Surface treatment solution composition, galvanized steel sheet manufactured using same, and manufacturing method thereof

Abstract

The present invention relates to a surface treatment solution composition of a zinc alloy-plated steel sheet widely used as a material for automobiles, home appliances, construction, and the like, a zinc alloy-plated steel sheet surface-treated using same, and a manufacturing method thereof.

Description

Surface treatment solution composition, zinc-plated steel sheet manufactured using the same, and method for manufacturing the same

[0001] The present invention relates to a surface treatment solution composition for zinc alloy plated steel sheets, which are widely used as materials for automobiles, home appliances, construction, etc., a zinc alloy plated steel sheet surface-treated using the same, and a method for manufacturing the same.

[0002] To prevent corrosion of the substrate steel, galvanized steel sheets utilizing sacrificial methods, such as zinc, zinc-iron, and zinc-magnesium-aluminum alloys, have been developed and are in use. Due to the active ionization reaction of zinc, white rust, a zinc oxide on the surface, is prone to occur when the surface plating layer is exposed to general corrosive environments, particularly in humid atmospheres. If zinc oxidation occurs rapidly, the loss of the plating layer reduces the corrosion resistance period of the substrate steel and causes aesthetic problems.

[0003] To solve these problems, conventionally, an organic film was formed after a pretreatment film was formed on the metal surface as part of the anti-corrosion treatment. Corrosion resistance and resistance to blackening have been secured by applying hexavalent chromium or chromate treatment to plated steel plates to form the pretreatment film. However, worker safety was a concern due to heavy metals such as hexavalent chromium contained in the pretreatment agent, and environmental pollution was a serious problem because chromium ions leached out during use or disposal of chromate-treated plated steel plates.

[0004] To address these issues, chromium-free methods have been proposed as alternatives to hexavalent chromium; however, they have been found to be unable to provide sufficient corrosion resistance and blackening resistance. Consequently, a commercially viable alternative is the trivalent chromate coating using trivalent chromium (Patent Document 1). However, trivalent chromium was listed as an SVHC substance in 2010 and a regulated substance in 2013 as a suspected carcinogen, mutagenic, respiratory and skin sensitizing, and reproductive toxicant, and has been used since 2017 following its approval. In 2020, the European Commission issued approvals for five uses for trivalent chromium, including plating and surface treatment agents; however, given the possibility that trivalent chromium may become subject to regulation in the future, the development of chromium-free products is necessary.

[0005] Therefore, there is a need for a method that can secure the corrosion resistance and processability of zinc-plated steel sheets without containing chromium.

[0006] (Patent Document 1) Korean Published Patent Application No. 10-2020-0064580

[0007] According to an embodiment of the present invention, a surface treatment composition for a zinc-plated steel sheet that can secure excellent corrosion resistance without using chromium, an environmental pollutant, and a zinc-plated steel sheet using the same and a method for manufacturing the same can be provided.

[0008] The problems of the present invention are not limited to those described above. A person skilled in the art to which the present invention pertains will have no difficulty understanding additional problems of the present invention from the overall contents of this specification.

[0009] A surface treatment solution composition according to one embodiment of the present invention is,

[0010] It includes solids and solvent,

[0011] Based on 100 weight%, the above solid content comprises 80 to 95 weight% of an organic-inorganic composite resin, 0.2 to 10 weight% of a metal chelate, and 10 weight% or less (including 0%) of an additive, and

[0012] The Si and N included in the above organic-inorganic composite resin may satisfy the conditions of the following relationship 1.

[0013] [Relationship 1]

[0014] log [Si / N]: 2.5~10

[0015] The above Si and N are the content (at.%) of Si and N contained in the resin.

[0016] The above organic-inorganic composite resin comprises an organosilicon compound, and the organosilicon compound is among bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,9-bis(trimethoxysilyl)nonane, bis(trimethoxysilylpropyl)amine, bis(triethoxysilylpropyl)amine, bis(trimethoxysilylmethyl)amine, bis(triethoxysilylmethyl)amine, bis(trimethoxysilylpropyl)amine, and bis(triethoxysilylpropyl)amine. It may be of type 1 or two or more types.

[0017] The above organic-inorganic composite resin includes a polymer resin, and the polymer resin may be a modified urethane acrylic resin.

[0018] The above modified urethane acrylic resin may be included in an amount of 5 to 30 weight percent based on 100 weight percent of the solid content of the surface treatment composition.

[0019] The above organic-inorganic composite resin comprises a silane coupling agent, and the silane coupling agent may be one or more selected from vinyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycyloxypropyltriethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, N-2-(aminoethyl))-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 2-perfluorooctylethyltrimethoxysilane.

[0020] The above metal chelate may be one or more chelating agents selected from the group consisting of silane-based, titanium-based, and zirconium-based chelating agents.

[0021] The above silane-based chelating agent may include vinyl trimethoxysilane, 3-glycyloxyproc trimethoxysilane, 3-glycyloxypropyl triethoxysilane, 3-glycyloxyproc trimethoxysilane, N-2-(aminoethyl))-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and mixtures thereof.

[0022] The above titanium-based chelating agent may include titanium acetylacetonate, iso-butoxytitanium ethyl acetoacetate, tetraisopropyl titanate, tetranormal butyl titanate, and mixtures thereof.

[0023] The above zirconium-based chelating agent may include tetranormal-propyl zirconate, tetranormal-butyl zirconate, sodium, potassium, lithium, and ammonium salts of zirconium carbonate, triethanolamine zirconate, hexafluorozirconate, and mixtures thereof.

[0024] A zinc-plated steel sheet according to another embodiment of the present invention is,

[0025] Steel sheet;

[0026] A zinc-based plating layer formed on at least one surface of the above-mentioned base steel plate; and

[0027] It includes a film layer formed on the above zinc-based plating layer, and

[0028] The above film layer comprises, in weight percent of the film layer itself, 80 to 95 weight percent of an organic-inorganic composite resin, 0.2 to 10 weight percent of a metal chelate, and 10 weight percent or less (including 0%) of an additive, and the Si and N included in the organic-inorganic composite resin may satisfy the conditions of the following relationship 1.

[0029] [Relationship 1]

[0030] log [Si / N]: 2.5~10

[0031] The above Si and N are the content (at.%) of Si and N contained in the resin.

[0032] The thickness of the above film layer may be 0.2 to 10 μm.

[0033] The above zinc-based plating layer may be any one of a hot-dip galvanized layer (GI), an alloyed zinc plating layer (GA), and a ternary zinc alloy plating layer of Zn-Al-Mg.

[0034] A method for manufacturing a zinc-plated steel sheet according to another embodiment of the present invention is,

[0035] A step of coating the surface treatment solution composition described above onto a zinc-plated steel sheet having a zinc-based plating layer formed thereon; and

[0036] The method may include the step of drying the above-mentioned coated surface treatment solution composition to form a film layer.

[0037] The adhesion amount of the surface treatment solution composition during the above coating is 250 mg / m² 2 Up to 1500 mg / m² 2 It can be done with the amount of attachment.

[0038] The above drying can be performed at a temperature of 70 to 150°C based on the final reached temperature (PMT).

[0039] A zinc-plated steel sheet treated with a chrome-free surface treatment coating according to one embodiment of the present invention has excellent corrosion resistance, particularly corrosion resistance after processing.

[0040] In addition, it can provide excellent results without concerns regarding the installation of additional facilities for chromium processing, increased manufacturing costs, or environmental pollution.

[0041] The various and beneficial advantages and effects of the present invention are not limited to those described above and will be more easily understood in the process of explaining specific embodiments of the present invention.

[0042] Figure 1 is a photograph observed after evaluating the corrosion resistance of a specimen performed in an embodiment of the present invention.

[0043] Preferred embodiments of the present invention are described below. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

[0044] In addition, embodiments of the present invention are provided to more fully explain the present invention to those with average knowledge in the relevant technical field.

[0045] In describing the embodiments of the present invention, if it is determined that a detailed description of known technology related to the present invention may unnecessarily obscure the essence of the present invention, such detailed description will be omitted. Furthermore, the terms described below are defined considering their functions in the present invention, and these may vary depending on the intentions or conventions of the user or operator. Therefore, such definitions should be based on the content throughout this specification. The terms used in the detailed description are merely for describing the embodiments of the present invention and should not be limited in any way. Unless explicitly stated otherwise, expressions in the singular form include the meaning of the plural form.

[0046] In this description, expressions such as “include” or “equipped” are intended to refer to certain characteristics, numbers, steps, actions, elements, parts or combinations thereof, and should not be interpreted to exclude the existence or possibility of one or more other characteristics, numbers, steps, actions, elements, parts or combinations thereof other than those described.

[0047] In this specification, terms such as 'top', 'upper', 'upper surface', 'lower', 'lower surface', 'lower surface', and 'side surface' are based on the drawings and may actually vary depending on the direction in which the elements or components are arranged.

[0048] Additionally, throughout the specification, when it is said that one part is 'connected' to another part, this includes not only cases where they are 'directly connected,' but also cases where they are 'indirectly connected' with other elements in between.

[0049] The present invention will be described in detail below through each embodiment or example of the invention. It should be noted that each embodiment or example described in this specification is not limited to a single embodiment or example, but may also be combined with other embodiments or examples. Accordingly, the citation of claims in the patent claims is merely an example of an embodiment, and the technical concept of the present invention should not be interpreted as being limited only to a combination with the cited claims; rather, combinations with various claims are also included within the scope of the technical concept of the present invention.

[0050]

[0051] First, a surface treatment composition, which is one embodiment of the present invention, will be described in detail.

[0052] The above surface treatment composition may comprise 80 to 95 weight% of an organic-inorganic composite resin, 0.2 to 10 weight% of a metal chelate, and 5 weight% or less of an additive, based on 100 weight% of the solid content. In addition to the solid content, the composition comprises a solvent.

[0053] (A) Organic-inorganic composite resin

[0054] The above organic-inorganic composite resin is a sol-gel type resin obtained by a composite reaction between an organosilicon compound (silane), a polymer resin, and a binder. If the content of the above organic-inorganic composite resin is less than 80% by weight of the total weight of the solid content, a solid film may not be formed, and if it exceeds 95% by weight, there is a problem in that it is difficult to secure sufficient corrosion resistance.

[0055] Specific examples of the above organosilicon compounds (silanes) include bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,9-bis(trimethoxysilyl)nonane, bis(trimethoxysilylpropyl)amine, bis(triethoxysilylpropyl)amine, bis(trimethoxysilylmethyl)amine, bis(triethoxysilylmethyl)amine, bis(trimethoxysilylpropyl)amine, and bis(triethoxysilylpropyl)amine, and one of these alone It may be used, and two or more types may be used in combination.

[0056] The above polymer resin may be of any type, such as urethane, epoxy, or ester, but a urethane-based modified urethane resin is most suitable. The type of modified urethane resin is not specifically limited, but as an example, it may be a modified urethane acrylic resin, and an EAA (ethylenyl acrylic acid) copolymer modified urethane resin is particularly preferred. In addition, the above modified urethane resin may be included in an amount of 5 to 30 weight% based on 100 weight% of the solid content of the surface treatment composition. If the content is less than 5 weight%, it is difficult to impart sufficient corrosion resistance and processability characteristics to the processed part, and if the content exceeds 30 weight%, corrosion resistance, blackening resistance, and alkali resistance may decrease.

[0057] In order to form a strong bond between the organic resin and the inorganic compound of the surface treatment composition, a silane coupling agent may be used to modify the organic resin and perform a coupling reaction. The present invention does not specifically limit the type of silane coupling agent, and it is sufficient if it is widely used in the technical field to which the present invention belongs. As a specific example, it may be one or more selected from vinyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycyloxypropyltriethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, N-2-(aminoethyl))-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 2-perfluorooctylethyltrimethoxysilane.

[0058] The Si and N included in the above organic-inorganic composite resin can satisfy the conditions of the following relationship 1.

[0059] [Relationship 1]

[0060] log [Si / N]: 2.5~10

[0061] The above Si and N are the content (at.%) of Si and N contained in the resin.

[0062] If the value of the above relationship 1 is less than 2.5, it may be difficult to ensure sufficient corrosion resistance, and if it exceeds 10, machinability and corrosion resistance of the machined part may be inferior.

[0063] (B) Metal chelate

[0064] The metal chelating agent is added to promote hardening and ensure high corrosion resistance, and preferably, one or more chelating agents selected from the group consisting of silane-based, titanium-based, and zirconium-based agents may be used as the metal chelating agent.

[0065] If the above metal chelate is less than 0.5 weight% based on solid content, it is difficult to secure sufficient corrosion resistance and the promotion of hardening may be hindered. On the other hand, if it exceeds 10 weight%, the unreacted chelate component remaining weakens the corrosion resistance, and it is not desirable because the cost increases too much economically.

[0066] Silane-based chelating agents may include vinyl trimethoxysilane, 3-glycyloxyproc trimethoxysilane, 3-glycyloxypropyl triethoxysilane, 3-glycyloxyproc trimethoxysilane, N-2-(aminoethyl))-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and mixtures thereof, and titanium-based chelating agents may include titanium acetylacetonate, iso-butoxytitanium ethyl acetoacetate, tetraisopropyl titanate, tetranormal butyl titanate, and mixtures thereof. Additionally, zirconium-based chelating agents may include tetranormal-propyl zirconate, tetranormal-butyl zirconate, sodium, potassium, lithium, and ammonium salts of zirconium carbonate, triethanolamine zirconate, hexafluorozirconate, and mixtures thereof.

[0067] (C) Additives

[0068] Other additives may include lubricants (wax), hardeners, etc.

[0069] The above lubricant may be included to impart lubricity to the surface treatment composition, particularly to improve processability due to lubrication characteristics during the customer's processing process. Such lubricant may be one or more selected from paraffin wax, olefin wax, carnauba wax, polyester wax, polyethylene wax, polypropylene wax, polyethylene-Teflon wax, and polyTeflon wax.

[0070] The above curing agent may be included to form a rigid resin film through cross-linking. The above curing agent may be one or more selected from the group consisting of melamine-based curing agents, carbodiimide-based curing agents, block isocyanate-based curing agents, aziridine-based curing agents, and oxazoline-based curing agents.

[0071] The above additive may be included in an amount of 10 weight% or less (including 0%).

[0072] The above surface treatment composition includes a solvent in addition to the solid component. In the present invention, water is included as the solvent. The water refers to deionized water or distilled water. The solvent is included as the remainder in addition to each component of the present invention. Meanwhile, alcohol may be included as an auxiliary solvent, and the alcohol may be ethanol or isopropyl alcohol. The alcohol may be included in an amount of 3 to 5 weight percent of the total solvent.

[0073]

[0074] Next, a zinc-plated steel sheet, which is another embodiment of the present invention, and a method for manufacturing the same will be described in detail.

[0075] The above zinc-plated steel sheet comprises a base steel sheet, a zinc-based plating layer formed on at least one surface of the base steel sheet, and a coating layer formed on the zinc-based plating layer. The coating layer prepared using the aforementioned surface treatment solution composition preferably comprises, in the weight percent of the coating layer itself, 80 to 95 weight percent of an organic-inorganic composite resin, 0.2 to 10 weight percent of a metal chelate, and 10 weight percent or less of an additive. The above organic-inorganic composite resin preferably satisfies the above relationship Equation 1.

[0076] It is preferable that the thickness of the above film layer be 0.2 to 10 μm.

[0077] The above-mentioned base steel plate is not specifically limited in type, and it is sufficient if it is recognized and usable in the technical field to which the present invention belongs.

[0078] In addition, the zinc-based plating layer is not specifically limited, and it is sufficient if it is recognized and usable in the technical field to which the present invention belongs. A preferred example may be a hot-dip galvanized layer (GI), an alloyed zinc plating layer (GA), or a ternary zinc alloy plating layer of Zn-Al-Mg.

[0079] The method for manufacturing the above-described zinc-plated steel sheet is produced by coating the surface treatment solution composition described above onto a zinc-plated steel sheet having a zinc-plated layer formed thereon, and then drying the coated surface treatment solution composition to form a film layer. This will be explained in more detail below.

[0080] Coating of surface treatment solution composition

[0081] The surface treatment solution composition described above is coated onto the zinc-plated steel sheet. The method of coating the surface treatment solution composition is not particularly limited as long as it is a conventionally performed coating method, but examples include roll coating, spraying, immersion, spray squeezing, and immersion squeezing.

[0082] The adhesion amount of the surface treatment solution composition during the above coating is 250 mg / m² 2Up to 1500 mg / m² 2 It can be done with the amount of coating. If the above coating amount is too small, the surface treatment solution composition is applied thinly to the rough areas of the steel plate, which may cause a problem of reduced corrosion resistance, and if it is too large, a thick film layer is formed, which may cause a problem of deterioration in weldability and workability.

[0083] dry

[0084] The drying process of the above-mentioned coated surface treatment solution composition is preferably carried out at a temperature of 70 to 150°C based on the final reached temperature (PMT) of the base steel sheet.

[0085] Meanwhile, it is preferable to carry out the above drying in a hot air dryer or an induction heating oven.

[0086] When drying a surface treatment coating composition using an induction heating furnace, it is preferable that the current applied to the induction heating furnace be 1000 to 4500 A.

[0087] The method for manufacturing a zinc alloy plated steel sheet according to one embodiment of the present invention may be carried out as a continuous process, and the speed of the continuous process is preferably 80 to 120 mpm.

[0088] The present invention will be described in detail below through examples. However, it should be noted that the examples described below are intended merely to illustrate and embody the present invention and are not intended to limit the scope of the present invention. This is because the scope of the present invention is determined by the matters described in the patent claims and matters reasonably inferred therefrom.

[0089] (Example)

[0090] 1. Preparation of surface treatment solution composition

[0091] A solution composition consisting of a solvent and a solid was prepared, and the solution composition was prepared according to the ratios in Table 1 below, with each composition ratio relative to 100 wt% of the solid. Water was used as the solvent. Specifically, (A) the organic-inorganic composite resin is a composite resin of tetraalkoxysilane and a modified urethane-based resin, (B) the metal chelate is tetraisopropyl titanate, and (C) the additive is composed of a polyester-based wax and a curing agent.

[0092] Classification (Weight%) (A)(B)(C) Relationship 1 Comparative Example 1950.34.70.5 Comparative Example 2951.041.5 Inventive Example 193345 Inventive Example 295149 Comparative Example 3925311 Comparative Example 48610415

[0093] 2. Preparation of a galvanized steel sheet having a film layer. An alloyed hot-dip galvanized steel sheet was cut into 7 cm × 15 cm (width × length) and oil was removed, then the above surface treatment solution composition was bar-coated and dried under conditions of PMT 100°C to prepare a specimen with a film layer thickness of 0.6 μm after drying.

[0094] For the zinc alloy plated steel sheet having the above film layer, plate corrosion resistance, processed part corrosion resistance, blackening resistance, and alkali resistance were evaluated, and the results are shown in Table 2 and Figure 1.

[0095] 3. Evaluation Methods and Criteria

[0096] For the specimens prepared above, plate corrosion resistance, processed part corrosion resistance, blackening resistance, and alkali resistance were evaluated, and the results are presented. The evaluation methods and criteria are explained in detail below.

[0097] (1) Plate corrosion resistance

[0098] Based on the method specified in ASTM B117, the white rust occurrence rate of the steel plate over time after treating the specimen was measured.

[0099] At this time, the evaluation criteria are as follows.

[0100] ◎: 120 hours or more

[0101] ○: 96 hours or more but less than 120 hours

[0102] △: 72 hours or more but less than 96 hours

[0103] X : Less than 72 hours

[0104] (2) Corrosion resistance of the processed parts

[0105] After pushing the specimen up to a height of 6 mm using an Erichsen tester, the degree of white rust development was measured after 24 hours.

[0106] At this time, the evaluation criteria are as follows.

[0107] ◎: Less than 5% incidence of white rust after 48 hours

[0108] △: 24 hours or more but less than 48 hours

[0109] X: Less than 24 hours

[0110] (3) Resistant to blackening

[0111] The color change of the specimen before and after the test (color difference: ΔE) was observed by leaving the specimen in a constant temperature and humidity chamber maintained at 50°C and 95% relative humidity for 120 hours.

[0112] At this time, the evaluation criteria are as follows.

[0113] ◎: ΔE ≤ 1

[0114] ○: 1.5 < ΔE ≤ 3

[0115] △: 3 < ΔE ≤4

[0116] X: ΔE > 4

[0117] (4) Alkali resistance

[0118] The specimens were immersed in an alkaline degreasing solution at 60°C for 2 minutes, rinsed with water, and air blowing, after which the color difference (ΔE) before and after was measured. The alkaline degreasing solution used was Finecleaner L 4460 A: 20g / 2.4L + L 4460 B 12g / 2.4L (pH=12) from Daehan Parkerizing.

[0119] At this time, the evaluation criteria are as follows.

[0120] ◎: ΔE ≤ 1

[0121] ○: 1.5 < ΔE ≤ 3

[0122] △: 3 < ΔE ≤ 4

[0123] X: ΔE > 4

[0124] Classification Plate Corrosion Resistance Processed Part Corrosion Resistance Blackening Resistance Alkali Resistance Comparative Example 1 X △ ◎ ○ Comparative Example 2 △ ◎ ◎ ◎ Invention Example 1 ◎ ◎ ◎ ◎ Invention Example 2 ◎ ○ ◎ ◎ Comparative Example 3 ○ X ○ ○ Comparative Example 4 ○ X △ △

[0125] From the results of Table 2 and Figure 1 above, in the case of Invention Examples 1 and 2, which satisfy the conditions of the present invention, excellent corrosion resistance was secured, while resistance to blackening and alkali resistance were secured. Comparative Examples 1 and 2 are cases where the conditions according to Equation 1 are not met, and in particular, it was found that Comparative Example 1 has less metal chelate, so the plate corrosion resistance is further reduced.

[0126] Comparative Examples 3 and 4 show that Equation 1 exceeds the proposed scope of the present invention, and thus the corrosion resistance of the processed part is inferior. In the case of Comparative Example 4, it was found that the metal chelate was somewhat excessive, resulting in a slight decrease in blackening resistance and alkali resistance.

Claims

1. Contains solids and solvent, Based on 100 weight%, the above solid content comprises 80 to 95 weight% of an organic-inorganic composite resin, 0.2 to 10 weight% of a metal chelate, and 10 weight% or less (including 0%) of an additive, and The Si and N included in the above organic-inorganic composite resin are a surface treatment solution composition that satisfies the conditions of the following relationship 1. [Relationship 1] log [Si / N]: 2.5~10 The above Si and N are the content (at.%) of Si and N contained in the resin.

2. In Paragraph 1, The above organic-inorganic composite resin comprises an organosilicon compound, and the organosilicon compound is among bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,9-bis(trimethoxysilyl)nonane, bis(trimethoxysilylpropyl)amine, bis(triethoxysilylpropyl)amine, bis(trimethoxysilylmethyl)amine, bis(triethoxysilylmethyl)amine, bis(trimethoxysilylpropyl)amine, and bis(triethoxysilylpropyl)amine. A surface treatment solution composition of one or more types.

3. In Paragraph 1, A surface treatment solution composition in which the above organic-inorganic composite resin comprises a polymer resin, and the polymer resin is a modified urethane acrylic resin.

4. In Paragraph 3, A surface treatment composition comprising the above modified urethane acrylic resin in an amount of 5 to 30 weight% based on 100 weight% of the solid content of the surface treatment composition.

5. In Paragraph 1, The above organic-inorganic composite resin comprises a silane coupling agent, and the silane coupling agent is one or more selected from vinyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycyloxypropyltriethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, N-2-(aminoethyl))-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 2-perfluorooctylethyltrimethoxysilane, forming a surface treatment composition.

6. In Paragraph 1, The above metal chelate is a surface treatment composition comprising one or more chelating agents selected from the group consisting of silane-based, titanium-based, and zirconium-based chelating agents.

7. In Paragraph 6, The above silane-based chelating agent is a surface treatment composition comprising vinyl trimethoxysilane, 3-glycyloxyproc trimethoxysilane, 3-glycyloxypropyl triethoxysilane, 3-glycyloxyproc trimethoxysilane, N-2-(aminoethyl))-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and mixtures thereof.

8. In Paragraph 6, The above titanium-based chelating agent is a surface treatment composition comprising titanium acetylacetonate, iso-butoxytitanium ethyl acetoacetate, tetraisopropyl titanate, tetranormal butyl titanate, and mixtures thereof.

9. In Paragraph 6, The above zirconium-based chelating agent is a surface treatment composition comprising tetranormal-propyl zirconate, tetranormal-butyl zirconate, sodium, potassium, lithium, and ammonium salts of zirconium carbonate, triethanolamine zirconate, hexafluorozirconate, and mixtures thereof.

10. In Paragraph 1, The above surface treatment solution composition is a surface treatment composition comprising 5 weight% or less (including 0%) of an additive.

11. Base steel plate; A zinc-based plating layer formed on at least one surface of the above-mentioned base steel plate; and It includes a film layer formed on the above zinc-based plating layer, and The above coating layer comprises, in weight percent of the coating layer itself, 80 to 95 weight percent of an organic-inorganic composite resin, 0.2 to 10 weight percent of a metal chelate, and 10 weight percent or less (including 0%) of an additive, and the Si and N included in the organic-inorganic composite resin satisfy the conditions of the following equation 1, a zinc-plated steel sheet. [Relationship 1] log [Si / N]: 2.5~10 The above Si and N are the content (at.%) of Si and N contained in the resin.

12. In Paragraph 11, A zinc-plated steel sheet having a film layer thickness of 0.2 to 10 μm.

13. In Paragraph 11, The above zinc-based plating layer is a zinc-based plated steel sheet that is any one of a hot-dip galvanized layer (GI), an alloyed zinc-based plating layer (GA), and a ternary zinc alloy plating layer of Zn-Al-Mg.

14. A step of coating a surface treatment solution composition of any one of claims 1 to 10 on a zinc-plated steel sheet having a zinc-based plating layer formed thereon; and Step of forming a film layer by drying the above-mentioned coated surface treatment solution composition A method for manufacturing a surface-treated zinc-plated steel sheet comprising 15. In Paragraph 14, The adhesion amount of the surface treatment solution composition during the above coating is 250 mg / m² 2 Up to 1500 mg / m² 2 A method for manufacturing a zinc-plated steel sheet using the amount of coating.

16. In Paragraph 14, A method for manufacturing a zinc-plated steel sheet in which the above drying is performed at a temperature of 70 to 150°C based on the final reached temperature (PMT).

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