KR100928798B1 - Chromium-free resin solution composition with improved alkali resistance and processability, surface treatment method and surface treated steel sheet using same - Google Patents

Abstract

The present invention provides a resin solution composition for steel sheet surface treatment, which has excellent corrosion resistance, alkali resistance, processability and conductivity, and chemical resistance, and does not contain any chromium components, a method for manufacturing a steel sheet using the same, and a surface-treated steel sheet prepared therefrom. It is about. The surface-treated steel sheet is a resin solution composition, a mixture of a soft urethane resin and a hard urethane resin, and one selected from the group consisting of Ti or Zr organic oxides, monoaluminum phosphates, aluminum dihydrogen phosphates, first zinc phosphate, and hydrated manganese phosphate. It is prepared by coating the resin solution composition containing the above materials and solvents on a steel sheet 300 to 1,800 mg / ㎡, wherein in the case of the resin solution composition, the urethane resin mixture is 10 to 90% by weight of the total solid of the solution composition, urethane In the resin composition, the amount of the soft urethane-based resin is 5 to 95% by weight, the amount of the hard urethane-based resin is 5 to 95% by weight, the Ti or Zr organic oxide is 1 to 20% by weight of the total solid of the resin solution composition, Mono aluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate and / or hydrated manganese phosphate It is present at 0.1 to 10.0% by weight of the total solids.

Surface treatment steel, anti-fingerprint steel plate, chromium free, corrosion resistance, alkali resistance

Description

Chromium free resin composition having good alkaline resistance and forming properties, method for surface treating steel sheet using the same and surface- treated steel sheet}

The present invention relates to a resin solution composition for steel sheet surface treatment, which is particularly excellent in alkali resistance and workability, and which does not contain any chromium component having excellent corrosion resistance, conductivity and chemical resistance, and a method for producing a steel sheet using the same and a surface-treated steel sheet prepared therefrom. It is about.

Recently, with increasing interest in environmental issues around the world, the use of environmental pollutants, ie, Cr, Pb, Cd, Hg, PBB, PBDE, etc., is being tightened. In particular, the Restriction of Hazardous Substances (RoHS) implemented by the EU (Restriction of Hazardous Substances, implemented in 6.7.1), Waste from Electrical and Electronic Equipment (WE6.7 implemented), and new environmental regulations. Typical examples include the Registration, Evaluation and Authorization of Chemicals (REACH) and End-of-Life Vehicles (ELV) enforcement (7.1.1). It is demanding active response to new environmental management policies, such as development, reduction of waste in factories and green procurement.

Conventionally, galvanized steel sheet and zinc-based alloy plated steel sheet, aluminum plated steel sheet, aluminum alloy plated steel sheet, cold rolled steel sheet, hot rolled steel sheet, etc., which are used for automobile materials, home appliances, building materials, etc., are provided with corrosion resistance and paint adhesion. In order to do this, a surface treatment method of coating a chromate coating mainly composed of chromium on the surface has been generally performed. The main chromate treatments include electrolytic chromate and coated chromate. Among them, electrolytic chromate treatment is composed of hexavalent chromium as a main component and a treatment solution containing various anions such as sulfuric acid, phosphoric acid, boric acid, and halogen. In general, a method of cathodic electrolysis of a metal plate is generally performed. On the other hand, in the coating type chromate treatment, a method in which an inorganic colloid and an inorganic ion are added to a solution in which a part of hexavalent chromium has been reduced to trivalent beforehand is used to deposit a metal plate therein, or to spray a treatment solution onto the metal plate. It is carried out by.

When using these methods, due to the toxicity of hexavalent chromium contained in the chromate treatment solution, various measures are required in the working environment and drainage treatment, and recycling and disposal of automobiles, home appliances, building products, etc. using the surface treatment metals. Treatment also causes human health and environmental pollution. In addition, in the case of applying trivalent chromium, there is a problem that a part of the trivalent chromium is converted to hexavalent chromium by the ambient environment such as temperature or microorganism.

Therefore, each steel company is focusing on developing a surface-treated steel sheet that does not contain hexavalent chromium and does not contain chromium that can satisfy various requirements such as corrosion resistance, alkali resistance and conductivity. Conventionally, after coating a metal salt film composed mainly of phosphate as a main component on the surface of a steel sheet, and then coating a resin based film composed mainly of acrylic, epoxy and urethane resin as a main component thereof, or manufacturing the secondary coating. The surface-treated metal steel sheet containing no chromium was prepared by forming a resin film and a secondary film, respectively.

However, these products often lower the electrical conductivity and weldability of the metal sheet according to the metal salt or the film thickness, and thus are not suitable for the use of electromagnetic wave suppression, internal noise suppression, and processability of copiers, printers, VCRs, and computers. There is a problem.

Also, in recent years, as most home appliances require surface-treated steel sheets that do not contain chromium having excellent conductivity, a coating steel sheet containing no chromium has been developed by coating only the first resin-based coating. However, unless the composition of the resin-based surface treatment composition is particularly excellent, there is a problem in that quality characteristics such as corrosion resistance are significantly lower than those of conventional chromium-treated or phosphate-treated base coated steel sheets. In recent years, however, major domestic and foreign home appliances manufacturers have established their own quality standards for materials and obtained quality certification for the development of environmentally friendly products for surface-treated steel sheets that do not contain chromium. I buy it.

Conventionally, Japanese Patent Application Laid-Open No. 8-92479 and Japanese Patent Application Laid-Open No. 8-500770 disclose a method of coating polyaniline on a metal plate as a coating method in consideration of conductivity without containing hexavalent chromium. However, since polyaniline having high rigidity and low adhesion exists between the metal and the resin film, the film can be easily peeled off from the polyaniline and the metal interface and the polyaniline and the resin interface. This causes a problem when the steel sheet is painted on top to impart designability, corrosion resistance and other functions. Low adhesion films are generally known to have low corrosion resistance. In addition, the solution stability is low, there is a lot of precipitates, a strong smell occurs, there is also a problem in the workability, such as inhibition of the overall working environment. In addition, by using a method of coating only the first coating with a resin on the galvanized layer, it showed an excellent effect of improving the characteristics such as conductivity, corrosion resistance, alkali resistance, high temperature, high humidity, etc. There is a problem that the resin layer and the plating layer of the processing friction portion is damaged in part, so that the resin layer is lost or the surface becomes black.

In addition, US Patent Publication No. 2004-54044 discloses a composition in which an organic film former, a hexafluoro complex such as titanium and zirconium, at least one inorganic compound, and the like are mixed with water, but it contains a fluoride complex. This may affect the environment, and the solution is acidic, so care must be taken when handling. In addition, Japanese Laid-Open Patent Publication No. 2002-030460 discloses a composition in which a vanadium compound, Zi, Ti, and the like are mixed with a mixed resin. There is a problem that must be accompanied. In addition, Korean Patent Publication No. 2006-76953 discloses an organic resin and an inorganic binder composite using a silane coupling agent and the like, and a surface treatment composition including a rust preventive agent and a metal chelating agent is disclosed, but an organic resin and an inorganic binder composite are disclosed. There is a disadvantage that must be prepared in advance. In addition, some products that require alkali resistance lacks alkali resistance, so that the resin layer is partially damaged when contacted with the alkaline solution, resulting in the loss of the resin layer or severe discoloration of the surface. In addition, Japanese Patent No. 3706518 discloses a resin composition containing a phosphate compound selected from organic resins, ammonium phosphate, sodium phosphate, and potassium phosphate. However, the purpose of using these phosphate compounds is to form a passivation layer on the upper part of the steel plate to improve corrosion resistance. It is limited to playing a role.

One object of the present invention is to provide a coating layer which does not contain chromium, which improves alkali resistance, processability, and is excellent in corrosion resistance, conductivity, chemical resistance, and the like, through a method of coating a resin solution composition on a steel sheet. It is for providing a surface treatment composition.

Another object of the present invention is to provide a surface-treated steel sheet coated with the surface treatment composition of the metal steel sheet.

Still another object of the present invention is to provide a method for producing a surface-treated steel sheet by forming a resin solution coating layer with the resin solution composition according to the present invention.

The object of the present invention is not limited to those mentioned above, and other objects that are not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, the present invention provides a resin solution composition applied to a steel sheet and / or a galvanized layer, a method for producing a surface-treated steel sheet using the same and a surface-treated steel sheet prepared by the above method,

As a first aspect of the present invention, a mixed urethane resin of a soft urethane resin and a hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate; And a solvent; a resin solution composition for surface treatment of a steel sheet, comprising:

As a 2nd viewpoint, mixed urethane resin of soft urethane resin and hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate; And a solvent; including, based on the solids of the total resin solution composition, 10 to 90% by weight of the mixed urethane resin; 1 to 20% by weight of Ti or Zr-based organic oxides; And 0.1 to 10.0 wt% of a compound selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate.

As a third aspect, the mixed urethane resin is a resin solution composition for surface treatment of a steel sheet, characterized in that composed of 5 to 95% by weight of a soft urethane resin and 5 to 95% by weight of a rigid urethane resin based on the urethane resin solid content,

As a fourth aspect, the soft urethane-based resin is a polyurethane solution prepared from isophorene diisocyanate, adipic acid, and polyhydric alcohol or a polyurethane solution resin composition for surface treatment of a steel sheet, characterized in that the polyurethane is prepared from polyisocyanate,

As a fifth aspect, the polyhydric alcohol is a resin solution composition for surface treatment of a steel sheet, characterized in that selected from acryl polyol, polyester polyol, polyether polyol, polyolefin-based polyol or a mixture thereof,

As a sixth aspect, the soft urethane resin has a number average molecular weight of 5,000 to 300,000, the resin solution composition for surface treatment of a steel sheet,

In a seventh aspect, the hard urethane-based resin is a polyurethane resin prepared from polycaprolactone polyol or polycarbonate polyol and diisocyanate, 4,4'-bis (ω-hydroxyalkyleneoxy) biphenyl and methyl-2, Resin solution composition for surface treatment of steel sheet, characterized in that it is selected from a polyurethane resin prepared from 6- diisocyanate hexanoate, and a polyurethane resin having an acetal bond,

As an eighth aspect, the hard urethane resin has a number average molecular weight of 200,000 to 2,000,000 resin solution composition for surface treatment of a steel sheet,

As a ninth aspect, the hard urethane resin has a Shore A hardness of 40 to 90, wherein the resin solution composition for surface treatment of a steel sheet,

As a tenth aspect, the diisocyanate is a paraphenylene diisocyanate, the resin solution composition for surface treatment of a steel sheet,

In an eleventh aspect, the Ti or Zr organic oxide is titanium diisopropoxide bis (acetylacetonate), titanium ortho ester, titanium (IV) butoxide, titanium (IV) (triethanolaminato) isopropoxide Tetrakis (triethanolaminato) zirconium (IV), titanium (IV) 2-ethylhexoxide, titanium (IV) isopropoxide, zirconium (IV) bis (diethyl citrato) -dipropoxide or these Resin solution composition for surface treatment of a steel sheet, characterized in that selected from a mixture of

As a twelfth aspect, the solvent is a resin solution composition for surface treatment of a steel sheet, characterized in that water,

In a thirteenth aspect, the solvent is an alkali solvent selected from alcohol solvents selected from ethanol, methanol, propanol, isopropanol and glycerol, amine compounds, N-methylpyrrolidone, sodium hydroxide, potassium hydroxide, sodium carbonate and ammonium hydroxide. A resin solution composition for surface treatment of a steel sheet, further comprising an aqueous solution or a mixture thereof,

As a fourteenth aspect, the resin solution composition for surface treatment of a steel sheet further comprises at least one or more of an additive consisting of a wetting agent, a crosslinking agent, a lubricant, and an antifoaming agent.

In a fifteenth aspect, at least one material selected from the group consisting of a mixed urethane resin of a soft urethane resin and a hard urethane resin, a Ti or Zr-based organic oxide, monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate and manganese hydrate hydrate And coating the resin solution composition containing a solvent on the upper surface of the steel sheet with a coating amount of 300 to 1,800 mg / m 2.

As a sixteenth aspect, Mixed urethane resin of soft urethane resin and hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate; And coating a resin solution composition comprising a solvent; and then coating the resin solution composition with an adhesion amount of 300 to 1,800 mg / m 2 on the upper portion of the steel sheet, based on the solids of the entire resin solution composition, 10 to 90 wt% of the mixed urethane resin; 1 to 20% by weight of Ti or Zr-based organic oxides; And 0.1 to 10.0 wt% of at least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate,

As a seventeenth aspect, the mixed urethane resin is a surface treatment method of a steel sheet, characterized in that composed of 5 to 95% by weight of a soft urethane resin and 5 to 95% by weight of a rigid urethane resin based on the urethane resin solids,

As a eighteenth aspect, the method of manufacturing a surface-treated steel sheet, further comprising the step of drying the steel sheet coated with a resin solution composition at a temperature PMT 80 ~ 200 ℃,

As a nineteenth aspect, the steel sheet is a cold rolled steel sheet, a galvanized steel sheet, a zinc-based electroplated steel sheet, a hot dip galvanized steel sheet, an aluminum plated steel sheet, a cobalt, molybdenum, tungsten, nickel, titanium, aluminum, manganese, iron, magnesium, Plated steel sheet containing tin, copper or a mixture of impurities or dissimilar metals thereof, aluminum alloy sheet containing silicon, copper, magnesium, iron, manganese, titanium, zinc or a mixture thereof, galvanized steel sheet coated with phosphate, Surface treatment method of the steel sheet, characterized in that selected from the group consisting of cold rolled steel sheet and hot rolled steel sheet,

As a twentieth aspect, the soft urethane-based resin has a number average molecular weight of 5,000 to 300,000, and is a surface treatment method of a steel sheet, characterized in that it is made from isophorene diisocyanate, adipic acid and polyhydric alcohol,

In a twenty-first aspect, the rigid urethane-based resin has a number average molecular weight of 200,000 to 2,000,000, and is a polyurethane resin prepared from polycaprolactone polyol or polycarbonate polyol and paraphenylene diisocyanate, 4,4'-bis (ω-hydride). A surface treatment method of a steel sheet, characterized in that it is selected from a polyurethane resin prepared from oxyalkyleneoxy) biphenyl and methyl-2,6-diisocyanatehexanoate, and a polyurethane resin having an acetal bond,

As a twenty-second aspect, the hard urethane resin has a Shore A hardness of 40 to 90, the surface treatment method of a steel sheet,

In a twenty-third aspect, or Zr organic oxide is selected from titanium diisopropoxide bis (acetylacetonate), titanium ortho ester, titanium (IV) butoxide, titanium (IV) (triethanolaminato) isopropoxide, tetra Keith (triethanolaminato) zirconium (IV), titanium (IV) 2-ethylhexoxide, titanium (IV) isopropoxide, zirconium (IV) bis (diethyl citrato) -dipropoxide or mixtures thereof Surface treatment method of the steel sheet, characterized in that selected from

In a twenty-fourth aspect, the solvent is water, the surface treatment method of a steel sheet,

In a twenty-fifth aspect, the solvent is an alkaline aqueous solution selected from alcohol solvents selected from ethanol, methanol, propanol, isopropanol and glycerol, amine compounds, N-methylpyrrolidone, sodium hydroxide, potassium hydroxide, sodium carbonate and ammonium hydroxide or Surface treatment method of the steel sheet, characterized in that it further comprises a mixture thereof,

In a twenty-sixth aspect, a steel sheet; And a resin solution coating layer, wherein the resin solution coating layer comprises a mixture of a soft urethane resin and a hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate; Surface-treated steel sheet, characterized in that the coating solution with a coating weight of 300 to 1,800 mg / ㎡ after drying the resin solution composition comprising a solvent;

In a twenty-seventh aspect, a steel sheet; And a resin solution coating layer, wherein the resin solution coating layer comprises a mixture of a soft urethane resin and a hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate; And a solvent; wherein the amount of the urethane resin is 10 to 90% by weight based on the total solids of the solution composition, the amount of the soft urethane resin is 5 to 95% by weight based on the total amount of the urethane resin, and the amount of the hard urethane resin is the urethane resin 5 to 95% by weight relative to the total amount of, Ti or Zr-based organic oxide is 1 to 20% by weight, at least one selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate and hydrated manganese phosphate The material is provided with a surface-treated steel sheet, characterized in that the resin solution composition of 0.1 to 10.0% by weight is coated on the steel sheet with an adhesion amount of 300 to 1,800 mg / ㎡.

As described above, the metal surface treatment composition and the surface treated steel sheet having the coating layer which is excellent in alkali resistance and corrosion resistance and do not contain chromium component are excellent in workability, conductivity, water deterioration resistance, solution stability, etc. It can be easily used as a material for processing.

Hereinafter, the present invention will be described in detail.

The present invention provides a mixture of a soft urethane resin and a hard urethane resin, at least one material selected from the group consisting of a corrosion resistant hardener composed of Ti or Zr organic oxides, monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate and manganese hydrate hydrate. By coating a resin solution composition containing no chromium composed of a solvent on a plated or unplated steel sheet, the surface for improving the alkali resistance and workability and producing a metal sheet having excellent conductivity, corrosion resistance, chemical resistance, etc. It relates to a resin solution composition for treatment.

In the resin solution composition of the present invention, a mixed urethane resin of the soft urethane resin and the hard urethane resin is used. Since the urethane resin has strong water resistance, chemical resistance, acid resistance and alkali resistance, and the coating film is soft and strong, It is used to prevent scratches of the surface by painting on steel sheets or aluminum plates, or is widely used to impart chemical resistance.

The said mixed urethane resin is 10 to 90 weight% with respect to solid content of the whole resin solution composition in solid content concentration. When the solids content of the entire urethane-based resin is less than 10% by weight, the chemical resistance against the saline resistance of the urethane resin and the penetration of chemicals against the penetration of corrosion ions is not exhibited, and thus the chemical resistance and the alkali resistance decrease. For this reason, when degreasing at 60 ° C. for 5 minutes with an alkaline solution having a pH of 10 or more, there is a problem of discoloration or peeling of the resin film, and if it exceeds 90% by weight, solution stability due to entanglement is lowered and the price increases. have.

However, since the urethane resin alone has limitations in implementing soft and strong properties, the present invention uses a mixed urethane resin in which a soft urethane resin and a hard urethane resin are mixed. The soft urethane resin is 5 to 95% by weight based on the solid content concentration of the mixed urethane resin. If the solid content concentration of the flexible urethane resin is less than 5% by weight, the workability is improved, but heat resistance and water deterioration resistance are lowered, and if it is 95% by weight or more, there is a problem in that the workability is not improved and corrosion resistance is greatly reduced.

In addition, the molecular weight of the soft urethane-based resin is preferably 5,000 to 300,000. If the molecular weight of the said soft urethane resin is 5,000 or less, workability will fall largely, and if it is 300,000 or more, there exists a problem that stability of a solution reduces.

The flexible urethane-based resins include polyurethane dispersion resins, polyurethane resins made from isophorene diisocyanates such as polyethylene-modified polyurethane resins, adipic acid and polyhydric alcohols, and acrylic-urethane resins, polyethylene-acrylic-modified polyurethane resins, and the like. Polyurethane resins prepared from acrylic polyols and polyisocyanates can be used. Here, as said polyhydric alcohol, an acryl polyol, polyester polyol, polyether polyol, polyolefin polyol, etc. can be used.

In addition, the molecular weight of the rigid urethane-based resin is preferably 200,000 to 2,000,000. If the molecular weight of the rigid urethane resin is 200,000 or less, there is no effect of improving workability, and if it is 2,000,000 or more, the stability of the solution decreases and the viscosity of the resin solution rises, thereby degrading workability.

The hard urethane-based resins are polycaprolactone polyols or polycarbonate polyols and isocyanates, in particular, polyurethane resins prepared from paraphenylene diisocyanate, 4,4'-bis (ω-hydroxyalkyleneoxy) biphenyl and methyl Polyurethane resins prepared from -2,6-diisocyanate hexanoate, polyurethane resins having acetal bonds, and the like can be used.

In addition, the hard urethane-based resin is preferred to use a Shore (Shore) A hardness of 40 to 90 when manufacturing a dry film. If the Shore A hardness is less than 40, the workability is not improved. If the Shore A hardness is more than 90, the coating film becomes too hard and is crushed during processing. Therefore, it is preferable to have the hardness in the above range.

Ti or Zr organic oxide is added to the urethane resin as a corrosion resistant hardener. As said corrosion-resistant hardening | curing agent, it is 1 to 20 weight% based on solid content of the whole resin solution composition. At this time, if the content of the anti-corrosion hardener is less than 1% by weight, the corrosion resistance is reduced and there is almost no additive effect. When the content of the anti-corrosion curing agent is more than 20% by weight, the concentration is saturated and a large amount of precipitate is generated, and the solution stability is lowered. The problem of decreasing hydrothermal deterioration appears.

Preferred examples of the Ti or Zr organic oxide include titanium diisopropoxide bis (acetylacetonate), titanium ortho ester, titanium (IV) butoxide, titanium (IV) (triethanol aminato) isopropoxide, Tetrakis (triethanolaminato) zirconium (IV), titanium (IV) 2-ethylhexoxide, titanium (IV) isopropoxide, zirconium (IV) bis (diethyl citrato) -dipropoxide and the like. It may comprise at least one compound selected from them.

In addition, the resin composition for surface treatment of the steel sheet of the present invention includes a material selected from one or more from monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, manganese hydrate phosphate and the like. These materials are added to improve the adhesion between the resin and the steel sheet, in particular the galvanized layer, and can form a passive film on the zinc layer to improve the corrosion resistance and at the same time can be expected to improve the conductivity and heat resistance by the metal salt effect.

Substances such as monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate are preferably added in an amount of 0.1 to 10.0% by weight based on the total solid content of the resin composition. When these substances are added at 0.1 wt% or less, the adhesion to the steel sheet is lowered, so that the resin is more likely to be peeled off in a process such as alkali degreasing. It is not preferable because it promotes an entanglement of and lowers the solution stability and lowers the adhesion between the resin and the steel sheet.

Components except the solids in the resin solution composition is a solvent, water may be used as the solvent. Furthermore, in order to enhance the properties such as wettability and dispersibility of the coating composition, a separate alcohol solvent and an alkaline aqueous solution may be further added. Ethanol, methanol, propanol, isopropanol, glycerol, and the like may be used as the alcohol solvent, and as the alkaline aqueous solution, an amine compound, N-methylpyrrolidone, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium hydroxide, or the like may be used. Can be.

Since the resin solution composition is dispersed in the particles of the corrosion-resistant curing agent uniformly reacts with the organic functional group of the resin, the stability of the resin solution is excellent and the corrosion resistance, conductivity, alkali resistance, high temperature and high humidity resistance of the anticorrosive coating layer is further improved. Effect.

In addition, the surface treatment composition of the present invention may further include one or more additives such as a wetting agent, a crosslinking agent, a lubricant, and an antifoaming agent. The wetting agent is effective in streaking and adhesion, the crosslinking agent in corrosion resistance and alkali resistance, the lubricant in friction coefficient and processability, and the antifoaming agent in further improving workability. These additives are preferably used in an amount of 5 to 25% by weight based on the solids content of the resin solution composition. If the content of the additive is less than 5% by weight, the use of additives such as corrosion resistance, alkali resistance does not appear, and if the content exceeds 25% by weight, the effect is saturated, and further addition is not meaningful, and there is a problem of reducing solution stability.

The wetting agent includes a deagglomerated wet dispersant, a polymer wet dispersant, and the like. Examples of the wetting agent include a wet dispersant commercially available from EFKA and Tego, and the like. EFKA 3580 (Ciba) and BW-W500 (Bumwoo Chemical) Or WET 500 (Ciba).

Examples of the crosslinking agent include vinylsilane, methoxysilane, acrylicsilane, epoxysilane, chlorosilane, alkoxysilane, silazane, silylating agent, melamine, melamine resin, alkylmelamine, alkylmelamine resin, fluorinated melamine and fluorinated melamine resin, and polyamine type. , Alkylated aromatic polyamine-based, polyamide-based or acid-anhydride-based curing agents and the like can be used.

The lubricant includes silicone wax, polyethylene wax, polypropylene wax, amide wax, polytetrafluoroethylene (PTFE) wax, paraffin wax, and the like.

The antifoaming agent may be an oil type, a modified type, a solution type, a powder type, or an emulsion type silicone antifoaming agent.

The coating weight of the coating layer coated with the composition of the resin solution of the present invention is preferably 300 to 1,800 mg / m2 as the coating weight after drying, and the drying temperature (PMT) is 80 ° C to 200 ° C which is similar to the drying temperature of a conventional resin-based surface treatment solution. to be. At this time, if the adhesion amount after drying is 300 mg / m 2 or less, there is no effect of improving the corrosion resistance and workability. In addition, the higher the drying temperature shows a tendency to improve the corrosion resistance of the resin film, but if the 80-200 ℃ is not unreasonable to meet the customer's quality requirements.

Further, the applicable metal sheet of the present invention may be a galvanized steel sheet, a zinc nickel plated steel sheet, a galvanized steel sheet, a zinc titanium plated steel sheet, a zinc magnesium plated steel sheet, a zinc manganese plated steel sheet, or a zinc-based electroplated steel sheet, such as a zinc aluminum plated steel sheet. Plated steel sheet, aluminum plated steel sheet, and plated steel sheet containing, for example, cobalt, molybdenum, tungsten, nickel, titanium, aluminum, manganese, iron, magnesium, tin, copper, etc., as dissimilar metals or impurities in these plating layers. Galvanized steel sheet in which inorganic materials such as silica and alumina are dispersed in these plating layers, or an aluminum alloy sheet containing silicon, copper, magnesium, iron, manganese, titanium, zinc, or the like, or a galvanized steel sheet coated with phosphate, cold rolled steel sheet, hot rolled steel Steel plate or the like. Moreover, it is applicable also to the multilayer plating board which processed two or more types sequentially during said plating.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited by the following examples.

[Example 1-13 and Comparative Example 1-14]

1-1. Preparation of Resin Solution Composition

As the monomer of the flexible urethane resin, a urethane resin having a number average molecular weight of 100,000 composed of isophorene diisocyanate, adipic acid, and a polyhydric alcohol monomer was prepared. As a monomer of the hard urethane resin, an acrylic resin having a number average molecular weight of 1,000,000 was prepared from a paraphenylene diisocyanate and a polycarbonate polyol monomer. As the corrosion resistant hardener, Ti organic oxide (trade name Tyzor TE® titanium (IV) (triethanol aminato) isopropoxide) was used. Aluminum phosphate dihydrogen phosphate was used for aluminum phosphate. At this time, the quality characteristics of the soft urethane resin and the hard urethane resin, Ti corrosion-resistant curing agent, aluminum dihydrogen phosphate, and other additives were adjusted as shown in Table 1.

The additives include 10% by weight of colloidal silica (Snowtex-40 by Nissan Chemical), 0.5% by weight of siloxane-based wetting agent (Ciba EFKA 3580), silane-based crosslinking agent (Aldrich, 3-glycidoxy propyl trimethoxy silane) ) 1.2% by weight, amine-based curing agent (Cytec Cymel 303) 2.5% by weight, polyethylene-based lubricant (Noveon Lanco PE 1500) 1.5% by weight were added in bulk. Solid content concentration of the surface treatment composition was about 15% by weight. For reference, water was used as the main component except solids, and about 3% by weight of ethanol and about 0.5% by weight of amine compound were added as an alkaline solvent.

1-2. Manufacture of Coated Steel Sheet

1) Specimen: An electro galvanized steel sheet (EG) having an adhesion amount of 20 g / m 2 on one side was used as a material steel sheet for applying the surface treatment composition.

2) Coating method: The resin solution was coated on the top of the sample using a continuous roll coating simulator, and dried under PMT conditions as shown in Table 1. The deposition amount of the film was 1,000 mg / m 2.

1-3. Performance Evaluation Method

(1) Machinability: After measuring the friction coefficient using a drawbead friction tester (load 1,000kgf, speed 1,000mm / min, distance 100mm), the resin film of the specimen was scratched on the bead surface of the friction tester and damaged. The evaluation was made according to the following criteria.

○: less than 5% damage area

△: damage area of 5% or more but less than 10%

×: damage area 10% or more

(2) Corrosion resistance: The specimens were subjected to a salt spray test according to JIS-Z2371 for 96 hours, and the degree of corrosion was evaluated according to the following criteria.

○: 5% or less white blue

△: more than 5% of white rust less than 20%

×: 20% or more of white blue

(3) Conductivity: The surface of the specimen coated with resin coating was measured by a surface resistance meter (Loresta-GP), and evaluated according to the following criteria.

○: Surface resistance 1mΩ or less

△: surface resistance 1Ω or less

×: extremely poor conductivity or weldability with surface resistance of 1Ω or more

(4) Alkali resistance: After washing with water for 5 minutes by dipping in alkaline solution (Gardoclean 4292L, pH12), the color difference and peeling degree of the resin coating layer were visually observed and evaluated by the following criteria.

○: no peeling, color difference change 2.0 or less

△: no peeling, color difference change 2.0 or more occurs

×: Peeling occurrence

(5) Water deterioration resistance: After immersion in water for 30 minutes, the color difference after reciprocating friction 30 times with a finger was measured and evaluated by the following criteria.

○: color difference 1.0 or less

△: 1.0 or more color difference

×: Peeling occurrence

(6) Solution stability: After 100 days of leaving 100g of the surface treatment composition in an oven at 50 ℃, the degree of precipitation, gelation and separation of the solution was evaluated according to the following criteria.

○: No precipitation, gelation or separation

△: One of fine precipitation, gelation and separation

×: at least one of precipitation, gelation and separation occurs to some extent

The evaluation results are shown in Table 1 below.

Resin / Hardener Solid Composition (%) Other additives Quality characteristic Urethane Resin (Flexible / Hard Mixing Ratio) Ti hardener Dihydrogen Phosphate Aluminum  Machinability  Corrosion resistance  conductivity Alkali resistance Water resistance Solution stability     Example One 10 (90/10) 10 2 5 ○ ○ ○ ○ ○ ○ 2 10 (70/30) 10 3 5 ○ ○ ○ ○ ○ ○ 3 20 (30/70) 10 4 5 ○ ○ ○ ○ ○ ○ 4 20 (30/70) 10 5 5 ○ ○ ○ ○ ○ ○ 5 20 (50/50) 10 One 5 ○ ○ ○ ○ ○ ○ 6 30 (40/60) 10 2 5 ○ ○ ○ ○ ○ ○ 7 30 (5/95) 5 3 5 ○ ○ ○ ○ ○ ○ 8 30 (80/20) 10 4 5 ○ ○ ○ ○ ○ ○ 9 50 (10/90) 10 5 5 ○ ○ ○ ○ ○ ○ 10 50 (10/90) 10 One 5 ○ ○ ○ ○ ○ ○ 11 25 (50/50) 5 4 5 ○ ○ ○ ○ ○ ○ 12 70 (40/60) 10 5 10 ○ ○ ○ ○ ○ ○ 13 30 (40/60) 8 4 2 ○ ○ ○ ○ ○ ○     Comparative example One 5 (90/10) 5 0 5 × × ○ △ × ○ 2 10 (100/0) 10 One 5 △ ○ ○ ○ × ○ 3 30 (3/97) 10 2 5 △ ○ ○ ○ ○ ○ 4 20 (50/50) 0 2 20 △ × × △ △ ○ 5 25 (50/50) 0 0 8 △ × △ × × ○ 6 30 (80/20) 2 5 8 ○ × △ ○ ○ ○ 7 20 (50/50) 8 20 2 ○ △ ○ ○ △ × 8 25 (45/55) 8 0 2 ○ × ○ × △ ○ 9 Epoxy resin 5 5 5 △ △ ○ △ ○ △ 10 Vinyl resin 5 5 5 × △ ○ ○ ○ ○ 11 Ester Resin 5 5 5 △ △ ○ ○ ○ ○ 12 20 (30 / acrylic resin 70) 5 5 5 △ △ △ △ ○ ○ 13 30 (40/60) 8 Ammonium Phosphate 5 5 △ ○ ○ △ ○ ○ 14 30 (40/60) 8 Phosphoric Acid 5 5 △ ○ ○ △ ○ ×

[Examples 14-19 and Comparative Examples 15-17]

2-1. Manufacture of Coated Steel Sheet

1) Specimen: An electro galvanized steel sheet (EG) having an adhesion amount of 20 g / m 2 on one side was used as a material steel sheet for applying the surface treatment composition.

2) Application method: Example The application of the pretreatment solution was immersed in the pretreatment solution for 3 seconds and then dried under PMT conditions as shown in Table 2.

In addition, the resin solution of the Example was prepared in the composition of Example 4 of Table 1, the resin solution composition was applied to the upper portion of the steel sheet using a continuous roll coating simulator, and dried in the adhesion amount and PMT conditions as shown in Table 2.

2-3. Performance Evaluation Method

The workability, conductivity and corrosion resistance of the specimen prepared under the above conditions were evaluated by applying the evaluation method shown in [Table 1].

2-4. Evaluation results

Table 2 shows the performance of the metal surface treatment composition under the above conditions.

Resin treatment condition Quality characteristic Amount of Attachment (mg / ㎡) PMT (℃) Machinability conductivity Corrosion resistance Example 14 1,000 180 ○ ○ ○ Example 15 500 180 ○ ○ ○ Example 16 800 180 ○ ○ ○ Example 17 1,500 180 ○ △ ○ Example 18 1,000 120 ○ ○ ○ Example 19 1,200 150 ○ ○ ○ Comparative Example 15 200 180 × ○ × Comparative Example 16 2,000 180 ○ × ○ Comparative Example 17 1,000 110 × ○ ×

As described in Table 2, the surface-treated steel sheets of Examples 14 to 19 according to the present invention showed excellent quality characteristics, but Comparative Examples 17 to 19 showed deteriorated characteristics.

1 is a schematic structural diagram of a steel sheet manufactured by applying a resin solution coating layer as an example of the present invention.

Figure 2 compares the degree of surface damage after evaluating the processing characteristics of one embodiment of the present invention and the existing invention material with a draw bead friction tester.

Figure 3 compares the degree of surface appearance after evaluating the alkali resistance characteristics of one embodiment of the present invention and the existing invention with a degreasing solution.

Claims (27)

Mixed urethane resins of the soft urethane resin and the hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate; And a solvent; and a resin solution composition for surface treatment of a steel sheet. Mixed urethane resins of the soft urethane resin and the hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate; And solvents; 10 to 90% by weight of the mixed urethane resin based on the solids content of the total resin solution composition; 1 to 20% by weight of Ti or Zr-based organic oxides; And 0.1 to 10.0 wt% of a compound selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate. The resin solution composition for surface treatment of a steel sheet according to claim 2, wherein the mixed urethane resin is composed of 5 to 95% by weight of a soft urethane resin and 5 to 95% by weight of a hard urethane resin based on the urethane resin solid content. The steel sheet according to any one of claims 1 to 3, wherein the soft urethane-based resin is a polyurethane made from isophorene diisocyanate, adipic acid and polyhydric alcohol or a polyurethane made from acrylic polyol and polyisocyanate. Resin solution composition for surface treatment of a resin. The resin solution composition for surface treatment of a steel sheet according to claim 4, wherein the polyhydric alcohol is selected from acryl polyol, polyester polyol, polyether polyol, polyolefin polyol or a mixture thereof. The resin solution composition for surface treatment of a steel sheet according to claim 4, wherein the soft urethane resin has a number average molecular weight of 5,000 to 300,000. 4. The hard urethane resin according to any one of claims 1 to 3, wherein the hard urethane resin is a polyurethane resin, 4,4'-bis (ω-hydroxyalkylene) prepared from polycaprolactone polyol or polycarbonate polyol and diisocyanate. A resin solution composition for surface treatment of a steel sheet, characterized in that it is selected from a polyurethane resin prepared from oxy) biphenyl and methyl-2,6-diisocyanate hexanoate, and a polyurethane resin having an acetal bond. 8. The resin solution composition for surface treatment of a steel sheet according to claim 7, wherein the hard urethane resin has a number average molecular weight of 200,000 to 2,000,000. The resin solution composition for surface treatment of a steel sheet according to claim 7, wherein the hard urethane resin has Shore A hardness of 40 to 90. 8. The resin solution composition for surface treatment of a steel sheet according to claim 7, wherein the diisocyanate is paraphenylene diisocyanate. The method of claim 1, wherein the Ti or Zr organic oxide is titanium diisopropoxide bis (acetylacetonate), titanium ortho ester, titanium (IV) butoxide, titanium (IV) (Triethanol aminato) isopropoxide, tetrakis (triethanol aminato) zirconium (IV), titanium (IV) 2-ethylhexoxide, titanium (IV) isopropoxide, zirconium (IV) bis (diethyl sheet Rato) -dipropoxide or a mixture thereof, the resin solution composition for surface treatment of a steel sheet. The resin solution composition for surface treatment of a steel sheet according to any one of claims 1 to 3, wherein the solvent is water. 13. The aqueous solution of claim 12, wherein the solvent is an alcohol solvent selected from ethanol, methanol, propanol, isopropanol and glycerol, an amine compound, N-methylpyrrolidone, sodium hydroxide, potassium hydroxide, sodium carbonate and ammonium hydroxide. Or a resin solution composition for surface treatment of a steel sheet, characterized in that it further comprises a mixture thereof. The resin solution composition for surface treatment of a steel plate according to any one of claims 1 to 3, further comprising at least one or more of an additive consisting of a wetting agent, a crosslinking agent, a lubricant, and an antifoaming agent. Mixed urethane resin of soft urethane resin and hard urethane resin, Ti or Zr organic oxide, monoaluminum phosphate, aluminum dihydrogen phosphate, at least one phosphoric acid compound and solvent selected from the group consisting of first zinc phosphate and manganese phosphate hydrate Method of surface treatment of the steel sheet comprising the step of coating the resin solution composition to the coated steel 300 to 1,800 mg / ㎡ after drying the upper portion. Mixed urethane resins of the soft urethane resin and the hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate; And comprising a step of coating a resin solution composition comprising a solvent; and then coated with an adhesion amount of 300 to 1,800 mg / ㎡ on the steel sheet, 10 to 90% by weight of the mixed urethane resin based on the solids content of the total resin solution composition; 1 to 20% by weight of Ti or Zr-based organic oxides; And 0.1 to 10.0 wt% of at least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, first zinc phosphate, and hydrated manganese phosphate. 17. The method of claim 16, wherein the mixed urethane resin is composed of 5 to 95% by weight of a soft urethane resin and 5 to 95% by weight of a hard urethane resin based on the urethane resin solid content. 18. The surface treatment method according to any one of claims 15 to 17, further comprising drying the steel sheet coated with the resin solution composition at a temperature of PMT 80 to 200 ° C. 18. The method according to any one of claims 15 to 17, wherein the steel sheet is a cold rolled steel sheet, a galvanized steel sheet, a zinc-based electroplated steel sheet, a hot dip galvanized steel sheet, an aluminum plated steel sheet, or a coating layer with cobalt, molybdenum, tungsten, nickel, titanium , Aluminum, manganese, iron, magnesium, tin, copper or a plated steel sheet containing impurity or dissimilar metals thereof, or aluminum alloy sheet containing silicon, copper, magnesium, iron, manganese, titanium, zinc or a mixture thereof And a phosphate coated zinc plated steel sheet, a cold rolled steel sheet and a hot rolled steel sheet. 18. The method according to any one of claims 15 to 17, wherein the flexible urethane resin has a number average molecular weight of 5,000 to 300,000 and is selected from polyurethane or acrylic polyol and polyisocyanate prepared from isophorene diisocyanate, adipic acid and polyhydric alcohol. Surface treatment method of the steel sheet, characterized in that the polyurethane produced. 18. The polyurethane resin according to any one of claims 15 to 17, wherein the rigid urethane resin has a number average molecular weight of 200,000 to 2,000,000, and is a polyurethane resin prepared from polycaprolactone polyol or polycarbonate polyol and paraphenylene diisocyanate. And a polyurethane resin prepared from 4'-bis (ω-hydroxyalkyleneoxy) biphenyl and methyl-2,6-diisocyanatehexanoate, and a polyurethane resin having an acetal bond. Surface treatment method of steel sheet. 22. The method of claim 21, wherein the rigid urethane resin has Shore A hardness of 40 to 90. 18. The method of claim 15, wherein the Ti or Zr organic oxide is titanium diisopropoxide bis (acetylacetonate), titanium ortho ester, titanium (IV) butoxide, titanium (IV) (Triethanol aminato) isopropoxide, tetrakis (triethanol aminato) zirconium (IV), titanium (IV) 2-ethylhexoxide, titanium (IV) isopropoxide, zirconium (IV) bis (diethyl And citrate) -dipropoxide or mixtures thereof. 18. The method for surface treatment of a steel sheet according to any one of claims 15 to 17, wherein the solvent is water. The aqueous alkali solution of claim 24, wherein the solvent is an alcohol solvent selected from ethanol, methanol, propanol, isopropanol and glycerol, an amine compound, N-methylpyrrolidone, sodium hydroxide, potassium hydroxide, sodium carbonate and ammonium hydroxide. Or a surface treatment method of a steel sheet, characterized in that it further comprises a mixture thereof. Steel plate; And a resin solution coating layer; consisting of, the resin solution coating layer A mixture of a soft urethane resin and a hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, zinc zinc phosphate, and hydrated manganese phosphate; And menstruum; Surface-treated steel sheet characterized in that the resin solution composition comprising a coated with a coating amount of 300 to 1,800 mg / ㎡ after drying on the upper steel sheet. Steel plate; And a resin solution coating layer; consisting of, the resin solution coating layer A mixture of a soft urethane resin and a hard urethane resin; Ti or Zr-based organic oxides; At least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, zinc zinc phosphate, and hydrated manganese phosphate; And menstruum; It includes, the amount of the urethane resin is 10 to 90% by weight based on the total solid content of the solution composition, the amount of the soft urethane-based resin is 5 to 95% by weight relative to the total amount of the urethane resin, the amount of the hard urethane-based resin to the total amount of the urethane resin 5 to 95% by weight, Ti or Zr-based organic oxide is 1 to 20% by weight, at least one material selected from the group consisting of monoaluminum phosphate, aluminum dihydrogen phosphate, zinc zinc phosphate and manganese phosphate hydrate 0.1 The surface-treated steel sheet, characterized in that the resin solution composition of 1 to 10.0% by weight is coated on the upper surface of the steel sheet with an adhesion amount of 300 to 1,800 mg / m 2.

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