KR101775994B1 - Manufacturing Method of Environment-Friendly Lamination Steel Sheet Having Excellent Section Corrosion Resistance - Google Patents

Manufacturing Method of Environment-Friendly Lamination Steel Sheet Having Excellent Section Corrosion Resistance Download PDF

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KR101775994B1
KR101775994B1 KR1020150181712A KR20150181712A KR101775994B1 KR 101775994 B1 KR101775994 B1 KR 101775994B1 KR 1020150181712 A KR1020150181712 A KR 1020150181712A KR 20150181712 A KR20150181712 A KR 20150181712A KR 101775994 B1 KR101775994 B1 KR 101775994B1
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weight
steel sheet
film
coating composition
layer
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KR1020150181712A
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Korean (ko)
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KR20170073152A (en
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이은섭
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포스코강판 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2503/00—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2504/00—Epoxy polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2508/00—Polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Laminated Bodies (AREA)

Abstract

An object of the present invention is to provide a method of manufacturing an environmentally friendly laminated steel sheet excellent in cross-sectional corrosion resistance, which improves the cross-sectional corrosion resistance of the steel sheet to the cut surface and prevents the harmful substances from being discharged by burning the film.
To this end, the present invention provides a method of manufacturing a steel sheet, comprising the steps of: forming a pretreatment layer (20) on both sides of a base steel sheet (10); Applying a coating composition to the upper pretreatment layer (20) to form an upper coating layer (30); Applying a coating composition to the lower pretreatment layer (30) to form a lower coating layer (60); And a step of laminating a film (F) to the upper coating layer (30), wherein the base steel sheet (10) is made of a hot-dip zinc-aluminum-magnesium alloy coated steel sheet, The coating layer 30 is formed by applying a polyurethane coating composition 30 'and the lower coating layer 60 is formed by applying a polyester coating composition 60' or an epoxy coating composition 60 ' The film F is formed by laminating a polyethylene terephthalate (PET) film 50 and a polypropylene (PP) film 40, and then laminated on the backing steel sheet 10.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing an environmentally friendly laminated steel sheet having excellent corrosion resistance,

More particularly, the present invention relates to a method of manufacturing an environmentally friendly laminated steel sheet excellent in cross-sectional corrosion resistance, and more particularly, to a method of manufacturing an eco- The present invention can improve the corrosion resistance of the steel sheet material by lowering the cost and the workability of the steel sheet material and can prevent harmful substances such as phthalate, formaldehyde, and chlorine gas from occurring in conventional PVC (polyvinylchloride) To a method of manufacturing an eco-friendly laminated steel sheet excellent in end-face corrosion resistance.

Generally, a lamination steel sheet refers to a laminated steel sheet which is obtained by laminating various films on the surface of a steel sheet made of an electro-galvanized steel sheet, a hot-dip galvanized steel sheet, a cold rolled steel sheet, a stainless steel sheet, a galvarium steel sheet, Product.

The laminated steel sheet has been developed for use as an outer case of household appliances such as a refrigerator, a washing machine, and an air conditioner, and has an advantage in that it has excellent appearance characteristics and workability as compared with general coated steel sheets.

As the film used for the laminated steel sheet, materials such as PVC and PET are mainly used.

On the other hand, the laminated steel sheet used as the interior / exterior of the building must be subjected to a separate processing step after the steel sheet is manufactured and the film should be adhered thereto, so that the conditions such as excellent workability, adhesiveness, weather resistance, and corrosion resistance must be satisfied.

However, the conventional laminated steel sheet has a problem that the corrosion resistance is deteriorated due to moisture penetrated through the cut surface at the time of processing.

Particularly, in the case of a steel sheet having a large thickness, there is a problem that corrosion is severely generated at the cut surface portion at the time of processing.

On the other hand, Korean Patent Laid-Open No. 10-2014-0110519 discloses "an adhesive for film lamination and a method for producing the same. &Quot;

The above-mentioned prior art is characterized in that 20 to 100 parts by weight of MEK, 20 to 100 parts by weight of MIBK, 30 to 150 parts by weight of xylene, 20 to 100 parts by weight of butyl carbitol and 10 to 100 parts by weight of functional additive 10 To 70 parts by weight of a one-component thermosetting adhesive for film lamination and a rubber (NBR) and a phenoxy resin in a mixed solvent containing a ketone; Introducing an acrylic resin composed of an acrylic monomer and an acrylic reaction catalyst into the melt to promote reaction during adhesive reaction and lamination; Terminating the reaction and cooling the reaction solution using cooling water and xylene; Adding TEA as an additive to the semi-finished solution to inhibit further reaction; Adding isocyanate as a curing agent to the reaction solution and mixing with the reaction solution; And diluting the cured reaction solution.

The above-mentioned prior art is advantageous in that PVC has excellent processability and ductility, and is excellent in adhesion between a steel sheet and a PVC film.

However, the above-described prior art has a problem that harmful substances such as chlorine gas and phthalate are discharged by the combustion of the PVC film when a fire occurs.

In addition, Korean Patent Laid-Open No. 10-2015-0124309 discloses "a highly corrosion-resistant laminate colored steel sheet and a manufacturing method thereof ".

The above-mentioned prior art is characterized by comprising the steps of: forming a pretreatment layer having a chemical conversion coating on a base steel sheet with a phosphoric acid coating, a chromate or a non-chromate; Applying a solvent-type coating composition on the pretreatment layer to form an undercoat layer; Applying a thermoplastic polyolefin-based coating composition on the undercoat layer to form an overcoat layer; And laminating a thermoplastic polyolefin film on the top coat layer to improve corrosion resistance.

However, the above-mentioned conventional technique can improve the corrosion resistance to the flat portion, but can not secure the corrosion resistance (hereinafter referred to as " cross-sectional corrosion resistance "

That is, according to the prior art, there is a problem that Fe in the plating layer is exposed to the atmosphere at the cut surface portion, causing red and white rust.

On the other hand, as the seriousness of environmental pollution has recently been emphasized, the use of harmful substances has been strengthened, and development of environmentally friendly products has been demanded.

Korean Patent Laid-Open No. 10-2014-0110519 Korean Patent Publication No. 10-2015-0124309

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems occurring in the prior art, and it is an object of the present invention to provide a method of manufacturing a laminated steel sheet, It has its purpose.

Another object of the present invention is to provide a method of manufacturing a laminated steel sheet capable of improving the adhesion between a steel sheet material and a film.

A further object of the present invention is to make it possible to widely use it for household appliances and outdoor purposes while preventing the deterioration of processability while improving the cross-sectional corrosion resistance.

It is still another object of the present invention to provide an eco-friendly product which can meet the criteria for use of toxic substances which are gradually strengthened.

According to an aspect of the present invention, there is provided a method of manufacturing a steel sheet, comprising: forming a pretreatment layer on both surfaces of a steel sheet; Applying a coating composition to the upper pretreatment layer to form a top coat layer; Applying a coating composition to the lower pretreatment layer to form a lower coating layer; The method of manufacturing a laminated steel sheet according to any one of the preceding claims, wherein the upper coating layer is formed of a hot-dip zinc-aluminum-magnesium alloy coated steel sheet, and the upper coating layer is coated with a polyurethane coating composition And the lower coating layer is formed by applying a polyester coating composition or an epoxy coating composition. The film is formed by laminating a PET film and a PP film, and is then laminated to a base steel sheet.

The plating layer of the molten zinc-aluminum-magnesium alloy base steel sheet may contain 95 to 98% by weight of zinc, 0.1 to 3% by weight of aluminum, 1 to 4% by weight of magnesium, and inevitable impurities .

The pretreatment layer preferably contains 1 to 5% by weight of ammonium zirconyl carbonate, 1 to 5% by weight of vanadium, 1 to 10% by weight of silicon dioxide, 80 to 95% by weight of water, And other additives.

The polyurethane-based coating composition for forming the upper coating layer has 13.5 to 16.5% by weight of a polyester polyol having a weight average molecular weight of 80,000 or more and a polyester polyurethane polyol having a weight average molecular weight of 35,000 or more, based on the total weight, By weight of a leveling agent, 0.1 to 0.2% by weight of an antifoaming agent, 0.1 to 0.2% by weight of an antifoaming agent, 0.1 to 0.2% by weight of an antifoaming agent, 3 to 4% by weight of an isocyanate trimer, and 67 to 73% by weight of ethyl acetate.

The coating thickness of the polyurethane coating composition forming the upper coating layer is 4 to 10 탆, and the PMT is dried at 220 to 240 캜.

The polyester coating composition for forming the lower coating layer preferably contains 21 to 37% by weight of a polyester resin, 10 to 20% by weight of a titanium dioxide, 2 to 15% by weight of a bisphenol A type epoxy resin based on the total weight ratio, By weight and an organic solvent in an amount of 50 to 60% by weight.

The epoxy coating composition for forming the lower coat layer preferably comprises 20 to 30% by weight of a bisphenol A type epoxy resin, 10 to 20% by weight of a polyester oligomer having a molecular weight of 1,000 or less, Is contained in an amount of 50 to 60% by weight.

The thickness of the PET film forming the film (F) is 20 to 70 占 퐉, and the thickness of the PP film is 10 to 100 占 퐉.

Further, printing, vapor deposition or embossing is added to the PET film.

According to the present invention, there is an effect that the harmful combustion gas is not discharged when the film is burned, while improving the cross-sectional corrosion resistance to the cut surface of the steel sheet.

In addition, there is an effect that the adhesive force between the steel sheet material and the film is improved by an adhesive having an excellent adhesive force.

Further, since the processability is not lowered while the cross-sectional corrosion resistance is improved, there is an effect that the laminated steel sheet can be widely used for domestic and outdoor use.

In addition, there is an effect that commerciality can be improved by supplying an eco-friendly product that can meet the gradually increasing standards for the use of toxic substances.

1 is a schematic sectional view of a laminated steel sheet according to the present invention.
2 is a flowchart illustrating a manufacturing process of a laminated steel sheet according to the present invention.

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

As shown in FIGS. 1 and 2, a method of manufacturing an environmentally friendly laminated steel sheet having excellent cross-sectional corrosion resistance according to the present invention includes the steps of: forming a pretreatment layer 20 on both sides of a base steel sheet 10; Applying a coating composition to the upper pretreatment layer (20) to form an upper coating layer (30); Applying a coating composition to the lower pretreatment layer (30) to form a lower coating layer (60); And laminating the film (F) to the upper coating layer (30).

The upper coating layer 30 is formed by coating a polyurethane coating composition 30 ', and the lower coating layer 60 is formed by coating the upper coating layer 30 with a polyurethane coating composition 30' Is formed by applying a polyester-based paint composition (60 ') or an epoxy paint composition (60' ').

The film F is formed by laminating a polyethylene terephthalate (PET) film 50 and a polypropylene (PP) film 40, and then laminated to the base steel sheet 10.

That is, in the present invention, the PET film (50) and the PP film (40) are first laminated to form a film (F), and then the laminate is laminated to the steel sheet (10).

Accordingly, it is possible to produce an environmentally friendly laminated steel sheet in which noxious gas is not generated by burning of the film.

On the other hand, the plating layer forming the base steel sheet 10 of the molten zinc-aluminum-magnesium alloy is composed of 95 to 98% by weight of zinc, 0.1 to 3% by weight of aluminum, 1 to 4% by weight of magnesium, , And inevitable impurities as the remainder.

The magnesium promotes the formation of a dense corrosion product, Simonkolleite, in a very stable state.

The Simonclear forms a kind of film layer on the surface of the plated layer to prevent corrosion of the base steel sheet, in particular, the cross section.

However, when the content of magnesium exceeds 4 wt%, the workability of the base steel sheet 10 is lowered. Therefore, it is preferable that the content of magnesium is 1 to 4 wt%.

The pretreatment layer 20 may contain 1 to 5% by weight of ammonium zirconyl carbonate, 1 to 5% by weight of vanadium, 1 to 10% by weight of silicon dioxide, 80 to 95% by weight of water, %, And other additives as the remainder.

The polyurethane-based paint composition 30 'forming the upper coat layer 30 may contain, based on the total weight, 13.5 to 16.5% by weight of a polyester polyol having a weight average molecular weight of 80,000 or more and a weight average molecular weight of 35,000 or more The epoxy resin-containing organosilane coupling agent is 0.4 to 0.5% by weight, the defoaming agent is 0.1 to 0.2% by weight, the leveling agent is 0.1 to 5% by weight, 0.2 to 4 weight% of isophorone diisocyanate trimer, and 67 to 73 weight% of ethyl acetate.

The thickness of the polyurethane coating composition 30 'forming the upper layer 30 is preferably 4 to 10 탆, and the PMT is preferably dried at 220 to 240 캜.

On the other hand, the lower coating layer 60 may be formed of a polyester coating composition 60 'or an epoxy coating composition 60' '.

When the steel sheet is used as an interior material, the lower coating layer 60 is formed of a polyester coating composition 60 ', and when the steel sheet is used as a sheathing material, the lower coating layer 60 is coated with an epoxy coating composition 60 ").

 First, the polyester coating composition 60 'forming the lower coating layer 60 has a polyester resin content of 21 to 37% by weight, a titanium dioxide content of 10 to 20% by weight, a bisphenol A Type epoxy resin is contained in an amount of 2 to 15% by weight and an organic solvent is contained in an amount of 50 to 60% by weight.

The epoxy coating composition 60 "forming the lower coating layer 60 has 20 to 30% by weight of a bisphenol A type epoxy resin and 10 to 10% by weight of a polyester oligomer having a molecular weight of 1,000 or less, based on the total weight ratio. By weight to 20% by weight, and the organic solvent is 50 to 60% by weight.

It is preferable that the thickness of the polyethylene terephthalate (PET) film 50 forming the film F is 20 to 70 μm and the thickness of the polypropylene film 40 is 10 to 100 μm.

Further, printing, vapor deposition or embossing may be added to the PET film 50.

Hereinafter, a manufacturing process of an eco-friendly laminated steel sheet excellent in cross-sectional corrosion resistance according to the present invention will be described with reference to FIG.

First, the coil-shaped base steel sheet 10 is inserted into the continuous coating line CCL to remove oil and foreign matter from the base steel sheet 10 (S10).

Next, the pretreatment layer 20 is coated on both sides of the base steel sheet 10 and dried (S20). A polyurethane coating composition is applied to the top of the base steel sheet 10 at a temperature of 220 to 240 ° C by PMT at 4 to 10 μm, A coating layer 30 is formed (S30).

Subsequently, a polyester coating composition 60 'or an epoxy coating composition 60' 'is applied to the lower portion of the substrate steel sheet 10 to form a lower coating layer 60 (S40).

At this time, the polyester paint composition 60 'is applied when a steel sheet is to be used as an interior material, and the epoxy paint composition 60' 'is applied when it is used as an exterior material.

When the film F is laminated on the upper coat layer 30 (S60) after the PET film 50 and the PP film 40 are laminated (S50) Is completed.

The steel sheet thus produced is rolled up into a coil and packed or processed to a size required by the customer (S70).

According to the conventional manufacturing method of laminating a film on a zinc-aluminum alloy steel sheet, the corrosion resistance to the flat portion can be improved. However, when the steel sheet is cut for machining, corrosion resistance on the cut surface can not be ensured.

That is, it is inevitable that the cut surface portion is exposed to the atmosphere to cause a red or white rust phenomenon.

In addition, the conventional laminating steel sheet has a drawback that harmful combustion gas is generated by burning of the film.

However, according to the present invention, the corrosion resistance to the cut surface of the steel sheet can be improved by adding magnesium, and the scratch resistance and chemical resistance are also improved.

Further, by laminating the PET film and the PP film with each other after laminating the PET film and the PP film, it is possible to improve the adhesive force between the steel sheet material and the film, and to produce an environmentally friendly product in which harmful substances are not generated.

As a result, it can be widely used for home appliances cases, interior materials for buildings, housing for using chemicals, or building exterior materials exposed to the atmosphere.

Hereinafter, experiments of Examples and Comparative Examples of the present invention will be described.

 ≪ Example 1 >

In the first embodiment of the present invention, the pretreatment layer 20 is applied on the upper surface of the hot-rolled steel sheet 10 of the molten zinc-aluminum-magnesium alloy and dried, and then the polyurethane upper coat layer 30 is formed to 2 to 3 탆 After the PMT was dried at 190 to 210 ° C, the film (F) in which the PET film (50) and the PP film (40) were laminated was laminated to a base steel sheet.

≪ Example 2 >

In Example 2 of the present invention, the pretreatment layer 20 is applied on the upper surface of the hot-rolled steel sheet 10 of the molten zinc-aluminum-magnesium alloy and dried, and then the polyurethane upper coat layer 30 is formed to 4 to 5 탆 After the PMT was dried at 220 to 240 ° C, the film (F), in which the PET film (50) and the PP film (40) were laminated, was laminated to a base steel sheet.

≪ Example 3 >

In the third embodiment of the present invention, the pretreatment layer 20 is applied on the upper surface of the hot-rolled steel sheet 10 of the hot-dip zinc-aluminum-magnesium alloy and dried, and then the polyurethane upper coat layer 30 is formed to 5 to 6 탆 After drying at a temperature of 240 to 260 ° C, the film (F) having the PET film (50) and the PP film (40) laminated together was laminated to a base steel sheet.

<Example 4>

In Example 4 of the present invention, the pretreatment layer 20 is applied to the upper surface of the hot-rolled steel sheet 10 of the molten zinc-aluminum-magnesium alloy and dried, and then the polyurethane upper coating layer 30 is formed to 9 to 10 탆 After the PMT was dried at 220 to 240 ° C, the film (F) having the PET film (50) and the PP film (40) laminated was laminated to a base steel sheet.

&Lt; Comparative Example 1 &

In Comparative Example 1, a pretreatment layer was applied to the upper surface of a GI (Galvanized Iron) base steel sheet, and then a PVC film laminated with a PET film was laminated to a base steel sheet.

&Lt; Comparative Example 2 &

In Comparative Example 2, a pretreatment layer was applied to the upper surface of a GI (Galvanized Iron) base steel sheet, and then the PET film was laminated to the base steel sheet.

The following test pieces were subjected to the following physical property tests.

<Glossiness>

The gloss was measured using a gloss meter at 60 °.

<Processability>

The workability was evaluated by a method of T-bending a test piece using a vise, attaching a transparent adhesive tape, and peeling the tape at an angle of 60 占 between 0.5 and 1 second.

<Pencil hardness>

The test piece was fixed to the pencil hardness tester and the end portion was smoothly cut so that the core of the Mitsubishi pencil was exposed to about 3 mm. The pencil was bound to a hardness tester, and a line was repeatedly drawn five times so as to have a length of 20 mm or more by applying a load of 1 kg. The test area was erased with an eraser and observed with the naked eye.

<CCET>

A cross-cut of 5 mm in the shape of # was formed on the surface of the test piece, and the moisture resistance and the temperature and humidity resistance were evaluated by 8 mm Erichsen Test.

The temperature of the hot water bath was maintained at 80 ℃. After 30 minutes, the specimens were taken out from the hot water bath and washed.

In addition, the temperature and humidity resistance were evaluated after a lapse of 120 hours at 95% RH and 60 ° C.

<SST>

SST (Salt Spray Test) was performed at 5% NaCl to evaluate the corrosion resistance of the cross section.

[Table 1] shows the results of the physical property test.

The results of the physical properties test of Examples and Comparative Examples according to the present invention Item Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Remarks Polish ◎ △ ◎ ◎ X △ 60 ° Processability ◎ ○ ◎ ◎ ◎ ○ Taping pencil
Hardness  scratch ○ ○ ○ ○ ○ ○ Mitubishi  Destruction ○ ○ ○ ○ ○ ○ CCET ◎ ◎ X ◎ △ ○ 8mm CCET + number of lights ○ X X ◎ △ X 8mm +
80 ° C X30min
CCET + constant temperature and humidity
○

X
X
◎
○
X 60 ° C X
95% RH X
120hrs SST
Sectional corrosion resistance
X
X
◎
◎
◎
◎
NaCl 5%  X: Bad, △ Normal, ○ Good, ◎ Excellent

As can be seen from the above physical properties test, Examples 1 to 4, in which a PET film and a PP film were laminated on a hot-dip zinc-aluminum-magnesium alloy steel sheet according to the present invention and laminated to a steel sheet, were subjected to general GI (Galvanized Iron) And exhibited a physical property equal to or higher than that of the comparative example in which a steel sheet was laminated with a PET film and a PVC film or a PET film.

In particular, Comparative Examples 1 and 2 were poor in cross-sectional corrosion resistance, but Examples 1 to 4 according to the present invention were confirmed to have excellent cross-sectional corrosion resistance.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It will be understood by those skilled in the art that various changes and modifications may be made without departing from the scope of the present invention.

10: Substrate steel
20: Pre-treatment layer
30: upper coating layer
40: PP (polypropylene) film
50: PET (Polyethylene Terephthalate) film
60: Lower coating layer

Claims (9)

Forming a pretreatment layer (20) on both sides of the base steel sheet (10); Applying a coating composition to the upper pretreatment layer (20) to form an upper coating layer (30); Applying a coating composition to the lower pretreatment layer (30) to form a lower coating layer (60); And laminating a film (F) on the upper coating layer (30), the method comprising the steps of:
The base steel sheet 10 is made of a molten zinc-aluminum-magnesium alloy-plated steel sheet,
The upper coating layer 30 is formed by applying a polyurethane coating composition 30 '
The lower coating layer 60 is formed by applying a polyester coating composition 60 'or an epoxy coating composition 60'
The film F is formed by laminating a polyethylene terephthalate (PET) film 50 and a polypropylene (PP) film 40 and then laminated on the backing steel sheet 10,
The polyurethane-based coating composition (30 ') forming the upper coating layer (30)
Based on the total weight, a polyester polyol having a weight average molecular weight of 80,000 or more of 13.5 to 16.5 wt%, a polyester polyurethane polyol having a weight average molecular weight of 35,000 or more of 5.4 to 6.6 wt%, a bisphenol A type epoxy resin of 4 to 5 wt By weight, the leveling agent is 0.1 to 0.2% by weight, the isophorone diisocyanate trimer is 3 to 4% by weight, the ethyl acetate is 67 to 73% by weight, the epoxy group-containing organosilane coupling agent is 0.4 to 0.5% by weight, the defoaming agent is 0.1 to 0.2% By weight based on the total weight of the laminate. The method according to claim 1,
The plating layer of the molten zinc-aluminum-magnesium alloy base steel sheet (10)
A process for producing an eco-friendly laminated steel sheet excellent in endurance corrosion resistance, which comprises 95 to 98% by weight of zinc, 0.1 to 3% by weight of aluminum, 1 to 4% by weight of magnesium, and inevitable impurities as the remainder Way. The method according to claim 1,
The pretreatment layer 20 may contain 1 to 5% by weight of ammonium zirconyl carbonate, 1 to 5% by weight of vanadium, 1 to 10% by weight of silicon dioxide, 80 to 95% by weight of water, And the other additive is contained as the remainder. The method of producing an eco-friendly laminated steel sheet excellent in cross-sectional corrosion resistance. delete The method according to claim 1,
A method for producing an environmentally friendly laminated steel sheet excellent in cross-section corrosion resistance, characterized in that the coating thickness of the polyurethane coating composition (30 ') forming the upper coating layer (30) is 4 to 10 μm and the PMT is dried at 220 to 240 ° C. . The method according to claim 1,
The polyester-based coating composition 60 'for forming the lower coating layer 60 may be prepared,
Wherein the polyester resin is contained in an amount of 21 to 37% by weight, the titanium dioxide is contained in an amount of 10 to 20% by weight, the bisphenol A type epoxy resin is contained in an amount of 2 to 15% by weight and the organic solvent is contained in an amount of 50 to 60% Resistant laminate steel sheet excellent in cross-sectional corrosion resistance. The method according to claim 1,
The epoxy coating composition 60 "for forming the lower coating layer 60 is a &quot;
Based on the total weight ratio, 20 to 30% by weight of a bisphenol A type epoxy resin, 10 to 20% by weight of a polyester oligomer having a molecular weight of 1,000 or less, and 50 to 60% by weight of an organic solvent Wherein the method comprises the steps of: The method according to claim 1,
The thickness of the polyethylene terephthalate (PET) film 50 forming the film F is 20 to 70 탆 and the thickness of the polypropylene film 40 is 10 to 100 탆. (JP) METHOD FOR MANUFACTURING ECOLOGICAL LAMINATED STEEL PANEL 9. The method of claim 8,
The method of manufacturing an eco-friendly laminated steel sheet according to claim 1, wherein the PET film (50) is subjected to printing, vapor deposition or embossing.

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