KR101391044B1 - Eco-friendly resin composition for surface treatment, and metal product using the same - Google Patents

Abstract

The present invention relates to a resin composition for metal surface treatment which improves eco-friendly properties of a material for a bag cover applied to a display electronic device for home use, and reduces the manufacturing cost; and to a metal product using the same. The resin composition for metal surface treatment contains 20-80 wt% of a water-soluble organic resin, 1-45 wt% of a pigment dispersing body, 5-50 wt% of a crosslinking agent, 0.1-5 wt% of an attachment increasing body, 0.1-5 wt% of wax, 1-10 wt% of an anti-corrosion agent, and 5-60 wt% of water.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition for an environmentally friendly metal surface treatment,

The present invention relates to a resin composition for eco-friendly metal surface treatment and a metal processed product using the resin composition. More particularly, the present invention relates to a resin composition for a back cover, To a black resin composition and an aqueous black resin steel sheet using the same.

A black resin steel sheet is used as a material for a back cover of a display electronic appliance for home appliances. A black resin steel sheet is produced by coating a surface of a steel sheet or a galvanized steel sheet with a resin composition for surface treatment containing a black pigment. Generally, such a resin composition for surface treatment uses a solvent-type resin composition, and the volatile solvent used as a solvent volatilizes during the film formation process and becomes a substance that pollutes the atmosphere. In addition, since such a solvent-type resin composition has poor adhesion to the surface of a metal, an aqueous basecoat solution is generally used to improve the adhesion, resulting in an additional production cost.

DISCLOSURE OF INVENTION Technical Problem Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a resin composition for metal surface treatment and a metal product using the resin composition, .

In order to achieve the above object, the present invention provides a water-based ink composition comprising 20 to 80 wt% of an aqueous organic resin, 1 to 45 wt% of a pigment dispersion, 5 to 50 wt% of a crosslinking agent, 0.1 to 5 wt% 1 to 10% by weight of rust inhibitor and 5 to 60% by weight of water.

In the present invention, the aqueous organic resin may be at least one selected from the group consisting of water-dispersible urethane resin, water-dispersed acrylic resin, water-soluble epoxy, water-soluble polyester resin, water-soluble amino resin, water-dispersible silicone resin and mixtures thereof.

In the present invention, the pigment dispersion may contain 10 to 80% by weight of an aqueous organic resin for dispersion, 5 to 60% by weight of pigment particles, 0.5 to 10% by weight of a dispersion stabilizer and 1 to 52% by weight of water.

In the present invention, the aqueous organic solvent for dispersion may be at least one selected from the group consisting of water-dispersible urethane resin, water-dispersible acrylic resin, water-soluble epoxy, water-soluble polyester resin, water-soluble amino resin and mixtures thereof.

In the present invention, the pigment particles may be at least one black pigment particle selected from the group consisting of carbon nanotubes, carbon fibers, carbon black, graphite and graphene.

In the present invention, the average particle size of the pigment particles may be 2 to 10,000 nm.

In the present invention, the dispersion stabilizer may be a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

n is an integer of 1 to 10,

R ₁ is an alkyl group having 1 to 5 carbon atoms,

R ₂ is ^{-OH, -ONa, -OK, -O -} NH 4 +, -COOH, -COONa, -COOK, -COO - NH 4 +, -SO 3 H, -SO 3 Na, -SO 3 K, -SO ₃ ^- NH ₄ ^+, can be selected from _{-PO 3 H 2, -HPO 3 Na} , -HPO 3 K, -PO 3 Na 2, the group consisting of -PO ₃ K _2, and -SO ₂ NHCOH.

In the present invention, the crosslinking agent may be at least one selected from the group consisting of a melamine crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and a mixture thereof.

In the present invention, the adhesion promoter may be at least one selected from the group consisting of a titanium-based adhesion promoter, a phosphate adhesion promoter, and a silane adhesion promoter.

In the present invention, the titanium-based adhesion promoter may be a compound represented by the following general formula (2).

(2)

In Formula 2,

R ₃ is H or an alkyl group having 1 to 5 carbon atoms,

R ₄ is _{-X 1 COX 2 COX 3, -X} 4 N (X 5) 2, -C (X 6) = is selected from the group consisting of _{CHCOX 7, X 1, X 2} , X 4 is a group having 1 to 5 carbon atoms X ₃ and X ₆ are each an alkyl group having 1 to 5 carbon atoms, X ₅ is a hydroxyalkyl group having 1 to 5 carbon atoms, and X ₇ is an alkyl group having 1 to 5 carbon atoms or O ^- NH ₄ ⁺ .

In the present invention, the phosphate adhesion promoting agent may be a compound represented by the following general formula (3).

(3)

In Formula 3,

R ₅ , R ₆ and R ₇ each independently represent a phenyl group containing an alkyl group having 1 to 9 carbon atoms.

In the present invention, the silane adhesion promoter may be a compound represented by the following general formula (4).

[Chemical Formula 4]

In Formula 4,

R ₈ is an alkyl group having 1 to 5 carbon atoms,

R ₉ is _{-Y 1 CH (Y 2) CH} (Y 3) NH 2, -Y 4 NHCONH 2, -Y 5 OY 6 CH (Y 7), -Y 8 NH 2, -Y 9 NH (Y 10) is selected from the group consisting of _{-Y 11 NCO, Y 1, Y} 4, Y 5, Y 6, Y 8, Y 9, Y 11 is a C 1 -C 5 alkylene group, Y ₂ is C 1 -C 5 Y ₃ is an alkyl group having 1 to 5 carbon atoms, Y ₇ is an epoxyalkyl group having 1 to 5 carbon atoms, and Y ₁₀ is an aryl group having 6 to 18 carbon atoms.

In the present invention, the wax may be at least one selected from the group consisting of vegetable wax and synthetic resin wax.

In the present invention, the vegetable wax may be at least one selected from the group consisting of candelilla wax, carnauba wax, caster wax, esophalt wax, ocherite wax, bayberry wax, jojoba wax, rice bran wax and soy wax .

In the present invention, the synthetic resin wax may be at least one selected from the group consisting of paraffin wax, polyethylene wax, Fischer-Tropsch wax, amide wax, polypropylene wax, polyolefin wax and modified waxes thereof.

In the present invention, the rust inhibitor is a sulfonic acid-based rust inhibitor including calcium, magnesium, sodium and amine; An alkanolamine-based rust inhibitor including ethanolamine, propanolamine, dimethylethanolamine, heptamnol, methanolamine, and the like.

The resin composition according to the present invention may further comprise 0.1 to 3% by weight of a catalyst, and the catalyst may be at least one selected from the group consisting of para-toluenesulfonic acid, alkyd benzenesulfonic acid, acetylacetone, benzyl alcohol, have.

In addition, the present invention provides a semiconductor device comprising: a metal layer; And a surface treatment layer formed on one surface or both surfaces of the metal layer and made of the resin composition described above.

In the present invention, the metal layer may be a steel sheet or a galvanized steel sheet.

In the present invention, the thickness after drying of the surface treatment layer may be 2 to 30 탆.

The metal workpiece according to the present invention can be applied to a back cover of a display electronic appliance for home use.

According to the present invention, it is possible to produce a metal finished product such as an aqueous black resin steel sheet which is eco-friendly and excellent in physical properties such as designability, corrosion resistance, coating film adhesion, lubricity, blackness and bending property.

1 is a side view of a metal workpiece according to the present invention.

Hereinafter, the present invention will be described in detail.

The present invention is characterized in that an aqueous type resin composition for surface treatment using an aqueous organic resin and water is used instead of a volatile solvent in order to produce a metal processed product such as a black resin steel sheet to be applied to a back cover of a household electric appliance Thereby minimizing the problems of environmental pollution and lowering the production cost.

Further, the present invention is characterized by using a water-soluble organic resin and using a pigment, a dispersion stabilizer, an adhesion promoter, an antirusting agent or the like which is in conformity therewith, thereby increasing the environmental friendliness of the processed metal product, It is possible to provide a metal workpiece having excellent physical properties such as lubricity, bending property, adhesion, and corrosion resistance.

The resin composition for metal surface treatment according to the present invention may comprise an aqueous organic resin, a black pigment dispersion, a crosslinking agent, an adhesion promoter, a wax, a rust inhibitor, a catalyst and water.

Aqueous organic resin

The aqueous organic resin serves to improve physical properties such as corrosion resistance, film adhesion, and designability.

The aqueous organic resin is not particularly limited, but preferably at least one selected from the group consisting of an aqueous dispersion urethane resin, an aqueous dispersion acrylic resin, a water-soluble epoxy, a water-soluble polyester resin, a water-soluble amino resin, have.

The content of the aqueous organic resin is not particularly limited, but is preferably 20 to 80% by weight based on the total weight of the resin composition for surface treatment. When the content of the aqueous organic resin is less than 20% by weight, physical properties such as corrosion resistance, film adhesion and designability may be deteriorated. If the content is more than 80% by weight, physical properties such as blackness may be deteriorated.

Pigment Dispersant

When the resin composition for metal surface treatment of the present invention is coated on a metal such as a steel sheet, it is possible to improve the blackness of the metal and the physical properties such as solution stability and designability of the metal, .

The black pigment dispersion is for realizing the blackness of a black resin solution and generally includes pigment particles having very small particle sizes and accordingly has a very large surface area per unit weight. Therefore, when the resin solution is directly stirred, It is difficult to realize proper dispersion stability, and since such a non-uniform dispersion state is not suitable for realizing proper blackness of the pigment, a dispersion is generally prepared in advance and added to the remaining resin composition.

The black pigment dispersion is preferably contained in an amount of 1 to 45% by weight based on the total weight of the resin composition for metal surface treatment. If the content of the black pigment dispersion is less than 1% by weight, physical properties such as blackness and decorative properties may be deteriorated. If it exceeds 45% by weight, physical properties such as corrosion resistance and film adhesion may be deteriorated.

The black pigment dispersion may contain 10 to 80% by weight of an aqueous organic resin for dispersion, 5 to 60% by weight of black pigment particles, 0.5 to 10% by weight of a dispersion stabilizer and 1 to 52% by weight of water.

The black pigment dispersion contains black pigment particles of very small size in order to ensure high blackness and decorative properties. The surface area of the black pigment particles becomes very wide, and the uniform dispersion of the pigment particles in the resin composition It can not be obtained by ordinary solution stirring and is generally obtained through a separate dispersion process called milling. For such a dispersion process, the aqueous organic resin for dispersion is used in the present invention. By using the aqueous organic resin for dispersion, properties such as solution stability and designability of the resin composition can be improved.

The water-soluble organic resin for dispersion is not particularly limited, and any aqueous organic resin capable of dispersing the above-mentioned black pigment particles can be used without limitation. In the composition of the present invention, at least one selected from the group consisting of water-dispersible urethane resin, water-dispersible acrylic resin, water-soluble epoxy, water-soluble polyester resin, water-soluble amino resin, And an aqueous dispersion urethane resin can be preferably used, but the present invention is not limited thereto.

The content of the aqueous organic resin for dispersion is preferably 10 to 80% by weight based on the total weight of the black pigment dispersion. If the content of the aqueous organic resin for dispersion is less than 10% by weight, physical properties such as solution stability and designability may be deteriorated, and if it exceeds 80% by weight, properties such as blackness and decorative properties may be deteriorated.

Pigment particle

The black pigment particles serve to improve physical properties such as blackness and decorative properties of the resin composition.

The black pigment particles are not particularly limited, but preferably at least one selected from the group consisting of carbon nanotubes, carbon fibers, carbon black, graphite, and graphene having excellent properties such as blackness and dispersibility can be used.

The average particle diameter of the black pigment particles is not particularly limited, but may be in the range of preferably 2 to 10,000 nm. If the average particle diameter of the black pigment particles is less than 2 nm, the physical properties such as solution stability may be deteriorated. If the average particle diameter exceeds 10,000 nm, the blackness and physical properties such as design properties may be deteriorated.

The content of the black pigment particles is preferably 5 to 60% by weight based on the total weight of the black pigment dispersion. When the content of the black pigment particles is less than 5% by weight, physical properties such as blackness and decorative properties may be deteriorated. When the content of the black pigment particles exceeds 60% by weight, too much aggregation of pigment particles may result in degradation of physical properties such as solution stability and decorative properties .

Dispersion stabilizer

The dispersion stabilizer serves to improve physical properties such as solution stability and decorative properties of the black pigment dispersion and the resin composition.

The dispersion stabilizer is not particularly limited, but preferably one or more of the compounds represented by the following general formula (1) can be used.

[Chemical Formula 1]

In Formula 1,

n is an integer of 1 to 10,

R ₁ is an alkyl group having 1 to 5 carbon atoms,

R ₂ is ^{-OH, -ONa, -OK, -O -} NH4 +, -COOH, -COONa, -COOK, -COO - NH 4 +, -SO 3 H, -SO 3 Na, -SO 3 K, - ^{_{SO 3 - NH 4 +, -PO}} 3 H 2, -HPO 3 Na, -HPO 3 K, -PO 3 Na 2, -PO 3 K 2 And -SO can be a hydrophilic terminus selected from the group consisting of ₂ NHCOH.

The content of the dispersion stabilizer is preferably 0.5 to 10% by weight based on the total weight of the pigment dispersion. If the content of the dispersion stabilizer is less than 0.5% by weight, physical properties such as solution stability may be deteriorated. If the content is more than 10% by weight, physical properties such as design properties may be deteriorated.

Cross-linking agent

The crosslinking agent serves to improve physical properties such as hardness.

The crosslinking agent is not particularly limited, but one or more selected from the group consisting of a melamine crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and a mixture thereof may be preferably used.

The content of the crosslinking agent is not particularly limited, but is preferably 5 to 50% by weight based on the total weight of the resin composition. If the content of the cross-linking agent is less than 5% by weight, curing may not be completed, resulting in non-curing. If the content of the cross-linking agent is more than 50 parts by weight, physical properties such as bending properties may be insufficient.

Adhesion promoter

The adhesion promoter serves to improve physical properties such as coating film adhesion and corrosion resistance.

The adhesion promoter is not particularly limited, but preferably at least one selected from the group consisting of a titanium based adhesion promoter, a phosphate based adhesion promoter, and a silane based adhesion promoter can be used.

The titanium-based adhesion promoter is not particularly limited, but preferably one or more of the compounds represented by the following general formula (2) can be used.

(2)

In Formula 2,

R ₃ is H or an alkyl group having 1 to 5 carbon atoms,

R ₄ is _{-X 1 COX 2 COX 3, -X} 4 N (X 5) 2, -C (X 6) = is selected from the group consisting of _{CHCOX 7, X 1, X 2} , X 4 is a group having 1 to 5 carbon atoms X ₃ and X ₆ are each an alkyl group having 1 to 5 carbon atoms, X ₅ is a hydroxyalkyl group having 1 to 5 carbon atoms, and X ₇ is an alkyl group having 1 to 5 carbon atoms or O ^- NH ₄ ⁺ .

Preferably, R ₄ is _{-CH 2 COCH 2 COCH 3, -CH} 2 CH 2 N (CH 2 CH 2 OH) 2, -C (CH 3) = CHCOCH 3, -C (CH 3) = CHCOO - NH ₄ ⁺ . ≪ / RTI >

The phosphate adhesion promoter is not particularly limited, but preferably one or more of the compounds represented by the following formula (3) can be used.

(3)

In Formula 3,

R ₅ , R ₆ and R ₇ each independently represent a phenyl group containing an alkyl group having 1 to 9 carbon atoms.

The silane adhesion promoter is not particularly limited, but preferably one or more of the following compounds represented by the following general formula (4) can be used.

[Chemical Formula 4]

In Formula 4,

R ₈ is an alkyl group having 1 to 5 carbon atoms,

R ₉ is _{-Y 1 CH (Y 2) CH} (Y 3) NH 2, -Y 4 NHCONH 2, -Y 5 OY 6 CH (Y 7), -Y 8 NH 2, -Y 9 NH (Y 10) is selected from the group consisting of _{-Y 11 NCO, Y 1, Y} 4, Y 5, Y 6, Y 8, Y 9, Y 11 is a C 1 -C 5 alkylene group, Y ₂ is C 1 -C 5 Y ₃ is an alkyl group having 1 to 5 carbon atoms, Y ₇ is an epoxyalkyl group having 1 to 5 carbon atoms, and Y ₁₀ is an aryl group having 6 to 18 carbon atoms.

Preferably, R ₉ is _{-CH 2 CH (CH 2 NH 2} ) CH (CH 3) NH 2, -CH 2 CH 2 CH 2 NHCONH 2, CH 2 CH 2 CH 2 OCH 2 CH (OCH 2), - CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH (C ₆ H ₆ ), -CH ₂ CH ₂ CH ₂ NCO, and the like.

The content of the adhesion-promoting agent is not particularly limited, but is preferably 0.1 to 5% by weight based on the total weight of the resin composition. If the content of the adhesion promoting agent is less than 0.1% by weight, physical properties such as film adhesion and corrosion resistance can not be sufficiently improved, and if it exceeds 5% by weight, physical properties such as solution stability of the resin composition may be deteriorated.

Wax

The wax improves physical properties such as lubricity of the surface-treated metal sheet.

The wax is not particularly limited but is preferably selected from the group consisting of Candelilla wax, Carnauba wax, Caster wax, Esfatto wax, Ouerkyl wax, Bayberry wax, Jojoba wax, Rice bran wax, Vegetable wax such as wax; And synthetic waxes such as paraffin wax, polyethylene wax, Fischer-Tropsch wax, amide wax, polypropylene wax, polyolefin wax and modified waxes thereof.

The content of the wax is not particularly limited, but it is preferably 0.1 to 5% by weight based on the total weight of the resin composition for metal surface treatment. If the content of the wax is less than 0.1 wt%, the physical properties such as lubricity can not be sufficiently improved, and if it exceeds 5 wt%, the physical properties such as film adhesion can be lowered.

Anti-rust agent

The rust inhibitor has a role of improving physical properties such as corrosion resistance.

The rust inhibitor is not particularly limited, but is preferably a sulfonic acid-based rust inhibitor including calcium, magnesium, sodium, barium, zinc and amine; At least one selected from the group consisting of ethanolamine, propanolamine, dimethylethanolamine, heptamnol, and alkanolamine-based rust inhibitors including methanolamine can be used.

The content of the rust preventive agent is not particularly limited, but is preferably 1 to 10% by weight based on the total weight of the resin composition for metal surface treatment. If the content of the rust inhibitor is less than 1% by weight, the physical properties such as corrosion resistance can not be sufficiently improved. If the content is more than 10% by weight, physical properties such as solution stability may be deteriorated.

catalyst

The catalyst serves to further improve the curing rate of the coated metal sheet.

The catalyst is not particularly limited, but preferably at least one selected from the group consisting of para-toluenesulfonic acid, alkyd benzenesulfonic acid, acetylacetone, benzyl alcohol, and mixtures thereof can be used.

The content of the catalyst is preferably 3% by weight or less based on the total weight of the resin composition. If the content of the catalyst exceeds 3% by weight, the curing rate is not improved any more, and the physical properties such as solution stability may be lowered.

Metalwork

Fig. 1 is a side view of a metalwork product according to the present invention. The metalworkpiece may include a metal layer 2 and a surface treatment layer 1 formed on one or both surfaces of the metal layer 2. Fig.

The metal layer 2 may be a steel sheet or a galvanized steel sheet, and the surface treatment layer 1 may be made of the resin composition described above.

The thickness of the surface treatment layer 1 after drying is not particularly limited, but it may preferably be 2 to 30 탆. If the thickness after drying of the surface treatment layer 1 is less than 2 占 퐉, physical properties such as designability, self-healing property and corrosion resistance of the processed metal product may be deteriorated. If the thickness exceeds 30 占 퐉, The physical properties of the resin may be deteriorated.

The metal finished product according to the present invention may be, for example, a black resin steel sheet, and may be usefully applied to a back cover of a display electronic appliance for home use.

Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention and Comparative Examples which are not based on the present invention, but the scope of the present invention is not limited by the following Examples.

[Example 1]

(1) Production of resin composition for metal surface treatment

a. Production of black pigment dispersion

43.0% by weight of a polyurethane water-based resin (Sancure 898, Lubrizol) as a water-soluble organic resin for dispersion, 11.4% by weight of carbon black (FW 200, Evonik Degussa) as a black pigment, 8.3% by weight of ethoxylated betanaphthol as a dispersion stabilizer, 37.3% by weight of distilled water for adjustment and zirconia balls were added and the mixture was operated in a ball mill at 3,500 rpm for 2 hours to prepare a black pigment dispersion.

b. Resin composition manufacturing

52% by weight of a polyurethane water-based resin (Sancure 898, Lubrizol), 15.5% by weight of a black pigment dispersion prepared above, 8.4% by weight of a melamine crosslinking agent (Cymel 303, CYTEC) as a crosslinking agent, 2.5% by weight of Roxy bis (ammonium lactate) titanium (IV), 2.5% by weight of polyethylene wax (Microspersion 523, Micro powders, inc.) As wax, 3.6% by weight of calcium dinonylnaphthalene sulfonate as rust inhibitor, 0.6% by weight of toluene sulfonic acid (Nacure 2547, King) and 14.9% by weight of water were stirred at room temperature to prepare a resin composition.

(2) Manufacture of metalwork products

The resin composition for metal surface treatment prepared above was coated on an electrogalvanized steel sheet (steel sheet thickness: 0.45 mm) having a one-side zinc adhesion amount of 20 g / m 2 each using a roll coater, followed by drying and curing at 185 ° C to dry And the surface-treated steel sheet was made to have a thickness of 12 占 퐉.

[Examples 2 to 15]

(1) Production of resin composition for metal surface treatment

The content of aqueous organic resin for dispersion, the kind of black pigment, the size of black pigment and the content of black pigment, the chemical structure of dispersion stabilizer, the content of dispersion stabilizer and the content of distilled water in the preparation of black pigment dispersion were measured in the following Table 1 , The resin composition for metal surface treatment was prepared.

(2) Manufacture of metalwork products

The surface-treated steel sheet having the surface-treated layer formed thereon was prepared in the same manner as in Example 1.

In Table 1, the content is% by weight, CB is carbon black (FW200, manufactured by Evonik Daegu), CNT is carbon nanotube (CNTEC 3.0A, World tube), and Graphite is graphite (Graphitan 7525, manufactured by Ciba Geigy).

[Examples 16 to 33]

(1) Production of resin composition for metal surface treatment

In the production of the resin composition for metal surface treatment, the content of the aqueous organic resin, the content of the pigment dispersion, the content of the crosslinking agent, the type of the adhesion promoter, the content of the adhesion promoter, the content of the wax, the kind of the rust inhibitor, And the content of water were changed as shown in Table 2, the resin composition for metal surface treatment was prepared. In Table 2, the content is% by weight, and the composition of the pigment dispersion is the same as in Example 1. [

(2) Manufacture of metalwork products

The surface-treated steel sheet having the surface-treated layer formed thereon was prepared in the same manner as in Example 1.

[Comparative Examples 1 to 13]

(1) Production of resin composition for metal surface treatment

The content of the aqueous organic resin for dispersion, the kind of black pigment, the size of black pigment and the content of black pigment, the chemical structure of dispersion stabilizer, the content of dispersion stabilizer and the content of distilled water in the preparation of black pigment dispersion are shown in Table 3 , The resin composition for metal surface treatment was prepared.

(2) Manufacture of metalwork products

The surface-treated steel sheet having the surface-treated layer formed thereon was prepared in the same manner as in Example 1.

In Table 3, the content is% by weight, CB is carbon black (FW200, manufactured by Evonik Daegu), CNT is carbon nanotube (CNTEC 3.0A, World tube) and Graphite is graphite (Graphitan 7525, manufactured by Ciba Geigy).

[Comparative Examples 14 to 28]

(1) Production of resin composition for metal surface treatment

In the production of the resin composition for metal surface treatment, the content of the aqueous organic resin, the content of the pigment dispersion, the content of the crosslinking agent, the type of the adhesion promoter, the content of the adhesion promoter, the content of the wax, the kind of the rust inhibitor, And the content of water were changed as shown in Table 4, the resin composition for metal surface treatment was prepared. In Table 4, the content is% by weight and the composition of the pigment dispersion is the same as in Example 1. [

(2) Manufacture of metalwork products

The surface-treated steel sheet having the surface-treated layer formed thereon was prepared in the same manner as in Example 1.

[Test Example]

The physical properties of the resin composition and the surface-treated coated steel sheet prepared in Examples and Comparative Examples were measured by the following methods.

1. Blackness measurement

The L coordinate values (whiteness value) of the surface-treated steel sheets prepared in the above-mentioned Examples and Comparative Examples were measured using a Lab colorimeter (ColorEye XTH, GretagMacbeth Co.), and the blackness was measured according to the following evaluation criteria Respectively.

<Evaluation Criteria of Blackness>

?: When the L coordinate value of the surface-treated steel sheet is 26 or less

X: When the L coordinate value of the surface-treated steel sheet exceeds 26

2. Coating film adhesion measurement

The specimens were prepared by cutting the surface-treated steel sheets prepared in the above Examples and Comparative Examples to a size of 150 cm x 75 cm (width x length), and the surfaces of the specimens were cut with a cross-cut guide And a portion where the 100 cells were formed was pushed up to a height of 6 mm using an Erichsen tester and peeling tape (NB-1 , Ichiban Co., Ltd.) was attached and then peeled off to observe whether or not the Ericsson portion was peeled off.

&Lt; Evaluation Criteria of Coating Film Adhesion &

○: When there is no peeling of the surface

?: 1 to 3 of 100 peelings on the surface

X: When the peeling of the surface exceeds 3 out of 100

3. Bending property measurement

The bending resistance of the coated steel sheet was evaluated by coating the resin composition and hardening it with 0 T banding, observing the folded surface enlargedly and observing the following criteria.

[Evaluation standard]

○: 0%, 10%, 20% 0T banding and taping peeling after stretching are all clean without any cracks

△: There is no sign of crack at 0 T banding and taping peeling after 0% tensile, but at 0 T banding after peeling of 10% and 20% peeling,

X: 0%, 10%, 20% When 0T banding or taping peeling is performed after tensile, a partial crack or peeling of the entire film occurs

4. Measurement of lubricity

The surface friction coefficient was measured using a UMT-2MT from CETR (Center for Tribology Inc.) USA and evaluated according to the following criteria.

[Evaluation standard]

?: Friction coefficient (占 퐉) Less than 0.25

?: Friction coefficient (占 퐉)? 0.25 or more and less than 0.4

X: Friction coefficient (占 퐉) 0.4 or more

5. Corrosion resistance measurement

The specimen was subjected to a salt spray test in accordance with JIS-Z2371 for 144 hours, and the degree of smell was evaluated according to the following criteria.

[Evaluation standard]

○: less than 5% of white rye

△: White rice 5% or more and less than 20%

×: 20% or more of white rust

6. Designability Measurement

After curing of the coated steel sheet, surface defects were visually observed with a microscope and evaluated according to the following criteria.

[Evaluation standard]

○: When there is no obvious defect when observing 10 times magnification with naked eye and microscope

&Amp; cir &amp;: There was no obvious defect when observed with the naked eye, but when a 10-fold magnification was observed with a microscope, color change or partial peeling was observed

X: When a clear defect is observed when observing with the naked eye

7. Solution stability measurement

Immediately after the preparation of the resin composition for metal surface treatment prepared in Examples and Comparative Examples, the initial viscosity (Vi) was measured, and after cooling to 25 캜, the late viscosity (V 1) at 25 캜 was measured, (1), and the results were evaluated according to the following evaluation criteria.

[Equation 1]

? V = (Vi-Vi) / Vi x 100 (%)

<Evaluation Criteria for Solution Stability>

∘: ΔV is less than 20 (%) or gelation phenomenon is not observed by visual observation

占 V: ΔV is 20 (%) or more, or gelation phenomenon is observed upon visual observation

The results of the physical properties of the surface-treated steel sheets prepared in Examples 1 to 15 and Comparative Examples 1 to 13 are shown in Tables 5 and 6 below.

Example Blackness Coating film adhesion Bending ability Designability Solution stability One O O O O O 2 O O O O O 3 O O O O O 4 O O O O O 5 O O O O O 6 O O O O O 7 O O O O O 8 O O O O O 9 O O O O O 10 O O O O O 11 O O O O O 12 O O O O O 13 O O O O O 14 O O O O O 15 O O O O O

Comparative Example Blackness Coating film adhesion Bending ability Designability Solution stability One O O O X X 2 O O O X X 3 X O O X O 4 X O O X O 5 X O O X O 6 O X X X O 7 X O O X X 8 X O X X O 9 O O O X X 10 O O X X X 11 X O O X O 12 X O X X O 13 O X X X X

As shown in Tables 5 and 6, in Examples 1 to 15 according to the present invention, the content of the aqueous organic resin in the composition of the black pigment dispersion was in the range of 10 to 80% by weight, Of the dispersion stabilizer belongs to carbon nanotubes, carbon fibers, carbon black, graphite and graphene, the content and size of the black pigment particles fall within the range of 5 to 60% by weight and 2 to 10,000 nm, respectively, And the content of distilled water is in the range of 5 to 40% by weight. Thus, it can be seen that the blackness, the film adhesion, the bending property, the designability and the solution stability are excellent.

On the other hand, in the case of Comparative Examples 1 to 13 not according to the present invention, the content of the aqueous organic resin, the kind of the black pigment, the size of the black pigment, the content of the black pigment, The structure, the content of the dispersion stabilizer, and the content of the distilled water exceed the specific range in the present invention, it can be confirmed that at least two of the physical properties of the blackness, the film adhesion, the bending property, the designability and the solution stability are poor .

The results of measurement of the physical properties of the surface-treated steel sheets prepared in Examples 16 to 33 and Comparative Examples 14 to 28 are shown in Tables 7 and 8 below.

Example Blackness Coat
Adhesiveness solution
stability Bending ability Lubricity Corrosion resistance Designability 16 O O O O O O O 17 O O O O O O O 18 O O O O O O O 19 O O O O O O O 20 O O O O O O O 21 O O O O O O O 22 O O O O O O O 23 O O O O O O O 24 O O O O O O O 25 O O O O O O O 26 O O O O O O O 27 O O O O O O O 28 O O O O O O O 29 O O O O O O O 30 O O O O O O O 31 O O O O O O O 32 O O O O O O O 33 O O O O O O O

Comparative Example Blackness Coat
Adhesiveness solution
stability Bending ability Lubricity Corrosion resistance Designability 14 O X O X O O O 15 O O X X O O O 16 O X X X X O O 17 O O X O O O X 18 O O X X O O X 19 O X X X O O X 20 X X O X O X X 21 O X O X O X O 22 O X X O O X X 23 O X X O O O X 24 O X O X X X X 25 O X O X O X X 26 O X X X O X O 27 O X O X X X X 28 O O O O O X X

As shown in Tables 7 and 8, in Examples 16 to 33 according to the present invention, the content of the water-soluble organic resin in the composition of the resin composition for metal surface treatment falls within the range of 20 to 80% by weight, The content of the black pigment dispersion is in the range of 1 to 45% by weight, the content of the crosslinking agent is in the range of 5 to 50% by weight, and the component of the adhesion promoting agent is titanium, phosphate or silane adhesion promoting agent , The content of the adhesion promoter is in the range of 0.1 to 5 wt%, the content of the wax is in the range of 0.1 to 5 wt%, and the content of the rust inhibitor is selected from the group consisting of calcium, magnesium, sodium, An anti-rust agent, an alkanolamine-based rust inhibitor including ethanolamine, propanolamine, dimethylethanolamine, heptaminol, methanolamine, and the content of the rust inhibitor is 1 to 10% by weight , The content of the catalyst is in the range of 0.1 to 3 wt%, and the content of the distilled water is in the range of 5 to 60 wt%. Therefore, the blackness, the film adhesion, the solution stability, the bending property, It can be seen that the design is excellent.

On the other hand, in the case of Comparative Examples 14 to 28 not according to the present invention, the content of the aqueous organic resin, the content of the black pigment dispersion, the content of the crosslinking agent, the content and the content of the adhesion promoter, , At least one of the content and the content of the rust inhibitor, the content of the catalyst and the content of the water is out of the specific range in the present invention, the blackness, the film adhesion, the solution stability, the bending property, the lubricity, It can be confirmed that at least two or more ingredients are poor.

1: Surface treatment layer
2: metal layer

Claims (22)

Wherein the water-soluble organic resin comprises 20 to 80% by weight of the pigment dispersion, 1 to 45% by weight of the pigment dispersion, 5 to 50% by weight of the crosslinking agent, 0.1 to 5% by weight of the adhesion promoter, 0.1 to 5% 60% by weight,
The pigment dispersion contains 10 to 80% by weight of an aqueous organic resin for dispersion, 5 to 60% by weight of pigment particles, 0.5 to 10% by weight of a dispersion stabilizer and 1 to 52% by weight of water,
Wherein the dispersion stabilizer is a compound represented by the following Chemical Formula 1:
[Chemical Formula 1]

In Formula 1,
n is an integer of 1 to 10,
R ₁ is an alkylene group having 1 to 5 carbon atoms,
R ₂ is ^{-OH, -ONa, -OK, -O -} NH 4 +, -COOH, -COONa, -COOK, -COO - NH 4 +, -SO 3 H, -SO 3 Na, -SO 3 K, It is selected from ^{_{NH 4 +, -PO 3 H 2}} , -HPO 3 Na, -HPO 3 K, -PO 3 Na 2, the group consisting of -PO ₃ K _2, and -SO ₂ NHCOH ^- -SO _3.
The method according to claim 1,
Wherein said aqueous organic resin is at least one selected from the group consisting of water-dispersible urethane resin, water-dispersed acrylic resin, water-soluble epoxy, water-soluble polyester resin, water-soluble amino resin, Resin composition.
delete The method according to claim 1,
Wherein the aqueous organic resin for dispersion is at least one selected from the group consisting of water-dispersible urethane resin, water-dispersible acrylic resin, water-soluble epoxy, water-soluble polyester resin, water-soluble amino resin and mixtures thereof.
The method according to claim 1,
Wherein the pigment particles are at least one black pigment particle selected from the group consisting of carbon nanotubes, carbon fibers, carbon black, graphite and graphene.
The method according to claim 1,
Wherein the pigment particles have an average particle diameter of 2 to 10,000 nm.
delete The method according to claim 1,
Wherein the crosslinking agent is at least one selected from the group consisting of a melamine crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and a mixture thereof.
The method according to claim 1,
Wherein the adhesion promoter is at least one selected from the group consisting of a titanium-based adhesion promoter, a phosphate adhesion promoter, and a silane adhesion promoter.
10. The method of claim 9,
Wherein the titanium-based adhesion promoting agent is a compound represented by the following general formula (2): &lt; EMI ID =
(2)

In Formula 2,
R ₃ is H or an alkyl group having 1 to 5 carbon atoms,
R ₄ is _{-X 1 COX 2 COX 3, -X} 4 N (X 5) 2, -C (X 6) = is selected from the group consisting of _{CHCOX 7, X 1, X 2} , X 4 is a group having 1 to 5 carbon atoms X ₃ and X ₆ are alkyl groups having 1 to 5 carbon atoms, X ₅ is a hydroxyalkyl group having 1 to 5 carbon atoms, and X ₇ is an alkyl group having 1 to 5 carbon atoms or O ^- NH ₄ ⁺ .
10. The method of claim 9,
Wherein the phosphate adhesion promoting agent is a compound represented by the following formula (3): &lt; EMI ID =
(3)

In Formula 3,
R ₅ , R ₆ and R ₇ each independently represent a phenyl group containing an alkyl group having 1 to 9 carbon atoms.
10. The method of claim 9,
Wherein the silane-based adhesion promoting agent is a compound represented by the following formula (4): &lt; EMI ID =
[Chemical Formula 4]

In Formula 4,
R ₈ is an alkyl group having 1 to 5 carbon atoms,
R ₉ is _{-Y 1 CH (Y 2) CH} (Y 3) NH 2, -Y 4 NHCONH 2, -Y 5 OY 6 CH (Y 7), -Y 8 NH 2, -Y 9 NH (Y 10) is selected from the group consisting of _{-Y 11 NCO, Y 1, Y} 4, Y 5, Y 6, Y 8, Y 9, Y 11 is a C 1 -C 5 alkylene group, Y ₂ is C 1 -C 5 Y ₃ is an alkyl group having 1 to 5 carbon atoms, Y ₇ is an epoxyalkyl group having 1 to 5 carbon atoms, and Y ₁₀ is an aryl group having 6 to 18 carbon atoms.
The method according to claim 1,
Wherein the wax is at least one selected from the group consisting of vegetable wax and synthetic resin wax.
14. The method of claim 13,
Wherein the vegetable wax is at least one selected from the group consisting of candelilla wax, carnauba wax, caster wax, esport wax, ocherite wax, bayberry wax, jojoba wax, rice bran wax and soy wax. Resin composition for surface treatment.
14. The method of claim 13,
Wherein the synthetic resin wax is at least one selected from the group consisting of paraffin wax, polyethylene wax, Fischer-Tropsch wax, amide wax, polypropylene wax, polyolefin wax and modified waxes thereof.
The method according to claim 1,
The rust inhibitor may be a sulfonic acid-based rust inhibitor including calcium, magnesium, sodium, and amine; Wherein the resin composition is at least one selected from the group consisting of an alkanolamine-based rust inhibitor including ethanolamine, propanolamine, dimethylethanolamine, heptaminol and methanolamine.
The method according to claim 1,
And 0.1 to 3% by weight of a catalyst.
18. The method of claim 17,
Wherein the catalyst is at least one selected from the group consisting of paratoluene sulfonic acid, alkyd benzene sulfonic acid, acetylacetone, benzyl alcohol, and mixtures thereof.
A metal layer; And
And a surface treatment layer formed on one or both surfaces of the metal layer and made of the resin composition according to claim 1.
20. The method of claim 19,
Wherein the metal layer is a steel sheet or a galvanized steel sheet.
20. The method of claim 19,
Wherein the thickness of the surface treatment layer after drying is 2 to 30 占 퐉.
20. The method of claim 19,
Wherein the product is applied to a back cover of a display electronic product for home use.

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