JP2005206764A - Lubricating aqueous polyurethane resin composition, surface lubrication treating method of galvanized steel sheet using it, and the surface-treated steel sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin composition with which a film superior in corrosion resistance, alkali resistance, coating adhesion, and lubricating property is formed on the galvanized steel sheet. <P>SOLUTION: The above-mentioned resin composition contains a polyurethan resin (a) which has a polyester skeleton part and a polyether skeleton part, and also has a tensile breaking strength of 3.92 kN/cm<SP>2</SP>or higher (JIS 7113), a tensile breaking elongation of 50% or lower, and a glass transition temperature (Tg) of 80 to 150 °C (JIS K 7121); fine particles of an olefin resin (b) which has a melting point of 70 to 160 °C and particle sizes of 0.5 to 5 μm; and a coloidal silica (c) which has particle sizes of 5 to 50 nm; and to the total solid content of the above-mentiond components (a+b+c), the solid component content of the above mentioned component (a) is 50 to 93%, the solid component content of the above-mentioned component (b) is 2 to 20%, and the solid component content of the above-mentioned component (c) is 5 to 40%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a lubricating water-based polyurethane resin composition for a surface-lubricated steel sheet used in press processing of home appliances, building materials, etc., a surface treatment method using the same, and a product thereof.

  Conventionally, zinc or zinc-based alloy plated steel sheets have been widely used for home appliances, building materials, and the like. Since these steel sheets have insufficient corrosion resistance and paintability as they are, the surface obtained by coating the resin on the surface after applying the ground treatment such as chromate chemical conversion treatment or phosphate chemical conversion treatment. Treated steel plates have been used. Among these surface-treated steel sheets, there is a so-called lubricated steel sheet that can be processed without using press oil at the time of pressing, which is widely used in home appliances and the like.

  JP-A-2001-214182 (Patent Document 1), JP-A-08-267002 (Patent Document 2), JP-A-06-145559 (Patent Document 3) and the like are disclosed as conventional techniques relating to this lubricated steel sheet. Has been.

In JP-A-2001-214182 (Patent Document 1), an acrylic-styrene resin having an acid value of less than 10 is 30 to 95% by mass in terms of solid content, and a polyurethane resin is 5 to 5 in terms of solid content. Wax particles or thermoplastics having a melting point higher than the glass transition point of the mixed resin containing 70% by mass, the chromium compound and the two resins constituting the mixed resin, and an average particle diameter of 1 to 5 μm A coating layer formed of a mixture of 1 to 7% by mass of resin particles with respect to the total mass of the mixed resin and having a thickness of 0.5 to 4 μm is formed on at least one surface of the zinc-based plated steel sheet. A method of forming is disclosed. Japanese Patent Application Laid-Open No. 08-267002 (Patent Document 2) has a chromate film of 10 to ²⁰⁰ mg / m ² per side in terms of metallic chromium on both sides of zinc or zinc-based plated steel sheet, A resin composition layer containing the following mixed resin, 5 to 40 parts by weight of a curing agent, 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 organosilicon compound. A method of forming a coating weight of 0.1 to 1.0 g / m ² by dry weight is disclosed. However, the mixed resin is composed of two or more resins having a glass transition temperature of −30 ° C. to 90 ° C. having a plurality of hydroxyl groups, that is, one or more resins having a glass transition temperature of −30 ° C. or more and less than 30 ° C. Each component contains 10% by weight or more of a component and a component composed of one or more resins having a glass transition temperature of 30 ° C. to 90 ° C.

  Each of these technologies is characterized by blending several types of resins. However, when a film is formed, each resin is rarely distributed uniformly, and the characteristics of the resulting film are also highly variable. It is hard to say that the characteristics of each resin are utilized. For this reason, it is difficult to obtain sufficient performances such as lubricity, solvent resistance, and corrosion resistance that are required by the film obtained by the prior art method.

  Japanese Patent Laid-Open No. 06-145559 (Patent Document 3) discloses a water-dispersible ether-ester type polyurethane resin (a) having a bisphenol type skeleton, an ester skeleton and a carboxyl group and having an average molecular weight of 3000 or more, Or water-dispersible epoxy resin (b), polyolefin wax (c) having a melting point of 70 to 160 ° C. and an average particle size of 0.1 to 7.0 μm, and silica having an average particle size of 3 to 30 μm ( d), and the total amount of (a) and (b) is 0.50: 1 to 0.85: 1 in weight ratio of solids to total solids (e = a + b + c + d), (c) The weight ratio of solids to (e) is 0.03: 1 to 0.30: 1 and the weight ratio of (d) to (e) is 0.10: 1 to 0.40: 1 A technology related to a certain water-based lubricating coating composition is disclosed Has been.

  In the technique of Patent Document 3, the target performance is obtained by adding a crosslinking agent to a specific polyurethane resin. However, Patent Document 3 does not disclose any means for obtaining a performance equivalent to or higher than that using a polyurethane resin composition containing no crosslinking agent.

Japanese Patent Laid-Open No. 2001-214182, claim 1 JP-A-08-267002, claim 1 Japanese Patent Laid-Open No. 06-145559, claim 1

  In the present invention, a water-based polyurethane resin composition having excellent lubricity, solvent resistance, and corrosion resistance is solved, and zinc-based plating using the same is solved. It is an object of the present invention to provide a method for subjecting the surface of a steel plate to a lubricating treatment and a surface-treated steel plate obtained by the method.

As a result of intensive research on water-based chemicals that simultaneously satisfy the performances of lubricity, solvent resistance, and corrosion resistance, and surface-treated steel sheets using the same, the present inventors have identified the above problems mainly by specifying urethane resins. As a result, the present invention has been completed.
The lubricating water-based polyurethane resin composition of the present invention comprises the following components (a), (b) and (c):
(A) It has a polyester skeleton part and a polyether skeleton part, and has a tensile fracture strength of 3.92 kN / cm ² (400 kgf / cm ² ) or more measured by JISK 7113 and a tensile fracture elongation of 50% or less. And a polyurethane resin having a glass transition temperature (Tg) of 80 to 150 ° C. measured according to JIS K 7121,
(B) a water-based resin composition comprising a polyolefin resin fine particle having a melting point of 70 to 160 ° C. and a particle diameter of 0.5 to 5 μm, and (c) colloidal silica having a particle diameter of 5 to 50 nm. There,
With respect to the total solid content 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 ((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 It is -40 mass%.
In the lubricating water-based polyurethane resin composition of the present invention, the mass ratio of the polyester skeleton portion to the polyether skeleton portion in the polyurethane resin (a) is preferably in the range of 1/9 to 5/5.
In the method for lubricating a zinc-based plated steel sheet according to the present invention, the treatment liquid containing the lubricating water-based polyurethane resin composition according to the present invention is applied to the surface of the zinc-based plated steel sheet and dried to obtain a 0.1 to 5 g / m. A lubricating layer having a dry solid mass of ² is formed.
The surface-lubricated zinc-based plated steel sheet of the present invention is manufactured by the above-described method for lubricating a zinc-based plated steel sheet of the present invention.

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

The tensile fracture strength of the (a) polyurethane resin contained in the resin composition of the present invention is 3.92 N / cm ² (400 Kgf / cm ² ) or more, preferably 4.9 to 9.8 N / cm ² . The tensile elongation at break is 50% or less, preferably 1 to 40%, and the thermal transition temperature (Tg) is 80 to 150 ° C. (measured according to JIS K 7121). In a molding process represented by a press process, a resin film generally receives a strong shearing force. When this shear force exceeds the tensile fracture strength of the film, the film itself is damaged. That is, when the tensile fracture strength of the film is high, the film is hardly 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 Kgf / cm ² ) or more, the tensile elongation at break is 50% or less, and Tg is 80 It has been found that the target lubricity can be obtained when the temperature is ˜150 ° C. In the measurement of the tensile fracture strength and elongation rate of polyurethane resin, the resin was applied on the polyester sheet so as to have a dry film thickness of 50 μm, dried at room temperature for 24 hours, and then baked at 150 ° C. for 30 minutes. A film was prepared, and this film was gently peeled from the polyester sheet and subjected to a tensile test. The tensile test was performed according to JIS K 6732. The glass transition temperature of the polyurethane resin was measured using a commercially available dynamic viscoelasticity measuring device (Rheograph Solid S-1 manufactured by Toyo Seiki Seisakusho Co., Ltd.). At this time, a test piece having a film thickness of 100 μm, a width of 8 mm, and a length of 30 mm is used after being dried at 100 ° C. for 30 minutes, and has a measuring frequency of 100 Hz. It was.

  The solid content of the component (a) is 50 to 93%, preferably 55 to 90%, based on the total solid content mass (a + b + c) of the components (a), (b) and (c). More preferably, it is 50 to 85%. When the solid content of the component (a) is less than 50% of the total solid content mass (a + b + c) of the components (a), (b) and (c), the resulting polyurethane resin composition has a continuous film. The processability and adhesion of this polyurethane resin composition become insufficient because of its low properties. On the other hand, when the solid content of component (a) exceeds 93% of the total solid content mass (a + b + c) of components (a), (b) and (c), component (b) and component ( Since the addition effect of c) becomes poor, the corrosion resistance and processability of the resulting polyurethane resin composition film become insufficient.

The polyurethane resin for 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.
Examples of the polyester polyol compound for forming a polyester skeleton include low molecular weight polyols, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, and 1,2-butylene glycol. 1,3-butylene glycol, 1,4-butylene glycol, 3-methylpentanediol, hexamethylene glycol, hydrogenated bisphenol A, trimethylolpropane, glycerin and the like, and polybasic acids such as succinic acid, glutaric acid, By reaction with adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid, etc. It is one that is forming a compound having an ester structure and a terminal hydroxyl group.
Polyether polyols for forming a polyether skeleton include bisphenol skeleton-containing glycols such as methylene bisphenol, ethylidene bisphenol, butylidene bisphenol, isopropylidene bisphenol, etc., and alkylene oxides having 2 to 4 carbon atoms (for example, ethylene oxide, propylene). It is preferable to use a compound to which (oxide, butylene oxide) is added, and the number of added moles of alkylene oxide is preferably 1 to 10.

  The mass ratio of the polyester skeleton to the polyether skeleton of the polyurethane resin for component (a) is preferably in the range of polyester skeleton / polyether skeleton = 1/9 to 5/5. When the mass ratio of the polyester skeleton to the polyether skeleton is less than 1/9, the content ratio of the relatively rigid polyether skeleton is high, so the extensibility of the film itself is low, The resulting coating is brittle and its tensile fracture strength may be insufficient. On the other hand, when the mass ratio of the polyester skeleton to the polyether skeleton exceeds 5/5, the content ratio of the relatively flexible polyester skeleton is increased, so that the stretchability of the resulting film is high. The tensile fracture strength may become insufficient.

  The fine particles of the (b) polyolefin resin contained in the polyurethane resin composition of the present invention have a melting point of 70 to 160 ° C. and a particle diameter of 0.5 to 5 μm. Generally, the temperature of the molded product may reach 80 ° C. during press molding. For this reason, when the melting point of the polyolefin resin fine particles is less than 70 ° C., all the polyolefin resin fine particles in the film formed from the polyurethane resin composition are melted during the molding process. A film having lubricity cannot be obtained. On the other hand, when the melting point of the polyolefin resin fine particles exceeds 160 ° C., it becomes difficult for the polyolefin resin fine particles to melt due to sliding frictional heat, resulting in insufficient lubricity during sliding of the obtained film. Moreover, when the particle diameter of the polyolefin resin fine particles is less than 0.5 μm, the resulting resin film has insufficient lubricity. Moreover, when the particle diameter exceeds 5.0 μm, the polyolefin resin fine particles easily fall off from the obtained resin film. The shape of the polyolefin resin fine particles is preferably a true sphere in order to obtain a polyurethane resin composition having a high degree of processability.

  The solid content of the component (b) is 2 to 20%, preferably 3 to 20% with respect to the total solid content mass (a + b + c) of the components (a), (b) and (c). More preferably, it is 3 to 18%. When the solid content of the component (b) is less than 2% with respect to the total solid content mass (a + b + c) of the components (a), (b) and (c), the polyurethane resin composition obtained Lubricity becomes insufficient. When the solid content of the component (b) exceeds 20% with respect to the total solid content mass (a + b + c) of the components (a), (b) and (c), the resulting polyurethane resin composition Adhesiveness between the film formed from the object and the overcoating with respect thereto becomes 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. When the particle diameter of the component (c) colloidal silica exceeds 50 nm, the uniformity of the film formed from the resulting polyurethane resin composition becomes insufficient, and therefore the corrosion resistance and adhesion of the film are insufficient. become. On the other hand, when the particle size of the component (c) colloidal silica is less than 5 nm, production on an industrial basis becomes difficult and economically disadvantageous. The solid content of the component (c) is 5 to 40%, preferably 5 to 35%, based on the total solid content mass (a + b + c) of the components (a), (b) and (c). Preferably it is 5 to 30%. When the solid content of the component (c) is less than 5% with respect to the total solid mass (a + b + c) of the components (a), (b) and (c), the obtained polyurethane resin composition The effect of improving corrosion resistance becomes insufficient. When the solid content of the component (c) exceeds 40% with respect to the total solid content mass (a + b + c) of the components (a), (b) and (c), the resulting polyurethane resin composition The material film becomes brittle and its corrosion resistance, adhesion and workability are insufficient.

  In the water-based polyurethane resin composition for metal surface treatment of the present invention, a surfactant called a wettability improver for forming a uniform film on the coated surface of the metal material, a thickener for viscosity adjustment, welding One or more of a conductive material for improving the property, a coloring pigment for improving the design property, a rust preventive additive having an inhibitor effect, and a metal compound may be contained.

Although there is no restriction | limiting in particular in the metal material surface-treated with the lubricous water-based polyurethane resin composition of this invention, Generally it is the most effective to apply to a zinc system plating steel plate. Coating amount to be formed on the surface of the galvanized steel sheet is 0.1 to 5.0 g / m ² on a dry weight basis, preferably 0.2~4.0g / m ^2, more preferably 0.3 4 g / m ² . When the dry mass of the film formed on the surface of the galvanized steel sheet is less than 0.1 g / m ² , the effect of improving the lubricity by the polyurethane resin composition is insufficient. Further, when the dry weight of the coating formed on the surface of the galvanized steel sheet exceeds 5.0 g / m ² , the effect of improving lubricity is saturated, resulting in an economical disadvantage. In addition, examples of the 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. Moreover, there is no restriction | limiting in particular about the process temperature with respect to the apply | coated process liquid layer or its dry film | membrane, However, It is preferable to control reach | attainment board temperature in the range of 100-200 degreeC.

  In addition, for the surface-treated steel sheet of the present invention, there is no limitation on the type and conditions of the pretreatment process applied to the zinc-based plated steel sheet before the lubrication treatment process according to the present invention method. Degrease treatment to maintain, chromate treatment to improve corrosion resistance, phosphate treatment, non-chromate treatment that does not contain chromium compounds with excellent rust prevention effect, etc. Lubricity and adhesion can be obtained.

The invention is further illustrated by the following examples. The aqueous polyurethane resin compositions used in the following examples and comparative examples were produced as follows.
[Production Example 1]

Example Aqueous polyurethane resin a1 for production Example 1 was synthesized from adipic acid having a hydroxyl group at the terminal and 1,6-hexanediol, and 40 parts of polyester polyol having an average molecular weight of 1000 and 3 moles of bisphenol A propylene oxide having an average molecular weight of 660 were added. 160 parts of the product and 10 parts of 2,2-bis (hydroxymethyl) propionic acid were mixed in 100 parts of N-methyl-2-pyrrolidone and heated to 80 ° C. to dissolve. Thereafter, 120 parts of dicyclohexylmethane diisocyanate was added to the solution, the mixture was heated to 110 ° C. and reacted for 2 hours, and the reaction product was neutralized with 10 parts of triethylamine. The obtained solution was added dropwise under strong stirring to an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water to produce an aqueous polyurethane resin. This resin had a tensile fracture strength of 7.35 kN / cm ² (750 kgf / cm ² ), a tensile fracture elongation of 10%, and a Tg of 105 ° C. In this case, the mass ratio of the polyester skeleton to the polyether skeleton was polyester skeleton / polyether skeleton = 2/8.
[Production Example 2]

Production of Example Aqueous Polyurethane Resin a2 Synthesized from adipic acid having a hydroxyl group at the terminal and 1,6-hexanediol, 20 parts of polyester polyol having an average molecular weight of 1000 and 3 mol of bisphenol A propylene oxide having an average molecular weight of 660 were added. 180 parts of the product and 12 parts of 2,2-bis (hydroxymethyl) propionic acid were added to 100 parts of N-methyl-2-pyrrolidone, and the resulting mixture was heated to 80 ° C. and dissolved. To the obtained solution, 110 parts of dicyclohexylmethane diisocyanate was added, the mixture was heated to 110 ° C. and reacted for 2 hours, and the resulting reaction product was neutralized with 11 parts of triethylamine. This solution was dropped into an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water under strong stirring to produce an aqueous polyurethane resin. The tensile fracture strength of this resin was 7.84 kN / cm ² (800 Kgf / cm ² ), and the tensile fracture elongation was 5%. The Tg was 125 ° C. In this case, the mass ratio of the polyester skeleton to the polyether skeleton was polyester skeleton / polyether skeleton = 1/9.
[Production Example 3]

Production of aqueous polyurethane resin a3 for Examples : Adipic acid having a hydroxyl group at the production end and 1,6-hexanediol, 80 parts of polyester polyol having an average molecular weight of 1000, and 3 mol addition of bisphenol A propylene oxide having an average molecular weight of 660 120 parts of the product and 12 parts of 2,2-bis (hydroxymethyl) propionic acid were added to 100 parts of N-methyl-2-pyrrolidone, and this mixture was heated to 80 ° C. and dissolved. To this solution, 100 parts of dicyclohexylmethane diisocyanate was added, the mixture was heated to 110 ° C. and reacted for 2 hours, and the resulting reaction product was neutralized by adding 11 parts of triethylamine. This solution was dropped into an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water under strong stirring to produce an aqueous polyurethane resin. This resin had a tensile fracture strength of 6.37 kN / cm ² (650 Kgf / cm ² ), a tensile fracture elongation of 25%, and a Tg of 85 ° C. In this case, the mass ratio of the polyester skeleton to the polyether skeleton was polyester skeleton / polyether skeleton = 4/6.
[Production Example 4]

Comparative Example Aqueous Urethane Resin a4 Production of Adipic acid having a hydroxyl group at the production end and 1,6-hexanediol, 230 parts of polyester polyol having an average molecular weight of 1000, and 2,2-bis (hydroxymethyl) propion 15 parts of the acid was mixed in 100 parts of N-methyl-2-pyrrolidone and the mixture was heated to 80 ° C. to dissolve. To the obtained solution, 100 parts of dicyclohexylmethane diisocyanate was added, the resulting mixture was heated to 110 ° C. and reacted for 2 hours, and the resulting reaction product was neutralized with 11 parts of triethylamine. This solution was dropped into an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water under strong stirring to produce an aqueous urethane resin. This resin had a tensile fracture strength of 3.92 kN / cm ² (400 kgf / cm ² ), a tensile fracture elongation of 400%, and a Tg of 30 ° C. The mass ratio of the polyester skeleton to the polyether skeleton in the polyurethane resin was polyester skeleton / polyether skeleton = 10/0.
[Production Example 5]

Production of Comparative Example Aqueous Polyurethane Resin a5 200 parts of bisphenol A propylene oxide 3-mole adduct having an average molecular weight of 660 and 15 parts of 2,2-bis (hydroxymethyl) propionic acid in 100 parts of N-methyl-2-pyrrolidone The mixture was heated to 80 ° C. to dissolve. To this solution, 120 parts of dicyclohexylmethane diisocyanate was mixed, the mixture was heated to 110 ° C. and reacted for 2 hours, and the resulting reaction product was neutralized with 15 parts of triethylamine. This solution was dropped into an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water under strong stirring to produce an aqueous polyurethane resin. The tensile fracture strength of this resin was 6.37 kN / cm ² (650 kgf / cm ² ), and the tensile fracture elongation was 5%. The Tg was 140 ° C. 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 follows.
Raw materials (1) Electrical Zn-plated steel sheet (symbol: EG)
Plate thickness = 0.8 mm (Weight amount (front / back) = 20/20 (g / m ² ))
(2) Hot-dip Zn-plated steel sheet (symbol: GI)
Plate thickness = 0.8 mm (Weight per unit (front / back) = 60/60 (g / m ² ))
(3) 55% Al-Zn alloy-plated steel sheet (symbol: GL)
Plate thickness = 0.8 mm (Weight per unit (front / back) = 90/90 (g / m ² ))
(4) Electric Zn—Ni alloy-plated steel sheet with a Ni content of 12 wt% (symbol: ZL)
Plate thickness = 0.8 mm (Weight amount (front / back) = 20/20 (g / m ² ))
(5) Melted 11% Al-3% Mg-0.2% Si-Zn alloy-plated steel sheet (symbol: SD)
Plate thickness = 0.8 mm (Weight per unit (front / back) = 60/60 (g / m ² ))
As a degreasing agent, Fine Cleaner 4336 (trademark, active ingredient concentration = 20 g / l, manufactured by Nihon Parkerizing Co., Ltd.) was used, and this material was sprayed for 2 minutes at a temperature = 60 ° C. Immediately after the treatment, the degreased steel plate was washed with water and subjected to the following base chromate treatment, base zinc phosphate treatment or non-chromate treatment.
Base treatment (1) Chromate treatment Using Zinc Chrome 357 (trademark, manufactured by Nippon Parkerizing Co., Ltd.) as a chromate treatment agent, spray treatment (bath temperature = 50 ° C., time = 5 seconds) on the degreased steel plate. After the applied base film was washed with water, it was dried for 10 seconds at an atmospheric temperature of 220 ° C. (steel plate reaching plate temperature = 100 ° C.). The amount of chromium deposited by this treatment was 10 mg / m ² .
(2) Zinc phosphate treatment Using Palbond L3020 (trademark, manufactured by Nihon Parkerizing Co., Ltd.) as the zinc phosphate treatment agent, the steel sheet subjected to the degreasing treatment was subjected to immersion treatment (45 ° C, immersion for 2 minutes). This was washed with water and then air-dried. The formed chemical conversion film had a mass of 2.0 g / m ² .
(3) Non-chromate treatment As a non-chromate treatment agent, Palcoat 3841 (trademark, manufactured by Nihon Parkerizing Co., Ltd., containing a silane compound) is applied to the degreased steel sheet using a roll coater, and treated. The layer was immediately dried for 10 seconds at an ambient temperature of 220 ° C. (steel plate reached temperature = 100 ° C.). The dry film mass at this time was 0.2 g / m ² .

Table 1 shows the trademark, solid content concentration, and particle size of the aqueous dispersion of polyolefin resin used in Examples and Comparative Examples of polyolefin resin for component (6) . These were all made by Mitsui Chemicals.

Table 2 shows the trademark, solid content concentration, and particle size of the colloidal silica used in the examples and comparative examples of the colloidal silica for component (c) . These were all manufactured by Nissan Chemical.

Table 3 shows the compositions of the lubricating water-based polyurethane resin compositions d1 to d9 used in the composition examples of the lubricating water-based resin composition. Table 4 shows the compositions of the resin compositions d10 to d15 used in the comparative examples. In Tables 3 and 4, the values in parentheses indicate the ratio (%) of the solid content mass of each component to the total solid mass of the aqueous polyurethane resin composition.

Lubricating treatment The coating liquid containing the lubricating aqueous resin composition shown in Tables 3 and 4 was applied to the surface of the steel material with a bar coater, and the coating liquid layer was dried at an atmospheric temperature of 320 ° C. for 12 seconds. The steel material arrival temperature at this time was 100 to 200 ° C. (preferably 120 ° C.), and the coating amount was 1.0 g / m ² .
When the steel material arrival temperature was other than 120 ° C., the heating atmosphere temperature and the heating time were as follows.
100 ° C .: 320 ° C. × 9 seconds 150 ° C .: 320 ° C. × 16 seconds 180 ° C .: 320 ° C. × 22 seconds 200 ° C .: 320 ° C. × 27 seconds

Paint plate performance test (1) Corrosion resistance A salt spray test according to JIS-Z-2731 was conducted for 200 hours to observe the occurrence of white rust.
<Evaluation criteria>
◎ Rust generation area is less than 3% of total area ○ Rust generation area is 3% or more and less than 10% of total area △ Rust generation area is 10% or more and less than 30% of total area × Rust generation area is 30% or more of total area

(2) Alkali resistance After being immersed in an alkaline degreasing agent (Pulclean N364S, manufactured by Nippon Parkerizing Co., Ltd., concentration = 20 g / l, temperature = 60 ° C.) for 5 minutes, the corrosion resistance evaluation test was performed.
<Evaluation criteria>
◎ Rust generation area is less than 3% of the total area ○ Rust generation area is 3% or more and less than 10% of the total area △ Rust generation area is 10% or more of the total area and there is no performance deterioration × Rust generation area is 10% of the total area There is performance degradation above

(3) Paint adhesion Melamine-based paint (Amirac # 1000, manufactured by Kansai Paint Co., Ltd.) was applied so that the film thickness after baking and drying was 25 μm, baked at 125 ° C. for 20 minutes, and boiling water after 24 hours. For 2 hours, and an evaluation test was conducted after 24 hours. The paint adhesion evaluation method was evaluated by JIS-5400 by performing adhesion evaluation and blister evaluation by the Goban eyes Eriksen test, and evaluating these comprehensive evaluations.
<Evaluation criteria>
◎ No peeling of film, no blister ○ No peeling of film, slight blister generation △ 1-10%
× Over 10% coating removal

(4) Lubricity A blank plate having a diameter of 115 mmφ was used, and a high-speed cylindrical deep drawing test was performed under the conditions of punch diameter = 50 mmφ, wrinkle presser pressure 1 Ton, deep drawing speed 30 m / min. In the test, 2 g / m @ 2 of press oil (manufactured by Nippon Kosaku Oil, # 640) was applied as necessary. The aperture ratio at this time is 2.30.
<Evaluation criteria>
◎ No oiling, drawing out to 2.40.
○ No oil was applied and the drawing ratio = 2.30.
△ There was oiling and the drawing ratio was reduced to 2.30.
X Oil was applied, and drawing was not completed at a drawing ratio = 2.30.

Examples 1 to 74 and Comparative Examples 1 to 10
In each of Examples 1 to 74 and Comparative Examples 1 to 10, the zinc-based plated steel sheet shown in Tables 5 to 7 and Table 8 was used as a raw material, and a base treatment was applied thereto, and a lubricating resin composition treatment was performed thereon. Was given. The performance of the resulting lubricating resin composition film is shown in Tables 5 to 7 and Table 8.

  As apparent 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 zinc-based plated steel sheets, the aqueous polyurethane resin composition of the present invention When a film was formed by applying the product and then dried, the film exhibited good corrosion resistance, alkali resistance, paint adhesion, and lubricity. On the other hand, as shown in Table 8, in the case of Comparative Examples 1 to 10 different from the present invention, the obtained resin composition film has any performance of corrosion resistance, alkali resistance, paint adhesion, and lubricity. It was unsatisfactory.

  The lubricating hydrogen polyurethane resin composition of the present invention can form a surface film having excellent corrosion resistance, alkali resistance, paint adhesion and lubricity by applying it to the surface of a zinc-based plated steel sheet. Have high practical applicability.

Claims (4)

The following components (a), (b) and (c):
(A) It has a polyester skeleton part and a polyether skeleton part, and has a tensile fracture strength of 3.92 kN / cm ² (400 kgf / cm ² ) or more measured by JISK 7113 and a tensile fracture elongation of 50% or less. And a polyurethane resin having a glass transition temperature (Tg) of 80 to 150 ° C. measured according to JIS K 7121,
(B) a water-based resin composition comprising a polyolefin resin fine particle having a melting point of 70 to 160 ° C. and a particle diameter of 0.5 to 5 μm, and (c) colloidal silica having a particle diameter of 5 to 50 nm. There,
With respect to the total solid content 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 ((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 Lubricating water-based polyurethane resin composition, characterized in that it is -40% by mass.   The lubricating water-based polyurethane resin composition according to claim 1, wherein a mass ratio of the polyester skeleton portion to the polyether skeleton portion in the polyurethane resin (a) is in the range of 1/9 to 5/5. Lubricant having a dry solid mass of 0.1 to 5 g / m ² by applying a treatment liquid containing the lubricious water-based polyurethane resin composition according to claim 1 or 2 to the surface of a zinc-based plated steel sheet and drying it. A method for lubricating a galvanized steel sheet, comprising forming a layer.   A surface lubricated galvanized steel sheet produced by the method of lubricating a galvanized steel sheet according to claim 3.