WO2005071052A1

WO2005071052A1 - Lubricating aqueous polyurethane resin composition, method for lubricating surface of zinc-plated steel sheet using same, and surface-treated steel sheet

Info

Publication number: WO2005071052A1
Application number: PCT/JP2005/001287
Authority: WO
Inventors: Atsushi Morishita; Akira Takahashi; Yujiro Miyauchi; Hiroshi Kanai; Yasuhiro Kinoshita; Ryosuke Sako; Keichi Ueno
Original assignee: Nippon Steel Corporation; Nihon Parkerizing Co., Ltd.
Priority date: 2004-01-26
Filing date: 2005-01-24
Publication date: 2005-08-04
Also published as: TWI300094B; JP4671609B2; KR100744094B1; CN100554389C; CN1934232A; JP2005206764A; MY148579A; TW200536932A; KR20060126748A

Abstract

Disclosed is an aqueous polyurethane resin composition for forming a coating film over a zinc-plated steel sheet which film is excellent in corrosion resistance, alkali resistance, coating adhesiveness and lubricity. The aqueous polyurethane resin composition contains (a) a polyurethane resin having a polyester skeleton part and a polyether skeleton part, a tensile strength at break of not less than 3.92 kN/cm2 (JIS 7113), a tensile elongation at break of not more than 50%, and a glass transition temperature of 80-150˚C (Tg, JIS K 7121); (b) fine polyolefin resin particles having a melting point of 70-160˚C and a particle diameter of 0.5-5 μm; and (c) a colloidal silica having a particle diameter of 5-50 nm. Relative to the mass of the total solid content (a + b + c), the solid content of the component (a) is 50-93 mass%, the solid content of the component (b) is 2-20 mass%, and the solid content of the component (c) is 5-40 mass%.

Description

Lubricating water-based polyurethane resin composition, surface lubrication treatment method for zinc-based plating steel sheet using the same, and surface-treated steel sheet

Technical field

INDUSTRIAL APPLICABILITY The present invention is used for press processing of home appliances, building materials, etc.

The present invention relates to a lubricating aqueous polyurethane resin composition for a surface lubricated steel sheet, a surface treatment method using the same, and a product thereof.

book

Background art

Conventionally, zinc or zinc-based alloy steel sheets have been widely used for home appliances and building materials. Since these steel sheets have insufficient corrosion resistance and paintability as they are, they are subjected to a base treatment such as chromate conversion treatment and phosphate conversion treatment, and then coated with resin on the surface. The obtained surface-treated steel sheet came to be used. Some of these surface-treated steel sheets are lubricated steel sheets that can be processed without using press oil at the time of pressing, and are widely used in home appliances and the like.

As prior art relating to this lubricating steel plate, Japanese Patent Application Laid-Open No. 2001-214182 (Patent Document 1) and Japanese Patent Application Laid-Open No. 08-270702 (Patent Document 2) And Japanese Patent Application Laid-Open No. H06-145559 (Patent Document 3).

Japanese Unexamined Patent Publication No. 2000-1 — 2114182 (Patent Document 1) discloses that an acryl-styrene resin (a) having an acid value of less than 10 is converted to a solid content of 30%. A mixed resin (A) containing 5 to 70% by mass of the polyurethane resin (b) in terms of solid content, and a chromium compound (c) And resin particles (d) having a melting point higher than the glass transition point of the two resins constituting the mixed resin and having an average particle diameter of 1 to 5 μιη. A coating layer formed from 1 to 7% by mass of the mixture (B) with respect to the total mass of the mixed resin (A) and having a thickness of 0.5 to 4 μm is formed on a zinc-coated steel sheet. At least a method of forming on one side is disclosed. In addition, Japanese Patent Application Laid-Open No. 08-270702 (Patent Document 2) discloses that, on both sides of a zinc or zinc-based steel sheet, 10 to 200 mg per one side in terms of metal mouthpiece. has a click Rome bets coating Z m ^2, thereon, the following mixed resin, curing agent

Resin composition containing 5 to 40 parts by weight, 1 to 40 parts by weight of a lubricant having a melting point of 80 ° C. to 130 ° C., and 5 to 80 parts by weight of an organic silicon compound A method is disclosed in which a material layer is formed at an application amount of 0.1 to 1.0 g Zm ² by dry weight. However, the mixed resin has two or more kinds of resins having a glass transition temperature of from 130 ° C. to 90 ° C. having a plurality of hydroxyl groups, that is, a glass transition temperature of from 130 ° C. to 30 ° C. A component consisting of one or more resins having a glass transition temperature of 30 ° C. to 90 ° C. and a component consisting of one or more resins having a temperature of less than 10 ° C., each containing at least 10% by weight of the total resin It does contain it.

All of these technologies feature the use of several types of resins for blending.However, when this blend is formed into a film, it is important to note that each resin is uniformly distributed in the formed film. The properties of the obtained film are often varied, and it cannot be said that the properties of each resin are utilized. For this reason, it is difficult for the film obtained by the above-mentioned prior art method to sufficiently achieve the performances such as lubricity, solvent resistance, and corrosion resistance required by the present invention.

Japanese Patent Application Laid-Open No. 06-145559 (Patent Document 3) discloses a method having a bisphenol-type skeleton, an ester skeleton, and a lipoxyl group. A water-dispersible ether / ester type polyurethane resin having an average molecular weight of 300 or more (a), a water-soluble or water-dispersible epoxy resin (b), and a melting point of 70 to 160 ° C Containing a polyolefin wax (c) having an average particle size of 0.1 to 7 · O ^ m and a siliency (d) having an average particle size of 3 to 3Οππμμπι, (a) And the total amount of (b) is 0.50: 1 to 0.85: 1 in terms of the weight ratio of solids to the total solids (e = a + b + c + d). The solids weight ratio with respect to e) is 0.33: 1 to 0.30: 1, and the solids weight ratio of (d) with respect to (e) is 0.10: 1 to 0.40: The technology relating to the water-based lubricating coating composition, which is 1, is disclosed.

In the technique of Patent Document 3, the desired performance is obtained by adding a crosslinking agent to a specific polyurethane resin. However, Patent Document 3 does not disclose any means for using a polyurethane resin composition containing no cross-linking agent to obtain the same or better performance.

[Patent Literature 1] Japanese Patent Application Laid-Open No. 2000-2-1024182, Claim 1 [Patent Literature 2] Japanese Patent Application Laid-Open No. 08-266700, Claim 1 [Patent Document 3] Japanese Patent Application Laid-Open No. 06-145550, Claim 1, Disclosure of the Invention

SUMMARY OF THE INVENTION An object of the present invention is to solve the problem of the prior art of performance degradation due to non-uniformity of a film, and to use an aqueous polyurethane resin composition having excellent lubricity, solvent resistance, and corrosion resistance, and use of the same. Another object of the present invention is to provide a method of lubricating the surface of a zinc-based coated steel sheet and a surface-treated steel sheet obtained by the method.

The present inventors have intensively studied an aqueous chemical which simultaneously satisfies the properties of lubricity, solvent resistance and corrosion resistance, and a surface-treated steel sheet using the same. As a result of the repeated studies, they have found that the above problem can be solved mainly by specifying the urethane resin, and have completed the present invention.

The lubricating aqueous polyurethane resin composition of the present invention comprises the following components (a), (b) and (c):

(A) and a polyester skeleton part and a polyether skeleton part, and JISK 7 1 1 3 Ri measured by the ^{3. 9 2 k N / cm 2} (4 0 0 kgf / cm 2) or more tensile fracture A urethane resin having a tensile strength, a tensile elongation at break of 50% or less, and a glass transition temperature (T g) of 80 to 150 ° C. measured according to JISK7121;

(b) fine particles of a polyolefin resin having a melting point of 70 to 160 ° C and a particle size of 0.5 to 5 μππ, and

(c) a colloidal silica having a particle diameter of 5 to 50 nm, and an aqueous resin composition comprising:

For the total solid mass (a + b + c) of the components (a), (b) and (c),

The solid content (( _a ) / (a + b + c)) of the component (a) is 5O to 93% by mass,

The solid content ((b) / (a + b + c)) of the component (b) is 2 to 20% by mass, and

The solid content ((c) / (a + b + c)) of the component (c) is 5 to 40% by mass.

It is characterized by the following.

In the lubricating aqueous polyurethane resin composition of the present invention, the mass ratio of the polyester skeleton to the polyether skeleton in the polyurethane resin (a) is preferably in the range of 1 Z 9 to 5/5. New

The method for lubricating a zinc-based plated steel sheet according to the present invention comprises: Applying a treatment solution containing a sex aqueous poly urethane resin composition to the surface of the zinc-based main Tsu key steel and dried to form a lubricating layer having a dry solid weight of 0. l~ 5 g _ m ² that It is characterized by the following.

The surface-lubricated zinc-coated steel sheet of the present invention is manufactured by the method of lubricating a zinc-based plated steel sheet of the present invention.

By applying the lubricating water-based polyurethane resin composition of the present invention to the surface of a zinc-coated steel sheet, a film having excellent corrosion resistance, alkali resistance, coating adhesion, and lubricity can be formed.

The term “aqueous polyurethane resin composition” in the present invention means “a polyurethane resin composition that can be dissolved, dispersed or emulsified in a medium containing water”. BEST MODE FOR CARRYING OUT THE INVENTION

The (a) polyurethane resin contained in the resin composition of the present invention has a tensile rupture strength of at least 3.9 N / cm ² (400 kgf / cm ² ), preferably at least 4.9. 9.9.8 N / cm ² , tensile elongation at break is 50% or less, preferably 1 140%, and its thermal transition temperature (T g) is 80〜150 °. C (measured according to JISK 7121). In a molding process such as a press process, a resin film generally receives a strong shearing force. If this shear force exceeds the tensile strength of the coating, the coating itself will be damaged. That is, when the tensile strength of the coating is high, the coating is not easily damaged. As a result of intensive studies, the present inventors have found that the tensile strength of the resin film itself is 3.92 kN / cm ² (400 K gf Z cm ² ) or more, and the tensile elongation at break is 5%. It has been found that the target lubricity can be obtained when it is 0% or less and T g is 80 to 150 ° C. In measuring the tensile strength and elongation of the polyurethane resin, a dry film was placed on the polyester sheet. The resin is applied to a thickness of 50 μm, dried at room temperature for 24 hours, baked at 150 ° C for 30 minutes to produce a film, and the film is gently removed from the polyester sheet. Then, it was subjected to a tensile test. The tensile test was performed in accordance with JISK6732. Further, the glass transition temperature of the polyurethane resin was measured using a commercially available dynamic viscoelasticity measuring device (Leoguchi Graph Solid S-1 manufactured by Toyo Seiki Seisaku-sho, Ltd.). At this time, a test piece with a thickness of 100 μππι, a width of 8 mm, and a length of 30 mm was dried at 100 ° C for 30 minutes and used at a measurement frequency of 100 Hz. Yes, the glass transition temperature was determined from the inflection point of the elastic loss rate.

The solid content of the component (a) is 50 to 93% with respect to the total solid mass (a + b + c) of the components (a), (b) and (c). Preferably, it is 55 to 90%, more preferably 50 to 85%. When the solid content of the component (a) is the same as that of the components (a), (b) and

When the total solid content mass (a + b + c) of (c) is less than 50%, the film continuity of the obtained polyurethane resin composition is low, and thus the processability of the polyurethane resin composition is low. However, the adhesion becomes insufficient. On the other hand, when the solid content of the component (a) exceeds 93% of the total solid mass (a + b + c) of the components (a), (b) and (c), the component ( Since the effect of adding b) and component (c) is poor, the resulting polyurethane resin composition film becomes insufficient in corrosion resistance and workability.

The polyurethane resin for the component (a) used in the present invention has a polyester skeleton and a polyether skeleton. The polyester skeleton is obtained from a polyester polyol compound, and the polyether skeleton is obtained from a polyether polyol.

As a polyester polyol compound for forming a polyester skeleton, , F, low molecular weight polyols, ethylene glycol, ethylene glycol cornole, triethylene glycol, 1, 2 — propylene glycol cornole, 1, 3 — propylene glycol cornole, neopentinole glycolonele, 1, 2 Butylene glycol, 1,3—butylene glycol, 1,4—butylene glycol, 3-methylpentanediol, hexamethylenglycol, hydrogenated bisphenanol A, trimethylolpropane, glycerin, etc., and polybasic acids, For example, succinic acid, dalta / leic acid, adipic acid, sepatic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, endmethylene trahydrophthalic acid, and By reaction with hexahydrophtalic acid, etc. It is one that is forming a compound having an ester structure and a terminal arsenate Doroki sheet 7 Les group.

Examples of the polyether polyol for forming a polyether skeleton include glycols having a bisphenol skeleton, for example, methylenebisphenol, ethylidenebisphenol, butylidenebisphenol, and isopropylidenebis. In phenols and the like, phenols containing 24 carbon atoms (for example, ethylenoxide, propylene oxide, etc.)

, Butylene oxide-

) Is preferably used.

The number of additional monoles of the alkylene oxide is preferably 1 to 10.

The mass ratio of the polyester skeleton to the polyester skeleton of the polyurethane resin for the component (a) is preferably in the range of (polyester skeleton / polyether skeleton = 1Z9-5Z5). When the mass ratio of the polyester skeleton to the polyether skeleton is less than 1 Z9, the content ratio of the relatively rigid polyether skeleton is high, and the extensibility of the film itself is low. The resulting coating is brittle and may have insufficient tensile fracture strength. On the other hand, when the mass ratio between the polyester skeleton and the polyether skeleton exceeds 5 Z5, the content ratio of the relatively flexible polyester skeleton becomes high, so that The extensibility of the resulting film may be high, and its tensile strength may be insufficient. The fine particles of (b) the polyolefin resin contained in the polyurethane resin composition of the present invention have a melting point of 70 to 160 ° C. and a particle size of 0.5 to 5 μιη. Generally, during press molding, the temperature of the molded product can reach 80 ° C. For this reason, if the melting point of the polyolefin resin fine particles is less than 70 ° C, all of the polyolefin resin fine particles in the film formed from this polyurethane resin composition will melt during molding. Therefore, it is not possible to obtain a film having sufficient lubricity in the forming process. On the other hand, when the melting point of the polyolefin resin fine particles exceeds 160 ° C, melting of the polyolefin resin fine particles due to sliding frictional heat becomes difficult to occur, and the resulting film has poor lubrication during sliding. Will be enough. When the polyolefin resin fine particles have a particle size of less than 0.5 μιη, the resulting resin film has insufficient lubricity. If the particle size exceeds 5.Ομπι, the polyolefin resin fine particles are likely to fall off from the obtained resin film. As the shape of the polyolefin resin fine particles, a true spherical shape is preferable in order to obtain a polyurethane resin composition having high workability.

The solid content of the component (b) is 2 to 20% based on the total solid mass (a + b + c) of the components (a), (b) and (c). , Preferably 3 to 20%, more preferably 3 to 18%. When the solid content of the component (b) is less than 2% based on the total solid mass (a + b + c) of the components (a), (b) and (c), a component is obtained. The lubricity of the polyurethane resin composition becomes insufficient. Before When the solid content of the component (b) exceeds 20% with respect to the total solid mass (a + b + c) of the components (a), (b) and (c), Adhesion between the film formed from the polyurethane resin composition to be obtained and the overcoat paint is insufficient.

The particle diameter of the component (c) colloidal silica is 5 to 50 nm, preferably 5 to 40 nm, more preferably 5 to 30 nm. Component (c) If the particle diameter of the colloidal silicide exceeds 50 nm, the uniformity of the film formed from the obtained polyurethane resin composition will be insufficient, and therefore, the corrosion resistance and adhesion of the film will be insufficient. Etc. become insufficient. When the particle diameter of the component (c) colloidal silica is less than 5 nm, production on an industrial basis becomes difficult, and it is economically disadvantageous. The solid content of the component (c) is 5 to 40%, preferably 5 to 40%, based on the total solid mass (a + b + c) of the components (a), (b) and (c). 335%, more preferably 5-30%. If the solids content of component (c) is less than 5% of the total solids mass (a + b + c) of components (a), (b) and (c), the resulting poly The effect of improving the corrosion resistance of the urethane resin composition becomes insufficient. When the solid content of the component (c) exceeds 40% with respect to the total solid mass (a + b + c) of the components (a), (b), and (c), The resulting polyurethane resin composition film becomes brittle, and its corrosion resistance, adhesion, and workability become insufficient.

The aqueous polyurethane resin composition for metal surface treatment of the present invention includes a surfactant called a wettability improver for forming a uniform film on the surface to be coated with a metal material, and a thickener for adjusting viscosity. It may contain one or more of an agent, a conductive substance for improving the weldability, a coloring pigment for improving the design, a metal additive having an inhibitory effect, and a metal compound. The surface is treated with the lubricating aqueous polyurethane resin composition of the present invention. There are no particular restrictions on the type of metal material used, but it is generally most effective to apply it to zinc-based plating steel sheets. The amount of the film formed on the surface of the zinc-based medic steel sheet is 0.1 to 5.0 Og / m ² , preferably 0.2 to 4.0 g Zm ² , more preferably, dry mass. Is 0.3 to 4 g / m ² . If the dry weight of the coating formed on the surface of the zinc-based plating steel sheet is less than 0.1 g Zm ² , the effect of improving the lubricity of the polyurethane resin composition is insufficient. Further, when the dry weight of the film formed on the surface of the zinc-based plated steel sheet exceeds 5. OgZm ² , the lubricating effect is saturated, so that there is an economic disadvantage. Examples of a method for applying the treatment liquid containing the polyurethane resin composition of the present invention include a roll coater method, a dipping method, and an electrostatic coating method, but the method of the present invention is not particularly limited thereto. The treatment temperature for the applied treatment liquid layer or its dried film is not particularly limited, but it is preferable to control the ultimate plate temperature within the range of 100 to 200 ° C.

Further, regarding the surface-treated steel sheet of the present invention, there is no limitation on the type and conditions of the pretreatment step performed on the zinc-based steel sheet before the lubrication step by the method of the present invention, but the Pretreatment includes degreasing to maintain cleanliness, chromate treatment to improve corrosion resistance, phosphate treatment, and nonchromate treatment that does not contain chrome-based compounds that have excellent anti-dust effect. By applying, the lubricating polyurethane resin composition film formed thereon can exhibit excellent lubricity and adhesion. Example

The present invention is further described by the following examples. The aqueous polyurethane resin compositions used in the following Examples and Comparative Examples were prepared as follows. Manufactured.

Production Example 1

Production of Ice-based Polyurethane Resin a 1 for Examples

Bisphenol A propylene xylene having an average molecular weight of 100, synthesized from adipic acid having a hydroxyl group at the end and 1,6-hexanediol, 40 parts of an average molecular weight of 600 The mixture of 3 parts of adduct of 3 moles and 100 parts of 2,2-bis (hydroxymethyl) propionic acid in 100 parts of N-methyl-2-pyrrolidone was mixed at 80 ° C. To dissolve. Thereafter, 120 parts of dicyclohexylmethandiocyanate was added to the solution, the mixture was heated to 110 ° C and reacted for 2 hours, and the reaction product was treated with triethylamine 10%. Neutralized. The resulting solution was added dropwise to an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water under vigorous stirring to produce an aqueous polyurethane resin. . This resin has a tensile fracture strength of 7.35 kN / cm ² (750 kgf / cm ² ), a tensile elongation at break of 10%, and a T g of 105 ° C. Was. The mass ratio of the polyester skeleton to the polyether skeleton at this time was as follows: Polyester skeleton / polyether skeleton = 2Z8

Production of aqueous polyurethane resin a2 for Examples

Bisphenol A propylene having an average molecular weight of 600 and an average molecular weight of 600, synthesized from adipic acid having a hydroxyl group at the terminal and 1,6-hexanediol. Add 180 parts of a 3 molar adduct of xide and 12 parts of 2,2-bis (hydroxymethyl) propionic acid to 100 parts of N-methyl-2-pyrrolidone Q, The resulting mixture was heated to 80 ° C to dissolve. Gain To this solution was added 110 parts of dicyclohexylmethanediisocyanate, and the mixture was heated to 110 ° C and reacted for 2 hours. And neutralized by 1 part. This solution was added dropwise to an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water with vigorous stirring to produce an aqueous polyurethane resin. The tensile fracture strength of this resin was 7.84 kNZcm ² (80 OK gf / cm ² ), and the tensile elongation at break was 5%. Its T g was 125 ° C. The mass ratio of the polyester skeleton to the polyether skeleton at this time was polyester skeleton / polyester skeleton = 1Z9.

Production Example 3

Production of aqueous polyurethane resin a3 for Examples

Bisphenol A propylenoxide having an average molecular weight of 100 parts and an average molecular weight of 66, synthesized from adipic acid having a hydroxyl group at the end and 1,6-hexanediolone. 120 parts of the 3-molar adduct and 12 parts of 2,2-bis (hydroxymethyl) propionic acid are added to 100 parts of N-methyl-12-pyrrolidone, and the mixture is added to the mixture. It was dissolved by heating to 80 ° C. To this solution was added 100 parts of dicyclohexylmethanediisocyanate, the mixture was heated to 110 ° C. and reacted for 2 hours, and 11 parts of triethylamine was added to the obtained reaction product. Neutralized by addition. This solution was added dropwise to an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water with vigorous stirring to produce an aqueous polyurethane resin. The tensile breaking strength of the resin ^{6. 3 7 k N / cm 2} (6 5 0 K gf / cm 2), tensile fracture壌伸beauty rate was 25%, met the The T g 8 5 ° C Was. In this case, the mass ratio of the polyester skeleton to the polyether skeleton is expressed as follows: polyester skeleton Z polyether skeleton = 4 / It was 6.

Production Example 4

Production of water-based urethane resin a4 for comparative example

Synthesized from adipic acid having a hydroxyl group at the end and 1,6-hexanediol, 230 parts of polyester polyol having an average molecular weight of 100,000 and 2,2-bis (hydroxymethyl) pro 15 parts of pionic acid were mixed into 100 parts of N-methyl-12-pyrrolidone, and the mixture was dissolved by heating to 80 ° C. To the obtained solution, 100 parts of dicyclohexylmethanediisocyanate was added, the obtained mixture was heated to 110 ° C and reacted for 2 hours, and the obtained reaction product was treated with triethylamine. Neutralized by one part. This solution was added dropwise to an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water under vigorous stirring to produce an aqueous urethane resin. The tensile rupture strength of this resin is 3.92 kN / cm ² (400 kgf / cm ² ), the tensile rupture elongation is 400%, and its T g is 30 °. C. The mass ratio between the polyester skeleton and the polyether skeleton in the polyurethane resin was polyester skeleton / polyether skeleton = 10/0.

Production Example 5

Production of water-based polyurethane resin a5 for comparative example

Bisphenol A propylene oxide having an average molecular weight of 660, 3-mol adduct of 200 parts, and 15 parts of 2,2-bis (hydroxymethyl) propionic acid were combined with N-methyl-1-pyrrolidine. The mixture was mixed in 100 parts of Don and the mixture was dissolved by heating to 80 ° C. This solution was mixed with 120 parts of dicyclohexylmethanediacid, the mixture was heated to 110 ° C and reacted for 2 hours, and the resulting reaction product was treated with triethynoleamine 15 Neutralized. Add this solution to ethylenediamine 5 parts of deionized water and 570 parts of deionized water were mixed, and the mixture was dropped under strong stirring to produce an aqueous polyurethane resin. The tensile strength of this resin was 6.37 kN / cm ² (650 kgf / cm ² ), and the tensile elongation at break was 5%. Further, its T g was 140 ° C. Further, the mass ratio of the polyester skeleton to the polyether skeleton in the polyurethane resin was polyester skeleton / polyether skeleton = 0/10.

The metal materials used in the following examples and comparative examples were prepared as described below.

Raw materials

(1) Electric Z II plated steel plate (symbol: EG)

Thickness = 0. 8 mm (basis weight (Table / back) = 2 0/2 0 ( g / m 2))

(2) Hot-dip Zri coated steel sheet (symbol: G I)

Thickness = 0. 8 mm (basis weight (Table Z back) = 6 0/6 0 ( g / m 2))

(3) Melt 5 5% A 1 _ Z n alloy plated steel sheet (symbol: GL) thickness = 0. 8 mm (basis weight (Table / back) = 9 0 Z 9 0 ( g / m 2))

(4) Electric Zn-Ni alloy-coated steel sheet with Ni content of 12 wt% (symbol: ZL)

Thickness = 0. 8 mm (basis weight (Table Z back) = 2 0/2 0 ( g / m 2))

(5) Fused 1 1% A 1 — 3% Mg — 0.2% S i _ Zn alloy-plated steel sheet (symbol: SD)

Plate thickness = 0.8 mm (weight per unit area (front / back) = 60 Z 60 (g / m ² )) Degreasing treatment

Fine Cleaner 43336 (trademark, active ingredient concentration = 20 g / l, manufactured by Nippon Parkerizing Co., Ltd.) was used as a degreasing agent. , Sprayed for 2 minutes, and immediately after the degreasing treatment, the degreasing treated steel sheet was washed with water, and then subjected to the following base coat treatment, base zinc phosphate treatment, or non-chromate treatment.

surface treatment

(1) Chromate treatment

A spray treatment (bath temperature = 50 ° C, time = 5 ° C) was applied to the degreased steel sheet using Zinchrome 357 (trademark, manufactured by Nippon Parti Rising Co., Ltd.) as a chromate treatment agent. ) And the formed base film was washed with water, and then dried for 10 seconds at an ambient temperature of 220 ° C (plate temperature reaching the steel plate = 100 ° C). The chromium adhesion amount by this treatment was 1 O mg / m ² .

(2) Zinc phosphate treatment

Using Pal Pond L320 (trademark, manufactured by Nippon Pasco Rising Co., Ltd.) as a zinc phosphate treating agent, immersion treatment (45 ° C, 2 ° C) was performed on the degreased steel sheet. Immersion), washed with water, and air-dried. The mass of the formed chemical conversion film was 2. O g Zm ² .

(3) Non-chromatized processing

As a non-chromate treating agent, PARCOAT 384 1 (trademark, manufactured by Nippon Parkerizing Co., Ltd., containing silane compound) was applied to the degreased steel sheet using a roll coater. The treated layer was immediately dried for 10 seconds at an ambient temperature of 220 ° C. (attainment temperature of the steel sheet = 100 ° C.). At this time, the mass of the dried film was 0.2 g Zm ² .

Aqueous dispersion of "polyolefin tree for component (b)" Examples and 1; Table 1 shows the trademark, solid content concentration, and particle size of the aqueous dispersion of the polyolefin resin used in the comparative examples. These were all made by Mitsui Ichigaku.

table 1

Component of Examples and Comparative Examples Polyolefin resin aqueous dispersion for component (b)

Colloidal force for component (c)

Table 2 shows the trademark, solid content concentration, and particle size of the colloidal sily force used in Examples and Comparative Examples. These were all made by Nissan Chemical.

Table 2

Colloidal force for Examples and Comparative Examples

Composition of lubricating aqueous resin composition

The compositions of the lubricating aqueous polyurethane resin compositions d1 to (! 9 used in Examples are shown in Table 3. The compositions of the resin compositions d10 to d15 used in Comparative Examples are shown in Table 3. The results are shown in Table 4. The numbers in parentheses in Tables 3 and 4 The value indicates the ratio (%) of the solid content mass of each component to the total solid content mass of the aqueous polyurethane resin composition.

Table 3

Composition of aqueous polyurethane resin composition for Examples

No (a) urethane resin (b) polyolefin resin (c) co-idanoresili force d 1 a 1 (70) b 1 (1 0) c 1 (20) d 2 a 2 (75) b 1 (1 0) c 1 (1 5) d 3 a 3 (65) b 1 (1 0) c 1 (25) d 4 a 3 (60) b 1 (2) c 1 (38) d 5 a 1 (60) b 1 ( 20) c 1 (20) d 6 a 1 (80) b 1 (1 5) c 1 (5) d 7 a 1 (70) b 2 (1 0) c 1 (20) d 8 a 1 (70) b 3 (1 0) c 1 (20) d 9 a 1 (70) b 1 (1 0) c 2 (20)

Table 4

Composition of aqueous resin composition for comparative example

Lubrication processing

The coating liquid containing the lubricating aqueous resin composition shown in Tables 3 and 4 was applied to the surface of the steel material using a per coater, and the coating liquid layer was dried at an ambient temperature of 320 ° C for 12 seconds. . At this time, the temperature reached by the steel material was 100 to 200 ° C. (preferably 120 ° C.), and the coating weight was 1.0 g Zm ”.

When the steel temperature was other than 120 ° C, the heating atmosphere temperature and heating time were as follows. '

100 ° C: 320 ° C X 9 seconds

150 ° C: 320. C X 16 seconds

180 ° C: 320 ° C X 22 seconds 2 O 0 ° C: 32 0 ° C X 27 seconds

Painted board 'performance test (1) Corrosion resistance

A salt spray test using JIS—Z—2731 was performed for 200 hours, and the occurrence of whitening was observed.

4 鲭 Generated area is less than 3% of total area

3 鲭 Generated area is 3% or more and less than 10% of total area

2 鲭 Generated area is 10% or more and less than 30% of the total area

1 鲭 Generated area is 30% or more of total area

(2) Alkali resistance

After being immersed for 5 minutes in an Alkyr degreaser (trade name: Parc Lean N364S, manufactured by Nippon Pariki Rising Co., Ltd., concentration = 20 g / 1, temperature = 60 ° C) An evaluation test of corrosion resistance was performed.

4 鲭 Generated area is less than 3% of total area

3 鲭 Generated area is 3% or more and less than 10% of the total area

2 鲭 No performance degradation when the generated area is 10% or more of the total area

1 性能 Performance degradation occurs when the generated area is 10% or more of the total area

(3) Paint adhesion

A melamine-based paint (trademark: Amirac # 100, manufactured by Kansai Paint Co., Ltd.) is applied so that the film thickness after baking and drying is 25 / m. After baking for 24 minutes, 24 hours later, it was immersed in boiling water for 2 hours, and 24 hours later, an evaluation test was performed. The paint adhesion was evaluated according to JISK 540 by performing an evaluation of adhesion and a blister evaluation by the Goban-Erichsen test, and an overall evaluation of these. <Evaluation criteria>

4 No peeling, no pre-star 3 No coating film peeling, very slight blistering

2 Peeling of coating film 1 to 10%

1 Exfoliation of coating film> 10%

(4) Lubricity

Using a blank plate with a diameter of 115 mm φ, a high-speed cylindrical deep drawing test was performed under the following conditions: punch diameter = 50 mm ψ, wrinkle holding pressure 1 Ton, deep drawing speed 30 m / min. In the test, 2 _{g <} m2 of press oil (Nippon Kogyo Oil Co., Ltd., # 640) was applied as needed. The aperture ratio at this time was 2.30.

4 No oil was applied, drawing ratio was reduced to 2.40.

3 No oil was applied and the drawing ratio was reduced to 2.30.

2 With oiling, squeezed out to squeezing ratio = 2.30.

1 No oil was applied and no drawing was performed when the drawing ratio was 2.30. Examples 1 to 74 and Comparative Example 1: L 0

In each of Examples 1 to 74 and Comparative Examples 1 to 10, the zinc-based plated steel sheets shown in Tables 5 to 7 and Table 8 were used as raw materials, which were subjected to underground treatment. Was subjected to a lubricating resin composition treatment. Tables 5 to 7 and Table 8 show the performance of the obtained lubricating resin composition film.

Table 5

Performance evaluation results of water-based polyurethane resin composition of the present invention

* 1: The unit of the adhesion amount is gZm ² , and in the case of chromate treatment, it is converted into chromium metal. Table 6

Performance evaluation results of water-based polyurethane resin composition of the present invention (continued) Base treatment Lubricant resin composition treatment Film performance

Example temperature

Raw material adhesion amount

N o Type Type (g / m ² ) (° C) Corrosion resistance Alkali resistance Adhesion Lubricity

氺 1

氺 1 * 2

26 S D Chromate 0.02 d 1 1.0 120 4 4 4 4

27 S D Chromate 0.02 d 2 1.0 120 4 4 4 4

28 S D Chromate 0.02 d 3 1.0 120 4 4 4 4

29 S D Chromate 0.02 d 7 1.0 120 4 4 4 4

30 S D Chromate 0.02 d 8 1.0 120 4 4 4 4

31 EG Chromate 0.02 d 1 0.5 120 4 3 4 4

32 EG mat 0.02 d 1 3.0 120 4 4 4 4

33 G I Chromate 0.02 d 1 3.0 120 4 4 4 4

34 GL Chromate 0.02 d 1 3.0 120 4 4 4 4

35 Z L Mate 0.02 d 1 3.0 120 4 4 4 4

36 S D Chromate 0.02 dl 3.0 120 4 4 4 4

37 EG Chromate 0.02 d 1 5.0 120 4 4 4 4

38 EG chromate 0.001 d 1 1.0 120 3 4 3 4

39 EG Chromate 0.1 d 1 1.0 120 4 4 4 4

40 EG chromate 0.02 d 1 1.0 100 4 4 4 4 1 EG chromate 0.02 d 1 1.0 150 4 4 4 4

42 EG mate 0.02 d 1 1.0 180 4 4 4 4

43 G I Chromate 0.02 d 1 1.0 180 4 4 4 4

44 GL chromate 0.02 d 1 1.0 180 4 4 4 4

45 Z L Mate 0.02 d 1 1.0 180 4 4 4 4

46 S D Chromate 0.02 d 1 1.0 180 4 4 4 4

47 EG chromate 0.02 d 1 1.0 200 4 4 4 4

48 EG phosphate 2.0 d 1 1.0 120 4 4 4 4

49 EG phosphate 2.0 d 2 1.0 120 4 4 4 4

50 EG phosphate 2.0 d 3 1.0 120 4 4 4 4

51 EG phosphate 2.0 d 4 1.0 120 4 4 4 4

52 EG phosphate 2.0 d 5 1.0 120 4 4 4 4

53 EG phosphate 2.0 d 6 1.0 120 4 4 4 4 Table 7

Performance evaluation results of aqueous polyurethane resin composition of the present invention (continued)

[Note] Non-chrome: Non-chromate treatment

Table 8

Performance evaluation results of the resin composition of the comparative example

As is clear from Tables 5 to 7, in Examples 1 to 73 of the present invention, after forming a chromate, phosphate film or non-chromate film on various sub-plated steel plates, When the water-based polyurethane lubricating composition of the present invention was applied and dried to form a film, the resulting skin had all of the following properties: corrosion resistance, alkali resistance, paint adhesion, and lubricity. Was also good. On the other hand, as shown in Table 8, different from the present invention. In the case of Comparative Examples 1 to 10, the obtained resin composition film had corrosion resistance, anti-anorecalability, coating adhesion, One of the lubricating properties was unsatisfactory. Industrial applicability The lubricating water-based polyurethane resin composition of the present invention forms a surface film having excellent corrosion resistance, alkali resistance, paint adhesion and lubricity by coating it on the surface of a zinc-coated steel sheet. Therefore, it has high practicality.

Claims

1. The following components (a), (b) and (c):

(a) having a polyester skeleton portion and a polyether skeleton portion, and having a tensile rupture strength of 3.92 kN / cm ² (400 kgf / cm ² ) or more measured according to JISK7113 A polyurethane resin having a tensile elongation at break of 50% or less and a glass transition temperature (T g) of 80 to 150 ° C measured by JIS Blue K7112. ,

(b) fine particles of polyolefin resin having a melting point of 70 to 160 ° C. and a particle size of 0.5 to 5 μππι; and

For the total solid mass (a + b + c) of the components (a), (b) and (c),

The solid content ((a) / (a + b + c)) of the component (a) is 50 to 93% by mass,

The solid content ((c) / (a + b + c)) of the component (c) is 5 to 40% by mass.

A lubricating water-based polyurethane resin composition, characterized by comprising:

2. The lubricating aqueous polyurethane resin according to claim 1, wherein the mass ratio of the polyester skeleton to the polyether skeleton in the polyurethane resin (a) is in the range of lZ9 to 5/5. Composition.

3. A treatment liquid containing the lubricating water-based polyurethane resin composition according to claim 1 or 2 is applied to the surface of a zinc-based steel sheet, and dried. And燥, 0. l~ 5 g Zm lubrication treatment method of the zinc-based main luck steel sheet, characterized by that form a lubricating layer having a ^second dry solids weight.

4. A surface-lubricated zinc-coated steel sheet produced by the method for lubricating a zinc-coated steel sheet according to claim 3.