 3. As the content of the bifunctional acrylate increases, it shows a tendency to gelate by the reaction with the silane coupling agent, which may worsen the storage stability of the solution, and it is preferable to mix in the above range.
The acrylate may be included in an amount of 15 to 30% by weight in the total weight of the organic-inorganic composite coating solution of the present invention. When the content of the acrylate is less than 15% by weight, the inorganic zirconium, which is relatively inorganic, may have a high content, and thus inorganic materials that do not form networking with organic materials may exist, and thus may not provide sufficient corrosion resistance due to cracks in the coating portion of the steel sheet. Can be. On the other hand, when the content of the acrylate is more than 30% by weight, the inorganic content is high, the coating thickness on the steel sheet can be increased when forming a film. When the film is increased, it is not a problem in terms of securing corrosion resistance, but when forming a film for imparting temporary rust resistance during transportation or storage of steel sheets, it is usually formed to a thickness of about 1 μm, and thus it may be difficult to apply during actual operation. More preferably, the acrylate may be included in 15 to 20% by weight in the total weight of the organic-inorganic composite coating solution of the present invention.
Furthermore, the coating solution of the present invention comprises a photoinitiator. The photoinitiator is capable of initiating photocuring of the acrylate, and may be suitably used in the present invention as long as it is commonly used, and is not particularly limited. For example, as the photoinitiator, 1-hydroxycyclohexylphenyl ketone, benzophenone, benzyl dimethyl ketone, benzoin methyl ether, benzoin ethyl ether, p-chlorobenzophenone, 4-benzoyl-4-methyldiphenyl Sulfide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone -1, etc. can be mentioned. The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
The photoinitiator may be included in an amount of 0.5 to 2% by weight in the total weight of the organic-inorganic composite coating solution of the present invention. If the content is less than 0.5% by weight, there is a problem that an uncured part may occur in the one-pass ultraviolet curing process, and when the content exceeds 2% by weight, cracks in the film due to overcuring during UV irradiation may occur. There is a problem. More preferably, it may be included in an amount of 0.5 to 1.5% by weight.
The ultraviolet curable organic-inorganic composite coating solution of the present invention can be obtained by mixing the ultraviolet curable organic material and the photoinitiator with the zirconium sol. The ultraviolet curable organic-inorganic composite coating solution of the present invention may contain an additive as necessary, and is not particularly limited in the present invention.
After coating the obtained ultraviolet curable organic-inorganic composite coating solution on the surface of the steel sheet, the organic-inorganic composite coating can be formed on the surface of the steel sheet by irradiating with ultraviolet rays to cure. The method of coating the solution on the surface of the steel sheet is not particularly limited as it can be applied to the method that is commonly performed, for example, flow coating, immersion coating, spin coating, spray coating, curtain coating, It may be carried out by various known methods such as gravure coating, meyer bar coating, dip coating and the like.
It is preferable to clean the steel sheet surface before applying the ultraviolet curable organic-inorganic composite coating solution to the steel sheet surface. The cleaning is not particularly limited, and may be performed by various methods. For example, the cleaning may be performed by applying ultrasonic waves after immersion in acetone or the like.
After coating the surface of the steel sheet with the ultraviolet curable organic-inorganic composite coating solution provided by the present invention, a film can be easily formed by irradiating ultraviolet rays. The ultraviolet light is preferably irradiated with ultraviolet light in the UV-A region to perform curing. As long as it is a lamp which can irradiate the ultraviolet-ray of the said wavelength band, it can be used without particular limitation, For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, etc. are mentioned.
By the irradiation of ultraviolet rays, the ultraviolet curable compound is polymerized and cured, and the zirconium precursor is combined with the ultraviolet curable compound by a silane coupling agent to form a network structure to form a film. At this time, the film formed on the steel sheet is not particularly limited, but considering that a film having a thickness of about 1 μm is usually formed for temporary rust prevention of the coated steel sheet, it is preferable to have a range of 0.8 to 1.2 μm.
UV-curable zirconium-based organic-inorganic composite coating solution according to the present invention can ensure the storage stability of the solution without gel formation even if stored for a long time, when using this to form a film on the surface of the steel sheet cured using ultraviolet rays As a result, the curing rate can be increased as compared with the case of forming a film by thermal curing, the production rate can be improved, and the energy consumption for thermal curing can be reduced.
Furthermore, the steel sheet formed by the UV-curable zirconium-based organic-inorganic composite coating solution provided in the present invention not only has excellent corrosion resistance, but also because the inorganic material is complexed with the organic material after processing, so that the crack of the film is not formed to ensure corrosion resistance of the processed portion. can do. It also provides excellent adhesion with the coating formed on the coating.
Example
Hereinafter, an Example is given and this invention is demonstrated more concretely. However, the following embodiments are related to an example for describing the present invention, and the present invention is not limited thereto.
Example 1 to 3 and Comparative example 1 to 6
Preparation of Zirconium Sol
To prepare organic-inorganic hybrid coatings, zirconium tetra-propoxide (TPOZ, Sigma-Aldrich, USA, Zirconium (IV) propoxide) as an inorganic component, methacryloxypropyl trimme as silane coupling agent for networking with organics Toxisilane (MPTMS, Sigma Aldrich, USA, 98%), acetone as a solvent (SAMCHUN Inc., Korea) and 0.1 N methacrylic acid (MAA, Sigma-Aldrich, USA, methacrylic acid) as a catalyst as shown in Table 1 And an inorganic sol was prepared by stirring for 24 hours.
UV Curable Organic-Inorganic Composite Coating Solution
1,6-hexanediol diacrylate (HDDA, Gelest Inc., USA, 98%), which is a bifunctional monomer, and trimethylolpropane triacrylate (TMPTA, Sigma Aldrich., USA, 99%) and 1-hydroxycyclohexyl phenyl ketone (Sigma Aldrich., USA, 99%) as a photoinitiator was mixed in the content as shown in Table 1 to prepare an organic-inorganic composite coating solution.
In Table 1, the content of zirconium sol represents the weight% of each component to 100% by weight of the total zirconium sol, the content of the ultraviolet curable acrylic resin and photoinitiator represents the weight% relative to the total weight of the organic-inorganic composite coating solution, The balance is zirconium sol.
Coating layer formation
A galvalume steel sheet (plating layer: 55.1 wt% Al, 43.3 wt% Zn and 1.6 wt% Si, steel plate thickness: 1.5 mm) having a size of 75 mm x 150 mm was immersed in acetone and washed with ultrasonic waves for 3 minutes.
The galvalume steel sheet was immersed in the coating solution obtained in Examples 1 to 3 and Comparative Examples 1 to 6 using a dip coater (KSV-LM, CK trade Inc., Korea) while transferring at a rate of 0.1 mm / sec. Subsequently, it was cured by irradiating ultraviolet rays using a UV curing machine (EIT Inc., USA) to form an organic-inorganic composite film.
In this case, the coating solution used was diluted with acetone and mixed in a volume ratio of 1: 1 to control the adhesion amount.
The UV lamp used for curing was a 120W / cm mercury lamp (three medium pressure Hg lamp, wavelength 365nm) was used, the conveyor belt speed was used fixed to 2m / min. The amount of light using only before coating UV radiometer (radiometer) (EIT Inc., USA ) confirmed the UV-A 1072.582mJ / cm 2 and 157.780mW / cm 2 and to perform coating.
In order to verify whether the lamp of the UV wavelength band is adopted in curing the UV curable hybrid solution, the UV absorption degree of the solution of Example 1 was examined through UV-Vis spectroscopy measurement, and the results are shown in Figure 1 below. In the UV absorption peak of Figure 1, it can be seen that the absorption is occurring in the UV-A area as the entire absorption area is less than 290nm, through which it is reasonable to UV cured with the UV-A Hg lamp used in the experiment Could confirm.
<Evaluation of Physical Properties of Coating Layer>
The coating layers obtained from Examples 1 to 3 and Comparative Examples 1 to 6 were tested for corrosion resistance and top coat adhesion.
1. Corrosion resistance evaluation
Corrosion resistance of the obtained coating layer was evaluated by the electrochemical corrosion resistance according to the bipolar polarization characteristics measurement, the corrosion resistance according to the salt spray test (SST, salt spray test) and the corrosion resistance according to the salt spray test of the processing unit. In order to compare the corrosion resistance evaluation results, the corrosion resistance of the untreated galvalume steel sheet without a coating layer was compared together, which is shown as Comparative Example 7.
(1) Evaluation of electrochemical corrosion resistance
Potentiostat / Galvanostat (EG & G model 273A, USA) was used to fix the test piece for polarization test having an effective area of 10 mm × 10 mm in a polarization cell. A polarization curve was measured under a scan rate of 0.5 mV / sec using a saturated calomel electrode (SCE) as a reference electrode and a high density carbon rod as an auxiliary electrode.
Since the base metal is the same galvalume steel plate, the corrosion potential (corrosion potential, Ecorr) was -1.0V, which was almost the same. However, when the current density was evaluated, the steel sheets having the coating layers formed by the solutions of Examples 1 to 3 and Comparative Examples 1 to 6 all exhibited a similar degree of corrosion resistance.
Regarding the measured results, the electrochemical corrosion resistance measurement results for the steel sheet coated with the solution of Example 1 and Comparative Example 7 are shown in FIG. 2.
(2) salt spray test
Salt spray tests were performed using a salt spray tester (ASCOTT Inc., U.K.). The test was performed by spraying a 5% concentration of neutral saline with the specimen tilted 20 ° with respect to the vertical line while maintaining the ambient temperature in the spray chamber at 35 ± 2 ° C.
Surface observation of the specimens was observed at 12 hour intervals and tested for up to 72 hours. Evaluation of the corrosion resistance of the test piece was judged by the production time and area of white rust through the photograph taken, and as a result, it was judged that the corrosion resistance was good for the occurrence of less than 5%.
Salt spray test for 72 hours showed that all UV cured hybrid coated steel sheets exhibited good corrosion resistance. In comparison with before and after the salt spray test evaluation, it was confirmed that black and white rust occurred seriously after 72 hours in the case of the uncoated base metal, but almost no black and white rust occurred in the test coating coated with the UV curable coating. I could confirm it. It was confirmed that all of the corrosion resistance as a rust-preventive coating solution serving as a temporary rust preventive function of the galvalume steel sheet.
The photograph which photographed the surface of the test piece which concerns on Example 1 and Comparative Example 7 after 72 hours is shown in FIG.
(3) salt spray test of processing part
In order to evaluate the corrosion resistance after processing, the salt spray test and the steel sheet having a coating layer formed using the solution of Examples 1 to 3 and Comparative Examples 1 to 6 and a steel sheet without a coating layer were formed It was done in the same way. Corrosion resistance evaluation criteria are the same.
The steel sheets having the coating film formed by using the coating solution of Examples 1 to 3 and Comparative Examples 1 to 6 were all less than 5% of white rust was generated, it was confirmed that exhibits good corrosion resistance. In particular, in the case of Example 1, 2% level of white rust was generated and the corrosion resistance was good. The photograph which photographed the surface of the test piece which concerns on Example 1 and Comparative Example 7 after 72 hours is shown in FIG.
(4) tape peeling test
In addition, a widely used tape peel test was used to investigate the adhesion of the coating layer coated on the galvalume steel sheet surface. Powder coating was applied to the galvalume steel sheet coated with UV-curable hybrid coating, and then cross-cutted at intervals of 1 mm in 10 mm x 10 mm area, and the adhesion was evaluated as peeling of the coating layer when peeled off with 3M tape. It was.
As a result of the peel test, no peeling was observed in all the test pieces, indicating that excellent adhesion to the powder coating on the coating layer was shown. As a representative experimental result, a photograph of the surface of the test piece of Example 1 is shown in FIG. 5.
<Solution storage stability evaluation>
In order to evaluate the storage stability of the obtained organic-inorganic composite coating solution, after leaving the solution for 3 months, the storage stability of the solution was evaluated by checking the presence or absence of gel formation of the solution, and the results are shown in Table 2.
If there is no change in the solution it can be evaluated that the storage stability of the solution is excellent, when the gel is formed was evaluated as poor storage stability.
Accordingly, in Examples 1 to 3, no gel phase was observed in the solution, and the solution stability was good. However, in Comparative Examples 1 to 6, gel formation was observed in the solution, indicating that the solution stability was inferior. .
As can be seen from Table 1, it can be seen that the storage stability of the obtained organic-inorganic complex solution is very different depending on the blending ratio. It can be seen that the gel is formed in the solution as the amount of TPOZ is less, depending on the amount of TPOZ, which is a precursor for preparing a sol. This is due to the fact that when the amount of TPOZ is small, the silane coupling agent networking the inorganic and organic substances during the storage of the solution reacts with the oligomer and the monomer, which is an ultraviolet curable resin, to gel the resin.
From the above test results, the solutions of Examples 1 to 3 and Comparative Examples 1 to 6 exhibit good corrosion resistance as a temporary rust preventive solution in terms of corrosion resistance according to the content ratio of inorganic and organic, but the solution does not gel during storage. As a result, storage stability of the solution may not be secured, and thus it may be difficult to apply it in an actual process.
From these results, it can be seen that the UV-curable zirconium-based organic-inorganic composite solution provided by the present invention is suitable as a solution that can replace the chromate treatment for temporary rust prevention of the steel sheet. The coating solution provided by the present invention is an environmentally friendly solution that can replace the existing chromate solution, and by replacing the existing thermosetting process with a UV curing process in the steel manufacturing process, it is possible to suppress VOC generation and reduce energy, as well as to improve productivity. It is expected to contribute.
Claims (10)
15 to 30% by weight of an ultraviolet curable acrylic resin;
0.5 to 2 wt% photoinitiator; And
It contains a balance zirconium sol,
The UV-curable acrylic resin is a UV-curable organic-inorganic composite coating solution for forming a chromium-free coating of a galvanized steel sheet, which is a mixture of a bifunctional acrylic monomer and a trifunctional acrylic monomer.
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| KR100845403B1 (en) | 2007-04-16 | 2008-07-10 | 유창국 | Manufacturing method for organic-inorganic hybrid coating solution for ambient thermal polymerization |
| JP2008527413A (en) | 2004-12-30 | 2008-07-24 | スリーエム イノベイティブ プロパティズ カンパニー | High refractive index, durable hard coat |
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