JP4478056B2 - Resin coated metal plate - Google Patents

Description

  The present invention relates to a resin-coated metal plate, and more particularly to a chromium-free resin-coated metal plate excellent in corrosion resistance, paintability (coating film adhesion), blackening resistance, lubricity and tape peel resistance. is there.

  As materials used for automobiles, home appliances, and building materials, zinc-plated steel sheets such as electrogalvanized steel sheets and hot-dip galvanized steel sheets, or inorganic materials that have been chromated on the galvanized steel sheets for the purpose of further improving corrosion resistance Many surface-treated steel sheets are used. However, due to the recent increase in environmental awareness, there is an increasing demand for steel sheets not subjected to chromate treatment.

  As means for improving corrosion resistance in place of such chromate treatment, for example, methods using tannic acid have been proposed (for example, Patent Documents 1 and 2). However, these methods have failed to obtain sufficient corrosion resistance.

  Therefore, surface-treated steel sheets provided with a film mainly composed of a high molecular weight chelating agent have been proposed (Patent Documents 3 and 4). In these documents, it is proposed to use a high molecular weight chelating agent as the main component of the film. For comparison with these, low molecular weight chelating agents such as tannic acid and ethylenediaminetetraacetic acid (EDTA) are insufficient. It is listed as a comparative example that shows only corrosion resistance.

However, since the characteristics of the films described in Patent Documents 3 and 4 depend on the type of the high molecular weight chelating agent that is the main component, it is difficult to impart further characteristics other than corrosion resistance to the film. Further, in Patent Document 4, it is proposed that a chelate-forming group is imparted to an organic polymer matrix in order to produce a high-molecular-weight chelating agent, but a polymer reaction for imparting such a chelate-forming group is generally performed. As a result, the manufacturing cost of the surface-treated steel sheet increases.
JP-A-51-71233 JP 2001-89868 A Japanese Patent Laid-Open No. 11-158649 JP-A-11-166151

  Therefore, the object of the present invention is to have excellent corrosion resistance, and still have other excellent characteristics, specifically excellent paintability (coating film adhesion), blackening resistance, lubricity and tape peel resistance. It is providing the resin coating metal plate provided with the resin film.

  The resin-coated metal plate of the present invention that has solved the above-mentioned problems is a resin-coated metal plate provided with a resin film obtained from a film-forming composition containing a carboxyl group-containing polyurethane resin, The forming compositions are ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylidene diphosphonic acid (HEDP), N, N, N ′, N′-tetrakis (phosphonomethyl) ethylenediamine (EDTMP), nitrilotri Acetic acid (NTA) and hydroxyethylethylenediaminetetraacetic acid (HEDTA), and one or more chelating agents selected from the group consisting of salts thereof in a ratio of 100 mass parts of solid content of the film-forming composition. It contains 0.5 to 10 parts by mass.

  Preferred among the chelating agents are (1) a salt form containing Na ions, (2) at least one metal ion containing Na ions and selected from Mg, Ca, Co, Zn, Mn and Fe ions. (3) a salt form containing an amine ion or ammonium ion, or (4) a salt containing an amine ion or ammonium ion and selected from Na, Mg, Ca, Co, Zn, Mn and Fe ions A salt form of EDTA, DTPA, HEDP, EDTMP, NTA or HEDTA containing at least one metal ion.

  In a preferred embodiment of the present invention, the film-forming composition comprises: carboxyl group-containing polyurethane resin: 30 to 93.5 parts by mass; silica particles: 5 to 40 parts by mass; polyethylene wax particles: 0.5 to 15 parts by mass And an epoxy-based crosslinking agent: 1 to 15 parts by mass, and the polyurethane resin is obtained by subjecting a urethane prepolymer to chain extension reaction with a chain extender, and is a polyisocyanate constituting the urethane prepolymer As a component, at least one selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate is essentially used, and as a polyol component constituting the urethane prepolymer, 1,4-cyclohexanedimethanol, poly Ether polyols, Beauty, in which all of the polyol having a carboxyl group was used essentially. In a preferred embodiment, the film-forming composition has the same composition as described above, and a resin-coated metal with further improved corrosion resistance, paintability, and lubricity by using a polyurethane resin having a specific composition. A board can be obtained.

  Preferred as the chain extender is ethylenediamine or hydrazine. The mass ratio of the 1,4-cyclohexanedimethanol and the polyether polyol is preferably 1,4-cyclohexanedimethanol: polyether polyol = 1: 1 to 1:19. Also preferred as the polyether polyol is polyoxypropylene glycol or polytetramethylene ether glycol. The acid value of the carboxyl group-containing polyurethane resin is preferably 10 to 60 mgKOH / g.

  The polyethylene wax particles are preferably spherical and have an average particle diameter of 0.1 to 3 μm. The softening point of the polyethylene wax particles is preferably 100 to 140 ° C., for example. By setting the film forming temperature of the resin film to be lower than the softening point of the polyethylene wax particles, the shape of the polyethylene wax particles is held in a spherical shape in the resin film, and the lubricity can be further improved.

  The film-forming composition further comprises a second carboxyl group-containing resin having an acid value of 5 mgKOH / g or more, which is less than half the mass of the carboxyl group-containing polyurethane resin, and the second resin and the carboxyl It is also a preferred embodiment that a resin film in which the group-containing polyurethane resin is crosslinked with the second crosslinking agent is formed. The second crosslinking agent is preferably an epoxy crosslinking agent, a divalent metal crosslinking agent, or an aziridine crosslinking agent.

When the metal plate of the present invention is a zinc-based plated steel plate, a resin-coated metal plate in which a surface-modified layer is formed on the zinc-based plated layer and the resin film is formed on the surface-modified layer a is the surface modified layer, SiO ₂ of 1 to 30 mg / m ² in terms of ^{Si, P: 0.5~15mg / m 2,} Al: also contain 0.5 to 10 mg / m ² This is a preferred embodiment. Furthermore, when the content of Si, P, and Al contained in the surface modified layer satisfies the following relational expressions (1) and (2), the tape peeling resistance is further improved. Also, the tape peel resistance after alkaline degreasing is excellent.
0.5 ≦ Si / P ≦ 20 Equation (1)
0.7 ≦ P / Al ≦ 4.5 …… Formula (2)

  It is also a preferred embodiment that the surface modified layer further contains an organic resin. It is preferable that the absorption intensity (peak area) of FT-IR derived from the structure of the organic resin contained in the surface modified layer is 0.1 to 15.

The surface treatment agent of the present invention is a silica-containing phosphate surface treatment agent for forming the surface modified layer, and the treatment agent has a solid content concentration of 0.01 to 15% (mass%). Meaning the same), and the content and composition ratio (mass ratio) of Si, P, and Al contained in the treatment agent satisfy the following requirements.
Si: 0.002 to 4.5%
P: 0.0005 to 1.5%
Al: 0.0001 to 0.5%
4.5 ≦ Si / Al ≦ 230, 1.5 ≦ Si / P ≦ 60.

  It is also a preferable aspect that the surface treatment agent further contains an organic resin, and the addition concentration of the organic resin is 0.01 to 3 g / L.

  According to the present invention, a resin-coated metal plate having excellent corrosion resistance can be obtained. In particular, a film formed from a film-forming composition containing a small amount of a low molecular weight chelating agent such as EDTA or a salt thereof (0.5 to 10 parts by mass in a proportion of 100 parts by mass of the solid content of the composition) It is surprising that the resin-coated metal plate provided with has excellent corrosion resistance. This is because, conventionally, such a low molecular weight chelating agent has been considered to be insufficient in the effect of improving the corrosion resistance.

  Further, when a high molecular weight chelating agent that is considered preferable for imparting corrosion resistance is mixed with a film-forming composition containing an organic resin or the like, problems such as gelation may occur, but EDTA used in the present invention and its Low molecular weight chelating agents such as salts have good compatibility with other components of the film-forming composition and do not cause gelation, and can impart good corrosion resistance to the resin-coated metal plate.

  Furthermore, according to the present invention, in the film-forming composition, by adjusting the components other than the chelating agent such as EDTA and salts thereof and the composition thereof to those of the above preferred embodiments, Further favorable properties can be imparted to the film, namely excellent paintability, blackening resistance, lubricity and tape peel resistance. Moreover, the corrosion resistance implement | achieved by the chelating agent can further be improved by using the film forming composition of a preferable aspect.

BEST MODE FOR CARRYING OUT THE INVENTION

  The resin-coated metal plate of the present invention is formed on one or more chelating agents selected from the group consisting of EDTA, DTPA, HEDP, EDTMP, NTA and HEDTA, and salts thereof on at least one surface of the metal plate. It is provided with a film formed from a film-forming composition containing 0.5 to 10 parts by mass in a proportion of 100 parts by mass of the solid content of the composition. In this invention, solid content means the solid residue which remains on a metal plate as a film | membrane after evaporation of volatile components (for example, water or an organic solvent) by heat-drying the film forming composition. Therefore, the solid content includes a resin (including solid or liquid at room temperature), an inorganic solid (for example, silica), and the like.

  The low molecular weight chelating agents used in the present invention are EDTA, DTPA, HEDP, EDTMP, NTA and HEDTA, and salts thereof. Among these, it is an aqueous film-forming composition that uses a chelating agent in a salt form. From the viewpoint of solubility in water. The salt-form chelating agent in the present invention refers to a product obtained by neutralizing some or all of the plurality of acid functional groups contained in the chelating agent. Thus, for example, an EDTA salt is one in which only one of the four carboxyl groups is neutralized with a base such as NaOH (for example, a monosodium salt: EDTA · Na), and all carboxyl groups are neutralized with a base such as NaOH. The sum (for example, tetrasodium salt: EDTA · 4Na) is included. Further, in the salt form chelating agent, a part of the plurality of acid functional groups is neutralized with NaOH or the like, and another acid functional group is neutralized with an amine. Kirest M-50: EDTA · 2Na · amine salt) and the like.

  Preferred among the chelating agents in the salt form are (1) those containing Na ions (Na salts), (2) containing Na ions, and selected from Mg, Ca, Co, Zn, Mn and Fe ions. One containing at least one metal ion (a complex salt of Na and other metals), (3) One containing an amine ion or ammonium ion (amine or ammonium salt), or (4) An amine ion or ammonium ion And those containing at least one metal ion selected from Na, Mg, Ca, Co, Zn, Mn and Fe ions (a complex salt of amine or ammonium / metal).

  The chelating agent is commercially available from, for example, Kirest Co., Ltd., and as an EDTA chelating agent manufactured by Kirest Co., Ltd., Kirest Mg-40, Kirest M-50, Kirest OD, etc .; Examples include Cylest PC-45 and the like; Cylest PH-212 and Cylest PH-214 and the like as the HEDP system; Cylest HP and 540 as the EDTMP system; Cylest 70 and Cylest NTA as NTA; Cylest H and the like as HEDTA.

  Here, the mechanism by which a low molecular weight chelating agent such as EDTA or a salt thereof contributes to an improvement in corrosion resistance is not necessarily clear. However, for example, in the case of a zinc-based plated steel sheet, it elutes in the corrosive environment with these low molecular weight chelating agents. It is considered that metal ions such as Zn ions form a stable chelate compound, and this stable chelate compound covers a corroded portion, thereby preventing further corrosion.

  The content of the low molecular weight chelating agent such as EDTA or a salt thereof in the film forming composition of the present invention is 0.5 to 10 parts by mass in the solid content of 100 parts by mass of the film forming composition. . When the content of the low molecular weight chelating agent is less than 0.5 parts by mass, the production of a stable chelate compound is insufficient and the corrosion resistance is also insufficient. On the other hand, even if the low molecular weight chelating agent exceeds 10 parts by mass, the corrosion resistance tends to decrease. The reason why the corrosion resistance can be lowered by adding a large amount of low molecular weight chelating agent is not clear, but the chelating agent reacts with organic resin, crosslinking agent or silane coupling agent that can be included in the film forming composition. By doing so, it may be considered that the film forming property of the film is affected. From the viewpoint of the film-forming property of the film and the adhesion to other coating films, the more preferable upper limit of the chelating agent content is 5 parts by mass in the solid content of 100 parts by mass of the film-forming composition. A more preferred upper limit is 3 parts by mass, and a more preferred lower limit of the chelating agent content is 1 part by mass.

  The film-forming composition used in the present invention is not particularly limited, but an aqueous composition is preferably used. For example, an aqueous dispersion of a carboxyl group-containing polyurethane resin, silica particles, polyethylene wax The aqueous composition for film formation containing particle | grains and an epoxy-type crosslinking agent can be used conveniently. This is because if an aqueous composition is used as the film-forming composition, a resin film can be easily formed by applying to the surface of the metal plate and drying. In addition, the aqueous composition is more environmentally friendly than the solvent-based composition, and has less dangers such as safety and health problems and fires, and is easy to handle.

  The carboxyl group-containing polyurethane resin in a preferred embodiment of the present invention is obtained by subjecting a urethane prepolymer to a chain extension reaction with a chain extender, and the urethane prepolymer comprises a polyisocyanate component and a polyol component described later. Obtained by reaction. As the polyisocyanate component constituting the urethane prepolymer, at least one polyisocyanate selected from the group consisting of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (hydrogenated MDI) is essential. It is preferable to use for. This is because by using such a polyisocyanate, a resin film having excellent corrosion resistance and reaction control stability can be obtained.

  In addition to the above-mentioned essential polyisocyanates that are preferably used (hereinafter abbreviated as “essential polyisocyanates”), other polyisocyanates are used within a range that does not deteriorate the corrosion resistance and the stability of reaction control. However, the content of the essential polyisocyanate component is desirably 70% by mass or more of the total polyisocyanate component. This is because if the content of the essential polyisocyanate component is less than 70% by mass, the corrosion resistance and the stability of reaction control tend to be lowered. Examples of the polyisocyanate other than the essential polyisocyanate component include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecane methylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, and phenylene diisocyanate. The polyisocyanates may be used alone or in admixture of at least two or more.

  As the polyol component constituting the urethane prepolymer, all three types of polyols, ie, 1,4-cyclohexanedimethanol, polyether polyol, and polyol having a carboxyl group, are preferably used, preferably all three types Is preferably a diol. This is because by using such a polyol component, a resin film having excellent corrosion resistance and slidability can be obtained. Moreover, the antirust effect of the polyurethane resin obtained can be heightened by using 1, 4- cyclohexane dimethanol as a polyol component.

  The polyether polyol is not particularly limited as long as it has at least two hydroxyl groups in the molecular chain and the main skeleton is composed of alkylene oxide units. For example, polyoxyethylene glycol (simply “ Sometimes referred to as "polyethylene glycol"), polyoxypropylene glycol (sometimes simply referred to as "polypropylene glycol"), polyoxytetramethylene glycol (simply "polytetramethylene glycol" or "polytetramethylene ether") May be referred to as “glycol”), and commercially available ones can be used. Among the polyether polyols, it is preferable to use polyoxypropylene glycol or polytetramethylene ether glycol. The number of functional groups of the polyether polyol is not particularly limited as long as it is at least 2 or more, and may be, for example, trifunctional or tetrafunctional or more polyfunctional.

  The polyether polyol can be obtained, for example, by adding an alkylene oxide such as ethylene oxide or propylene oxide using a compound having active hydrogen as an initiator. Examples of the compound having active hydrogen include diols such as propylene glycol and ethylene glycol, triols such as glycerin, trimethylolpropane, hexanetriol, and triethanolamine, tetraols such as diglycerin and pentaerythritol, others, sorbitol, and sorbitol. Examples thereof include sugar and phosphoric acid. At this time, if a diol is used as an initiator to be used, a bifunctional polyether polyol can be obtained, and if a triol is used, a trifunctional polyether polyol can be obtained. Polyoxytetramethylene glycol is obtained, for example, by ring-opening polymerization of tetrahydrofuran.

  As the polyether polyol, it is preferable to use a commercially available product having an average molecular weight of about 400 to 4000, for example. This is because the resin film is hard when the average molecular weight is less than about 400, and too soft when it exceeds 4000. The average molecular weight was determined from the OH value (hydroxyl value) of the polyol.

  In the present invention, it is also a preferred embodiment that the mass ratio of 1,4-cyclohexanedimethanol and polyether polyol is 1,4-cyclohexanedimethanol: polyether polyol = 1: 1 to 1:19. It is because the antirust effect of the polyurethane resin obtained can be further enhanced by using a fixed ratio of 1,4-cyclohexanedimethanol having an antirust effect.

  The polyol having a carboxyl group used in the present invention is not particularly limited as long as it has at least one carboxyl group and at least two hydroxyl groups. For example, dimethylolpropionic acid, dimethylolbutanoic acid, dihydroxypropion Examples include acids and dihydroxysuccinic acid.

  In addition to the above-mentioned essential polyol component (hereinafter abbreviated as “essential polyol component”), other polyols can be used as long as the corrosion resistance is not lowered. The content of is desirably 70% by mass or more of the total polyol component. It is because there exists a tendency for corrosion resistance to fall that the content rate of an essential polyol component is less than 70 mass%. The polyol other than the essential polyol component described above is not particularly limited as long as it has a plurality of hydroxyl groups, and examples thereof include a low molecular weight polyol and a high molecular weight polyol. The low molecular weight polyol is a polyol having a molecular weight of about 500 or less. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol. Diols such as glycerol; triols such as glycerin, trimethylolpropane and hexanetriol.

  The high molecular weight polyol is a polyol having a molecular weight exceeding about 500. For example, a condensed polyester polyol such as polyethylene adipate (PEA), polybutylene adipate (PBA), polyhexamethylene adipate (PHMA); poly-ε-caprolactone ( Lactone polyester polyol such as PCL); polycarbonate polyol such as polyhexamethylene carbonate; and acrylic polyol.

  The chain extender that undergoes a chain extension reaction with the urethane prepolymer described above is not particularly limited, and examples thereof include polyamines, low molecular weight polyols, and alkanolamines. As the low molecular weight polyol, the same ones as described above can be used. Examples of the polyamine include aliphatic polyamines such as ethylenediamine, propylenediamine, and hexamethylenediamine; tolylenediamine, xylylenediamine, diaminodiphenylmethane. And alicyclic polyamines such as diaminocyclohexylmethane, piperazine and isophoronediamine; and hydrazines such as hydrazine, succinic dihydrazide, adipic dihydrazide and phthalic dihydrazide. Among these, it is preferable to use ethylenediamine and / or hydrazine as a chain extender component. Examples of the alkanolamine include diethanolamine and monoethanolamine.

  In the present invention, as described above, it is preferable to use an aqueous dispersion of a carboxyl group-containing polyurethane resin. The aqueous dispersion of the carboxyl group-containing polyurethane resin can be prepared by a known method. For example, the carboxyl group of the carboxyl group-containing urethane prepolymer is neutralized with a base and emulsified and dispersed in water to extend the chain. There are a method of reacting, and a method of emulsifying and dispersing a carboxyl group-containing polyurethane resin in the presence of an emulsifier with a high shear force to cause a chain extension reaction. Hereinafter, a method for preparing an aqueous dispersion of a polyurethane resin will be described based on a method of neutralizing a carboxyl group of a carboxyl group-containing urethane prepolymer with a base and emulsifying and dispersing in water, but the present invention is limited to such a method. Is not to be done.

  First, a relatively low molecular weight carboxyl group-containing isocyanate group-terminated urethane prepolymer is prepared by using the above-described polyisocyanate and the above-described polyol so that the isocyanate group becomes excessive in the NCO / OH ratio. Although the temperature which synthesize | combines a urethane prepolymer is not specifically limited, It can synthesize | combine at the temperature of 50-200 degreeC. Moreover, a well-known catalyst can be used for the synthesis | combination of a urethane prepolymer. Examples of the catalyst include monoamines such as triethylamine and N, N-dimethylcyclohexylamine; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine Polyamines such as 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), cyclic diamines such as triethylenediamine, and tin-based catalysts such as dibutyltin dilaurate and dibutyltin diacetate .

  In synthesizing the urethane prepolymer, a one-shot method may be adopted, or a prepolymer method may be adopted. The one shot method is a method in which polyisocyanate and polyol are reacted together, and the prepolymer method is a method in which polyisocyanate and polyol are reacted in multiple stages. For example, once a low molecular weight urethane prepolymer is synthesized. After that, the method further increases the molecular weight.

  In the present invention, for example, an embodiment in which all of the polyisocyanate and the essential polyol component are reacted together; first, the polyisocyanate and the essential polyol component are first reacted with the polyether polyol, and then 1,4-cyclohexanedimethanol A mode in which a polyol having a carboxyl group is further reacted, or a mode in which a polyether polyol and 1,4-cyclohexanedimethanol are first reacted, and then a polyol having a carboxyl group is reacted, among essential polyol components May be appropriately selected to synthesize a urethane prepolymer.

  In preparing the carboxyl group-containing isocyanate group-terminated urethane prepolymer, it is also a preferred embodiment to use a solvent from the viewpoint of adjusting the viscosity and improving the emulsifying dispersibility of the prepolymer. As the solvent, it is preferable to use a solvent that is inert to the isocyanate group and has a relatively high hydrophilicity, such as N-methylpyrrolidone, acetone, ethyl acetate, methyl ethyl ketone, N, N-dimethylformamide, and the like. N-methylpyrrolidone is preferably used. This is because N-methylpyrrolidone is highly soluble in a polyol having a carboxyl group and can uniformly carry out a reaction for preparing an isocyanate group-terminated urethane prepolymer. In addition, the reaction of a urethane prepolymer can obtain | require a reaction rate by calculating | requiring an isocyanate group density | concentration, for example by the dibutylamine titration method.

  After completion of the urethane prepolymer reaction, the resulting carboxyl group-containing isocyanate group-terminated urethane prepolymer is emulsified and dispersed in water by neutralization with a base. The neutralizing agent is not particularly limited, and ammonia; tertiary amines such as triethylamine and triethanolamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used. Preferably, triethylamine is used.

  After emulsifying and dispersing the carboxyl group-containing isocyanate group-terminated urethane prepolymer, a chain extension reaction can be carried out in water using a chain extender such as polymian. The chain extension reaction can be appropriately performed before or after emulsification dispersion, or after emulsion dispersion depending on the reactivity of the chain extender used.

  The acid value of the carboxyl group-containing polyurethane resin used in the present invention is preferably 10 mgKOH / g or more and 60 mgKOH / g or less. This is because when the acid value is less than 10 mgKOH / g, the stability of the aqueous polyurethane resin dispersion is lowered. Moreover, when an acid value exceeds 60 mgKOH / g, there exists a tendency for the corrosion resistance of the resin film obtained to fall. The acid value is measured according to JIS-K0070.

  The composition for forming a film used in a preferred embodiment of the present invention is in a ratio of parts by mass, the carboxyl group-containing polyurethane resin: 30 to 93.5 parts by mass; silica particles: 5 to 40 parts by mass; polyethylene wax particles : 0.5-15 mass parts; and epoxy-type crosslinking agent: 1-15 mass parts is contained. By setting the content of each component as described above, properties such as corrosion resistance, paintability, and lubricity can be further enhanced. In addition, it is preferable that the total content of the components is 100 parts by mass. Further, when the film forming composition is an aqueous composition, water is further contained in addition to the above components (total 100 parts by mass), and the water content is the coating property of the film forming aqueous composition. What is necessary is just to adjust suitably according to etc. Hereinafter, each component will be described.

  The preferred film-forming composition contains 5 parts by mass or more, more preferably 8 parts by mass or more and 40 parts by mass or less, more preferably 30 parts by mass or less of silica particles. The silica particles are effective for imparting corrosion resistance and paintability, and for suppressing the occurrence of wrinkling of the film during processing and the occurrence of blackening. When the content of silica is less than 5 parts by mass, the corrosion resistance and blackening resistance tend to decrease. Further, if the silica content exceeds 40 parts by mass, the film-forming property of the resin film is lowered, the corrosion resistance is lowered, or the silica acts as a lubricant, thereby increasing the coefficient of friction of the film and improving the lubricity. The processability may deteriorate due to the decrease. In order to maximize the effect of the silica particles, the average particle size of the silica particles is preferably in the range of 1 to 300 nm. The smaller the average particle size of the silica particles, the better the corrosion resistance of the resin film. However, when the average particle size is less than about 1 nm, the effect of improving the corrosion resistance tends to be saturated. This is because the stability is lowered and the gel is easily formed. On the other hand, when the average particle diameter of silica exceeds 300 nm, the film-forming property of the film is lowered and the corrosion resistance tends to be lowered.

  Examples of the method for measuring the average particle size of the silica particles include a Sears method, a BET method, and a dynamic light scattering method. For example, when the particle size is 4 to 6 nm, the Sears method is used. It is preferable to employ the BET method in the case of 10 to 100 nm, and the dynamic light scattering method in the case of chain silica. Examples of the silica particles include ST-series such as ST-XS, ST-40, ST-50, ST-XL, ST-OL, ST-ZL available from Nissan Chemical Industries, Ltd. .

  The film-forming composition in a preferred embodiment of the present invention contains 0.5 to 15 parts by mass of polyethylene wax particles. The polyethylene wax particles are effective for imparting lubricity to the resin film, and also for suppressing the occurrence of wrinkling of the resin film and the occurrence of a blackening phenomenon during press working. When the content of the polyethylene wax particles is less than 0.5 parts by mass, the lubricity of the resulting resin film is not sufficiently improved. Moreover, when the content of the polyethylene wax particles exceeds 15 parts by mass, the adhesion between the resulting resin film and the metal plate decreases, the film peels off during press processing, and the corrosion resistance after processing tends to decrease. . Furthermore, since the adhesiveness between the resulting resin film and the paint is reduced, the paintability may also be reduced.

  The softening point of the polyethylene wax particles is preferably 100 to 140 ° C. If the softening point is less than 100 ° C, the wax softens and liquefies due to the rise in the mold temperature during press processing, causing a liquid breakage state between the metal plate and the mold, and the punching processability decreases. is there. On the other hand, with a polyethylene wax particle having a softening point exceeding 140 ° C., good punching processability cannot be obtained. The softening point can be measured by the ring and ball method described in JIS-K2207.

  As the polyethylene wax particles, those having a spherical shape and an average particle diameter of 0.1 to 3 μm are preferably used. When the average particle diameter exceeds 3 μm, it becomes difficult to uniformly disperse in the aqueous polyurethane resin dispersion, and the adhesion of the resulting resin film to the metal plate and the paintability tend to decrease. On the other hand, when the average particle diameter of the polyethylene wax particles is smaller than 0.1 μm, the effect of improving the lubricity and punching processability of the resin film by adding the polyethylene wax particles may not be obtained. The average particle diameter of the polyethylene wax particles can be measured by a Coulter counter method. Examples of the polyethylene wax particles include Chemipearl (polyolefin aqueous dispersion) available from Mitsui Chemicals.

  In addition, if the drying temperature after application of the resin film-forming aqueous composition (hereinafter sometimes referred to as “film-forming temperature”) is less than the softening point of the polyethylene wax particles, the polyethylene wax is dispersed in the resin film. The shape of the particles can be held in a spherical shape, the lubricity can be further improved, and the effect of improving the paintability can be obtained.

  The film forming composition in the present invention preferably contains 1 to 15 parts by mass of an epoxy-based crosslinking agent. By using the cross-linking agent, the hardness of the resulting resin film is increased and the lubricity can be improved. The epoxy crosslinking agent is used because it has a high crosslinking reactivity with respect to the carboxyl group of the carboxyl group-containing polyurethane resin. The epoxy-based crosslinking agent is not particularly limited as long as it has two or more epoxy groups. For example, a bisphenol-based material can be used, and manufactured by Yuka Shell Epoxy Co., Ltd .: Epicoat 825, 828 or manufactured by Dainippon Ink & Chemicals, Inc .: Epicron CR75 or CR5L is exemplified.

  In the present invention, for the purpose of further improving the properties of the resin film formed on the surface of the metal plate, the film-forming composition may contain a second carboxyl group-containing resin having an acid value of 5 mgKOH / g or more. This is a preferred embodiment. The content of the second carboxyl group-containing resin in the film-forming composition is preferably less than half the mass of the carboxyl group-containing polyurethane resin content described above. The form of the second carboxyl group-containing resin is not particularly limited as long as it can be stably added to the aqueous film-forming composition, but is preferably in the form of, for example, an aqueous dispersion or an aqueous solution.

For example, if an ethylene / α, β-ethylenically unsaturated carboxylic acid copolymer resin is used as the second carboxyl group-containing resin, adhesion and flexibility can be imparted to the resin film. Examples of the ethylene / α, β-ethylenically unsaturated carboxylic acid copolymer resin include those composed of 60 to 99% by mass of ethylene and 1 to 40% by mass of α, β-ethylenically unsaturated carboxylic acid. . Examples of the copolymer resin include a random copolymer, a block copolymer, an unsaturated copolymer, a graft copolymer obtained by graft polymerization of an unsaturated carboxylic acid, and a terpolymer resin. Good.
For example, if the second carboxyl group-containing resin is an acrylic resin, a styrene resin, or a natural resin such as various copolymer resins, synthetic rubber, shellac, etc., the paintability of the resin film can be improved. The hardness of can be adjusted.

  Moreover, in order to improve the lubricity of the resin film, a synthetic wax can be added in the resin synthesis stage. Examples of the synthetic wax include modified waxes such as oxides such as polyethylene and polypropylene wax, and derivatives having these carboxyl groups. Further, there are copolymer waxes with ethylene and propylene, and oxidized waxes of ethylene copolymer wax. This system can be used in various ways including terpolymer systems depending on the copolymerization partner. Further examples include maleic acid addition waxes and fatty acid ester systems. Industrially preferred are polyethylene wax, polypropylene wax, modified wax, copolymer wax with ethylene and propylene, ethylene copolymer wax, oxides thereof, derivatives having a carboxyl group, etc. Paraffin wax, carnauba wax and the like.

  For waxes having no acid value or incompatibility, the emulsion is unstable, or the appearance of the coating when the emulsion is applied is poor, and phenomena such as wax bleeding occur. In the present invention, it is preferable to use a wax-based aqueous product having a carboxyl group in view of the necessity of emulsification of the wax resin, and the acid value of the wax is preferably 5 mgKOH / g or more, and the effect can be obtained with a commercially available wax.

  In order to emulsify these waxes, a method of using a surfactant, a method of self-emulsification, a mechanical dispersion method, and the like are taken according to the purpose of use. As the surfactant, an anionic surfactant, a nonionic surfactant, a reactive surfactant and the like can be usually used. Examples of the base used in the self-emulsification method include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and amines such as ammonia, morpholine and triethylamine.

In the present invention, it is also a preferred embodiment that the second carboxyl group-containing resin having an acid value of 5 mgKOH / g or more and the carboxyl group-containing polyurethane resin described above are crosslinked using a second crosslinking agent. The second crosslinking agent is not particularly limited as long as it can undergo a crosslinking reaction with a carboxyl group, and examples thereof include a metal-based crosslinking agent, an aziridine-based crosslinking agent, an epoxy-based crosslinking agent, and the like. Two or more kinds may be mixed and used. The metal-based crosslinking agents, for example Ba, Fe, Ca, Mg, Cu, 2 -valent metal compounds such as Zn and Mn, for example _{BaCO 3, FeCO 3, CaCO 3} , MgCO 3, CuCO 3, ZnCO 3, MnCO 3 Metal carbonates such as Ba (OH) ₂ , Fe (OH) ₂ , Ca (OH) ₂ , Mg (OH) ₂ , Cu (OH) ₂ , Zn (OH) ₂ , Mn (OH) ₂ Examples thereof include hydroxides, metal oxides such as ZnO, MgO and CaO. Other preferable calcium compounds are calcium lactate, calcium stearate, carboxymethylcellulose calcium, stearoyl calcium lactate, calcium propionate, calcium citrate, calcium glycerophosphate, calcium gluconate, calcium dihydrogen pyrophosphate, monohydrogen phosphate. Calcium, calcium dihydrogen phosphate, calcium trihydrogen phosphate, and the like, and the same applies to other metal systems used in combination as necessary.

  Preferred as the aziridine-based crosslinking agent used as the second crosslinking agent is an aziridine compound having an average of 1.5 to 3.5 active groups represented by the following chemical formula (1) in the molecule.

（式中、Ｒ¹〜Ｒ⁴は、水素または炭素数１〜４のアルキル基）

(Wherein R ^{1 to} R ⁴ are hydrogen or an alkyl group having 1 to 4 carbon atoms)

  Examples of the aziridine compound include ethylimine, triaziridinylphosphine oxide, aziridinylethyl methacrylate, hydroxyethylaziridine, hexamethylenebisaziridinecarboxyamide, diphenylmethanebisaziridinecarboxyamide, trimethylolpropane aziridinylpropionate, tetramethylol. Examples thereof include, but are not limited to, propaneaziridinylpropionate, toluenebisaziridinecarboxyamide, bisphthaloylmethylaziridine, trimethylolpropanemethylaziridinepropionate, and the like.

  The epoxy-based crosslinking agent that can be used as the second crosslinking agent is not particularly limited as long as it has at least two or more epoxy groups in the molecule. For example, it is used as a diepoxy compound, or a polyvalent epoxy compound and usually as a crosslinking agent. Any commercially available product can be used for the epoxy compound emulsion or water-soluble epoxy compound. The amount of the second crosslinking agent used is 0.01 times equivalent or more, more preferably 0.05 times equivalent or more, and more preferably 1 time equivalent or less, more preferably with respect to all carboxyl groups in the resin film. It is preferably 0.5 times equivalent or less. This is because if the amount of the crosslinking agent used is too small, a sufficient crosslinking effect cannot be obtained, whereas if the amount used is too large, the aqueous composition for forming a resin film thickens.

In the present invention, the adhesion amount of the resin film to the metal plate is preferably in the range of 0.3 to 2.5 g / m ² by dry weight. When the adhesion amount is less than 0.3 g / m ² , the film-forming composition cannot be uniformly applied, and the desired balanced performance such as lubricity and corrosion resistance can be sufficiently exhibited. Can not. In addition, if the adhesion amount exceeds 2.5 g / m ² , the amount of the resin film peeled off during press processing increases, and the peel film accumulates on the mold, causing trouble in press molding, In addition, the weldability tends to decrease. In addition, manufacturing costs are high.

  The metal plate used in the present invention is not particularly limited, but is preferably a zinc-based plated steel plate, for example, a hot-dip galvanized steel plate (GI), an alloyed molten Zn-Fe plated steel plate (GA), or an alloyed molten Zn. A −5% Al-plated steel plate (GF), an electric pure galvanized steel plate (EG), an electric Zn—Ni plated steel plate, an aluminum plate, a Ti plate and the like can be suitably used.

  The method for forming the resin film on the surface of the metal plate is not particularly limited. For example, the resin film can be formed by preparing an aqueous composition for forming a film, and applying and drying the aqueous composition on the surface of the metal plate. Before forming the resin film, the surface of the metal plate may be subjected to a treatment such as Co or Ni, an inhibitor treatment, or a base treatment of various non-chromates.

In the case of using a zinc-based plated steel sheet as the metal plate, it is a preferable aspect that the following surface modified layer is provided on the zinc-based plated layer and the above-described resin film is formed on the surface modified layer. . The surface modification layer provided on the zinc-based plating layer contains 1 to 30 mg / m ² of SiO ₂ in terms of Si, P: 0.5 to 15 mg / m ² , Al: 0.5 to 10 mg / m ² More preferably, the surface modification layer further contains an organic resin in addition to the SiO ₂ , P, and Al. The surface modified layer in this embodiment further enhances the above-mentioned characteristics such as corrosion resistance, workability, paintability, and lubricity, and enhances “tape peel resistance” pointed out by the non-chromate-treated zinc-based plated steel sheet. In the surface modified layer formed on the surface of the galvanized steel sheet, 1 to 30 mg / m ² SiO ₂ in terms of Si, P: 0.5 to 15 mg / m ² , and It is characterized in that Al: 0.5 to 10 mg / m ² is contained.

  In this embodiment, “tape peel resistance” refers to a surface treatment layer when the tape is peeled off after the adhesive label or adhesive tape is applied to the surface-treated zinc-based plated steel sheet and left to stand. Refers to the anti-peeling property that does not peel at the same time. In other words, the surface-treated steel sheet is shipped in the form of a roll of strip-shaped steel sheet, and is used as a cutting board after the coil is rewound by the customer. At that time, the end of the remaining coil is temporarily fixed with an adhesive tape. May be stored. Cut plates are processed into AV product cases and parts through processes such as punching, oiling, pressing, and alkaline degreasing. At that time, the product number, size, grade, etc. are displayed on the surface of the case and parts. Adhesive labels may be attached. Tape peeling is a phenomenon in which when the customer peels off the adhesive tape or adhesive label, the coating on the zinc-based plating surface peels off from the plating surface together with the tape. This is an extremely important issue for the quality of surface-treated steel sheets. When this occurs, it becomes a serious product defect. The degree of tape peel resistance varies depending on the type of pressure-sensitive adhesive tape used for the tape peel test, particularly the pressure-sensitive adhesive strength and the type of solvent or plasticizer contained therein.

  The reason why the top coat resin film and the surface modified layer are peeled off by the tape peeling is that the solvent or plasticizer contained in the adhesive of the pressure sensitive adhesive tape is formed on the surface modified layer or the top coat resin. It seems that the bonding force is reduced by diffusing and penetrating to the surface of the zinc-based plating layer through the film and accumulating at the bonding interface, and it seems to change considerably depending on the type and content of the solvent and plasticizer. Because.

However, even if there are some differences in the types and amounts of solvents, plasticizers, etc. that are blended as adhesives in ordinary adhesive tapes, there are no extreme differences in their diffusion / penetration rates, especially with respect to SiO ₂ -containing layers. Therefore, in this embodiment, as a standard evaluation standard, “Sliontec's filament tape“ Part No. # 9510 ”” or “Nichiban's“ Cellophane tape ”” is selected and used as a representative example. It is evaluated by sex.

The silica (SiO ₂ ) as the main component in the surface modified layer in the present embodiment is silicon oxide that is contained, for example, derived from colloidal silica or silicate, and the silica is essentially inorganic. Since it is a raw material and has a good affinity with the zinc-based plating layer, it exhibits an effect of enhancing the peel resistance between the zinc-based plating layer and forming it as a base layer of the overcoat resin film.

  By the way, as one of the causes of the tape peeling as described above, the following phenomenon can be considered. That is, when the surface-treated zinc-based plated steel sheet is stored in a state where an adhesive tape or the like is attached, especially when stored at a high temperature, a diffusible component such as a solvent or a plasticizer contained in the adhesive such as the adhesive tape. However, it diffuses and permeates through the overcoat to the surface modified layer and further to the zinc-based plating surface, and the adhesion force at the interface is reduced by accumulation of the solvent and plasticizer at the surface modified layer or the plating interface. This is considered to be a major cause of tape peeling.

However, silica contained as a main component in the surface modification layer of the present invention exhibits an excellent barrier effect against solvents and plasticizers that diffuse and permeate from the top coat layer as described above, and is based on zinc. It is thought that it exerts the function of preventing penetration into the plating surface or diffusion at the interface between the top coat and the surface modification layer, and the surface modification containing an appropriate amount of silica as will be clarified in the examples below. When the quality layer is formed, the tape peel resistance is remarkably improved. And when the present inventors investigated the quantitative relationship for effectively exhibiting the tape peel resistance improving action of such silica, the silica content in the surface modified layer was in the range of 1 to 30 mg / m ^{2 in} terms of Si. It was confirmed that the tape peel resistance could be significantly improved by adjusting to (2.14 to 64.3 mg / m ² SiO ₂ ).

Incidentally, when the silica content is less than 1 mg / m ^{2 in} terms of Si, the function as the barrier layer described above becomes insufficient, and satisfactory tape peel resistance is hardly exhibited. Therefore, the silica content in the surface modified layer is preferably 1 mg / m ² or more, more preferably about 3 mg / m ² or more, and further preferably 4 mg / m ² or more in terms of Si.

And as the silica content increases, the function as the barrier layer seems to increase. However, when the silica content is excessive, the tape peel resistance tends to decrease. The reason is considered as follows. That is, it is considered that the silica in the surface modified layer exists as an aggregate of fine particles, and when the silica content is increased, the fine particles are present in a multilayered state. Since the bonding force between the silica fine particle layers in the multi-layered state is not necessarily strong, when a tape peeling force acts on the silica fine particle layer, a force is applied in the direction of peeling the silica fine particle layer in the laminated state, It is conceivable that the silica fine particle layer tends to cause delamination. Therefore, in order to suppress delamination due to shear fracture of the surface-modified layer itself as much as possible, an upper limit of the silica content in the surface-modified layer should be set. Based on the results, the upper limit was determined to be 30 mg / m ^{2 in} terms of Si. Incidentally, when the silica content in the surface modified layer exceeds the upper limit, the tape peel resistance clearly shows a tendency to decrease. Further, since excessively increasing the silica content in the surface modified layer is economically wasteful, it is more preferable to keep it at 15 mg / m ² or less, more preferably 10 mg / m ² or less in terms of Si. .

  In this embodiment, when the surface-modified layer is formed, the surface of the plating layer that is appropriately roughened is usually derived from colloidal silica or the like while appropriately etching the surface of the zinc-based plating layer. It is preferable to deposit silica fine particles. As the etching component, for example, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and the like can be used, and particularly preferable as the etching component are aluminum salts such as phosphoric acid, heavy phosphoric acid, phosphorous acid, and biphosphorous acid. And an acidic aqueous liquid in which an appropriate amount of colloidal silica is dispersed is used. When such an acidic aqueous liquid is used as a surface treatment agent, a slightly soluble aluminum phosphate-based reaction layer is formed on the surface of the zinc-based plating layer while the surface of the zinc-based plating layer is etched by the acidic aqueous liquid. In addition, a fine reaction layer is formed between the zinc-based plating layer roughened by etching by depositing and taking in silica fine particles in the reaction layer, and an overcoat formed on the reaction layer. This is because the bond with the resin film becomes dense and strong, and naturally the tape peel resistance is remarkably improved. Further, as will be described later, by adding an aqueous solution of an organic resin to the acidic aqueous solution, the deposited state of the silica fine particles in the obtained surface modified layer can be further strengthened.

The reaction layer in which the poorly soluble aluminum phosphate and silica fine particles are combined and integrated has superior alkali resistance compared to the surface modified layer obtained using, for example, nitric acid as an etching agent. Excellent performance in tape peel resistance. However, when the silica-containing surface modified layer is formed using an aluminum salt such as phosphoric acid, deuterated phosphoric acid, phosphorous acid, biphosphorous acid as an etching component as described above, it is included in the surface modified layer. Depending on the respective contents of P and Al, there may be a significant difference in the alkali resistance of the surface-modified layer, and thus in the tape peeling resistance after alkali degreasing. And, in order to ensure stable and excellent tape peel resistance and tape peel resistance after alkaline degreasing, the P content in the surface modified layer is 0.5 mg / m ² or more and 15 mg / m ² or less. In addition, it is effective to control the Al content in the range of 0.5 mg / m ² or more and 10 mg / m ² or less.

  Incidentally, when a silica-containing surface modified layer is formed using an aluminum salt such as phosphoric acid as an etching component (hereinafter sometimes simply referred to as an aluminum phosphate salt) as described above, a reaction layer mainly composed of aluminum phosphate is used. As described above, the aluminum phosphate-based reaction layer excellent in alkali resistance is formed only by etching the surface of the zinc-based plating layer. When the amount of aluminum phosphate is excessively large, the alkali resistance tends to decrease even if aluminum phosphate and silica fine particles are combined and integrated.

Therefore, the P content and Al content in the surface-modified layer, which are preferable for securing a high level of tape peel resistance and tape peel resistance after alkaline degreasing, were examined. It has been found that it is extremely effective to control the Al content in the range of 5 mg / m ² or more and 15 mg / m ² or less and the Al content in the range of 0.5 mg / m ² or more and 10 mg / m ² or less.

Incidentally, when the P content or Al content is less than 0.5 mg / m ² , the above-mentioned effects brought about by using an aluminum phosphate salt, particularly the etching action and the formation of a dense reaction layer thereby, and the promotion of deposition of SiO ₂ fine particles The effect of improving the tape peel resistance due to is not exhibited effectively, and when the P content and Al content are excessively high, aluminum phosphate with insufficient alkali resistance is easily leached from the surface modification layer due to alkali erosion. Satisfactory tape peel resistance after alkaline degreasing cannot be obtained. Therefore, in order to significantly increase the tape peel resistance of the surface modified layer and the tape peel resistance after alkaline degreasing, the P content is set to 0.6 mg / m ² or more and 10 mg / m ² or less. It is a desirable mode to control the content to 0.6 mg / m ² or more and 7 mg / m ² or less.

Further, by adjusting the ratio of each content of Si, P, and Al contained in the surface modified layer so as to satisfy the relationship of the following formulas (1) and (2), further excellent tape peel resistance And tape peel resistance after alkaline degreasing can be ensured.
0.5 ≦ Si / P ≦ 20 ··· Formula (1)
0.7 ≦ P / Al ≦ 4.5 ・ ・ ・ ・ ・ ・ Formula (2)

The Si / P ratio is a factor that affects the etching action by phosphoric acid and the accompanying deposition promoting action on SiO _{2. When} this ratio is less than 0.5, the ratio of SiO ₂ in the surface-modified layer is relative. However, when this ratio exceeds 20, the amount of aluminum phosphate is insufficient compared to the silica content, and aluminum phosphate is used. This is considered to be because the above-mentioned action due to this is not effectively exhibited. From such a viewpoint, the more preferable ratio of Si / P in the surface modified layer is 1 or more, more preferably 2 or more, more preferably 15 or less, and still more preferably 10 or less.

  In addition, the content ratio of P / Al contained in the surface modification layer is considered to be a factor for maximally and effectively exerting the function of phosphoric acid as an etching component and the function of Al for making it hardly soluble. However, if this ratio is less than 0.7, a tendency of insufficient etching appears due to insufficient phosphoric acid, and conversely, if this ratio is too high exceeding 4.5, the poorly soluble aluminum salt produced after the etching treatment The amount decreases and the formation of a dense reaction layer becomes insufficient, and in any case, it is difficult to obtain satisfactory tape peel resistance after alkaline degreasing. A more preferable P / Al ratio is 1 or more and 2 or less in order to promote the formation of a hardly soluble aluminum salt while forming an appropriate etching action to form a sufficient amount of the reaction layer.

  The Si / P ratio and the P / Al ratio are adjusted by adjusting the content of silica and silicate in the surface treatment agent, the contents of phosphoric acid component and Al component, or the surface modification layer as described later. What is necessary is just to adjust by the water washing conditions at the time of formation (washing removal conditions of a phosphoric acid component or Al component). As described above, if the content of silica, P, and Al in the surface modified layer, and further the content ratio of Si, P, and Al are controlled within an appropriate range, the resulting surface modified layer is dense with no pinhole defects. It exhibits excellent performance not only in tape peel resistance under dry conditions but also in tape peel resistance after alkaline degreasing.

  Further, in this aspect, by incorporating an organic resin in the surface modified layer, the silica fine particles in the surface modified layer are strongly deposited, and tape peeling resistance, and further tape peeling resistance after alkali degreasing Can be further improved. Such an organic resin is not particularly limited, and examples thereof include acrylic resins, melamine resins, phenol resins, epoxy resins, urethane resins, polyester resins, alkyd resins, and polyethylene resins. Or 2 or more types can be used together.

  Further, the organic resin is preferably a water-soluble or water-dispersible organic resin, and it is preferable to use an organic resin composed of an organic acid and / or a salt thereof. As the organic resin composed of the organic acid, poly (meth) acrylic acid and / or a salt thereof is preferable. As described above, when the surface modified layer is formed, it is preferable to etch the galvanized layer using an acidic aqueous solution. However, the organic resin containing an organic acid as a constituent component and / or a salt thereof may be used. This is because the aqueous liquid contained is acidic, has an action of etching the galvanized layer itself, and is excellent in stability when blended into the acidic aqueous liquid.

By the way, the surface treatment agent used for forming the surface modified layer (hereinafter sometimes referred to as “undercoat treatment agent” or “undercoat surface treatment agent”) is colloidal silica as is apparent from the above. Is a base treatment agent containing silica fine powder such as phosphoric acid, an aluminum salt such as phosphoric acid, and, if necessary, an organic resin. The base treatment agent has a solid content concentration of 0.01 to It is desirable that the content (mass%) and composition ratio (mass ratio) of Si, P, and Al contained in the treatment agent are adjusted to satisfy the following requirements at 15%.
Si: 0.002 to 4.5%
P: 0.0005 to 1.5%
Al: 0.0001 to 0.5%
4.5 ≦ Si / Al ≦ 230, 1.5 ≦ Si / P ≦ 60

  By the way, if the solid content concentration of the base treatment agent is less than 0.01%, it is difficult to form a surface-modified layer having a satisfactory thickness by one treatment, and many treatments are required. It is not practical, and if the concentration exceeds 15%, solids are likely to be generated at the gas-liquid interface in the treatment liquid, and product defects such as push rods and blisters tend to occur. Will arise. Considering these points, the more preferable solid content concentration is 0.05% or more and 10% or less, and further preferably 0.1% or more and 5% or less.

On the other hand, when the Si concentration in the base treating agent is less than 0.002%, the silica content which is the main component of the barrier layer in the surface modified layer tends to be insufficient, and it is difficult to obtain satisfactory tape peel resistance. On the other hand, if the Si concentration exceeds 4.5%, the content ratio of silica in the treatment agent becomes excessively high, the silica content in the surface modified layer becomes excessive, and the tape peel resistance tends to decrease. It becomes like. In consideration of such a tendency, the more preferable Si concentration in the base treating agent is 0.01% or more, more preferably 0.03% or more, 4% or less, and further preferably 3% or less. The Si concentration in the base treatment agent may be adjusted mainly by the blending amount of SiO ₂ blended as colloidal silica or the like, and further silicate.

  Next, the P concentration in the surface treatment agent for the base depends on the amount of the phosphoric acid compound compounded as phosphoric acid, heavy phosphoric acid, phosphorous acid, biphosphorous acid, etc., and mainly etching effect and precise reaction It becomes an important factor governing the formation of the layer. That is, if the P concentration is too low, the etching action becomes insufficient, and the formation of the above-described dense aluminum phosphate-based reaction layer is also insufficient, and the effect of promoting the deposition of silica fine particles is reduced. And the alkali resistance becomes insufficient. Therefore, the P concentration in the treatment agent is 0.0005% or more, more preferably 0.001% or more, and still more preferably 0.01% or more. However, if the P concentration in the base treatment agent becomes excessively high, it becomes difficult to control the etching amount on the surface of the zinc-based plating, and the product tends to be defective in appearance, and the treatment liquid tank and the like are easily corroded. Since a problem also arises, it is preferable to keep it to 1.5% or less, more preferably 1% or less, and still more preferably 0.5% or less.

  Furthermore, the Al concentration in the base treatment agent depends mainly on aluminum salts such as phosphoric acid, and Al hydroxide that may be added if necessary. It serves as a generation source of poorly soluble aluminum phosphate produced as a layer, and plays an important role in enhancing the adhesion and alkali resistance of the surface modified layer by promoting the deposition of silica. In order to effectively exert such effects, it is desirable to adjust the Al concentration in the treatment agent to at least 0.0001%, preferably 0.0005%, more preferably 0.001%. However, if the Al concentration is excessively high, solids are likely to be generated at the gas-liquid interface in the processing liquid, and product defects such as push ridges and blisters are liable to occur, so at most 0.5% or less, preferably It is good to keep it at 0.4% or less, more preferably 0.2% or less.

  In addition, the respective content ratios of Si / Al and Si / P contained in the base treatment agent are determined by the amount of aluminum phosphate-based dense reaction layer produced at the initial stage of the surface treatment and the amount of silica deposited. If the Al or P content is insufficient relative to the Si content, the etching will be relatively insufficient, resulting in not only the denseness and generation amount of the reaction layer mainly composed of aluminum phosphate, but also silica. Also, the effect of promoting the deposition on the tape is reduced, and the tape peel resistance and the tape peel resistance after alkaline degreasing become insufficient. Conversely, if the Al or P content is excessively large relative to the Si content, the silica concentration in the reaction layer tends to be insufficient, resulting in insufficient tape peel resistance.

  Considering these advantages and disadvantages, when the preferred content ratio of Si / Al and Si / P contained in the base treatment agent was confirmed by experiments, the Si / Al ratio was 4.5 or more and 230 or less, more preferably Was 6 or more and 100 or less, and the Si / P ratio was confirmed to be 1.5 or more, more preferably 1.8 or more, and 60 or less, more preferably 20 or less.

  The method for adjusting the Si, Al, P content in the surface treatment agent for the base to a suitable range is not particularly limited, but the Si content is the same as the Al content depending on the content of silica, silicate, etc. in the surface treatment agent. Since the P content depends on the content of phosphoric acid, phosphate, etc. in the treatment agent depending on the content of Al phosphate and hydroxide in the treatment agent, What is necessary is just to carry out by controlling content of a component appropriately.

  Moreover, when the said surface treatment agent for base | substrates contains the organic resin mentioned above, it is preferable that the addition density | concentrations of the organic resin in this processing agent are 0.01-3 g / L. This is because when the addition concentration is less than 0.01 g / L, the addition effect of the organic resin is reduced. On the other hand, when the additive concentration exceeds 3 g / L, the tape peel resistance after alkaline degreasing may deteriorate.

  In the present invention, an acidic aqueous liquid containing an organic resin, aluminum salt such as phosphoric acid, heavy phosphoric acid, phosphorous acid, biphosphorous acid, and colloidal silica is particularly preferable as the surface treatment agent for the base. If the base treating agent is used, while the zinc-based plating layer on the steel sheet surface is etched under an acidic aqueous solution, a dense reaction layer mainly composed of hardly soluble aluminum phosphate is formed on the surface of the zinc-based plating layer, Silica is deposited and incorporated in the reaction layer, so that a dense reaction layer is formed with zinc eluted by etching, and the surface modification exhibits excellent tape peeling resistance and tape peeling resistance after alkali degreasing. A quality layer can be formed.

  More specifically, the surface treatment agent for the base is phosphoric acid (or heavy phosphoric acid, phosphorous acid, biphosphorous acid) Al salt in a mass ratio of the solid content thereof; 0.1 to 0.4% by mass; Colloidal silica; 1.0 to 1.5% by mass, organic resin; 0.1 to 3 g / L, preferably an acidic aqueous liquid having a pH in the range of 1.5 to 3.5.

Arbitrary means such as spraying, dipping or roll coating can be adopted as a method for treating the zinc-based plated steel sheet with the surface treatment agent for the base. Among them, the spray coating method is more effective for promoting the reaction with galvanizing. A preferable spray pressure is 20 to 500 kPa (about 0.2 to 5.0 kgf / cm ² ), and a spray time is in the range of 0.5 to 10 seconds.

After the surface treatment with the base treatment agent, the soluble components are removed by washing with water moderately, and then the water is dried and removed by heating to about 30 to 150 ° C., for example. Washing with water at this time is an extremely important treatment step for enhancing the alkali resistance of the finally obtained surface modified layer, and consequently the tape peeling resistance after alkali degreasing. That is, the present inventors have confirmed through various experiments that, in the modified layer that has been treated with the above-described surface treatment agent and then dried or baked, the P content in the surface modified layer and Al many content greatly exceeding the preferred Al content 0.5 to 10 mg / m ² and preferably P content 0.5-15 / m ² required for the surface modification layer described above, the resistance to tape peeling resistance after alkaline degreasing It was confirmed that it would be difficult to secure. The reason is considered as follows.

It has also been confirmed that the surface treatment in this embodiment is effective as a base treatment for improving the adhesion of the organic overcoat resin film. However, the present inventors have confirmed that the surface modification layer formed by the surface treatment agent containing silica fine particles and an aluminum phosphate salt contains a considerably large amount of an aluminum phosphate component. It reaches about 30 mg / m ² or more in terms of P and about 15 mg / m ² or more in terms of Al.

  And, in order to reduce these P and Al contents to the preferred range mentioned above, that these high P and Al contents have a particularly bad influence on tape peel resistance after alkali degreasing, After the base surface treatment, a water washing treatment is performed, and the water-soluble components in the phosphate-based aluminum component contained in the surface treatment (modified) layer are eluted and removed in advance, and reduced within the above-described preferable content range. I found out.

As the water washing method, a dipping method or a spray method can be considered, and the water washing condition varies depending on the content of water-soluble components in the phosphate-based aluminum component contained in the surface treatment (modified) layer. In this case, the washing time is about 1.5 to 15 seconds. In the case of the spray method, the washing time is about 1.5 to 15 seconds and the spray pressure is 20 to 500 kPa (about 0.2 to 5 kgf / cm ² ). If it is made into a grade, since the said water-soluble component can be removed more efficiently, it is preferable.

The content of P and Al in the surface modification layer may be small from the viewpoint of improving the tape peel resistance and may be substantially zero, but the above-mentioned etching action as a surface treatment agent. In a preferred embodiment of the present invention in which an aluminum phosphate compound is used in order to form a dense reaction layer and obtain a higher tape peel resistance, the minimum P content is about 0.5 mg / m ² The Al content is also required to be about 0.5 mg / m ² .

The amount of adhesion as the surface modification layer is not particularly limited, but a preferable range is 4 to 60 mg / m ² as a dry coating film after the water washing treatment. If the amount is too small, it will be difficult to cover the surface of the galvanized surface uniformly, and the tape peel resistance will be insufficient. Conversely, if the amount is too large, the reaction layer will become less dense due to insufficient etching of the galvanized surface. This is because the tape peel resistance of the steel tends to deteriorate.

  The amounts of Si, P, and Al in the surface modification layer may be confirmed by, for example, the fluorescent X-ray method. The presence of the organic resin in the surface modified layer is confirmed by the peak of FT-IR derived from the structure of the organic resin (such as ester bond, ketone, amino group, hydroxyl group, and carbon-hydrogen bond). be able to.

In this embodiment, the FT-IR absorption intensity (peak area of 1496 to 1776 cm ⁻¹ ) derived from the structure of the organic resin of the surface modified layer is preferably 0.1 to 15. The absorption strength of the FT-IR is an index of the content of the organic resin in the surface modified layer. By making the absorption strength of the FT-IR within a certain range, the tape peel resistance and the alkaline degreasing Later tape peel resistance can be improved.

[Evaluation methods]
(1) Corrosion resistance About the obtained resin coating metal plate (steel plate), the salt spray test was implemented according to JIS-Z2371, and it evaluated by the time until 1% of white rust generate | occur | produces.
(Evaluation criteria)
◎: 360 hours or more ○: 320 hours or more to less than 360 hours Δ: 240 hours or more to less than 320 hours ×: less than 240 hours

(2) Lubricity In order to evaluate the lubricity of the obtained resin-coated metal plate (steel plate), using a sliding test device, the load due to sliding when the applied pressure is 5.4 MPa and the drawing speed is 300 mm / min. And the dynamic friction coefficient was calculated.
(Evaluation criteria)
◎: 0.01 or more and 0.1 or less ○: More than 0.1 to 0.2 or less Δ: More than 0.2 to 0.3 or less ×: More than 0.3

(3) Workability (blackening resistance)
In order to evaluate the deep drawing workability of the resulting resin-coated metal plate (steel plate), a single press test was conducted using an 80-ton crank press machine, and the sliding surface of the sliding surface of the molded product, the mold The galling and blackening resistance was visually evaluated.
(Evaluation criteria)
◎: Extremely good ○: Good △: Bad ×: Extremely bad

(4) Paintability (coating adhesion)
The resulting resin-coated metal plate (steel plate) was bar-coated with a melamine alkyd paint so that the coating thickness was about 20 μm, and baked at a temperature of 130 ° C. for 20 minutes for post-coating. Subsequently, after immersing the test steel plate in boiling water for 1 hour, taking it out and letting it stand for 1 hour, 100 mm of 1 mm square grids were cut with a cutter knife, and a tape peeling test was carried out on this, The coating film adhesion was evaluated in 5 stages according to the number of residual cells.
(Evaluation criteria)
5: 100% coating film remaining rate
4: Coating film residual ratio 90% or more to less than 100% 3: Coating film remaining ratio 80% or more to less than 90% 2: Coating film remaining ratio 70% or more to less than 80% 1: Coating film remaining ratio less than 70%

(5) Tape peeling resistance Filament tape (Sliontec: # 9510) was affixed to the surface of the test steel plate and stored for 48 hours and 72 hours in an atmosphere of 40 ° C. × RH 98%, and then the filament tape was peeled off. Evaluation was based on the area ratio of the overcoated resin film remaining.
(Evaluation criteria)
◎: 100% film remaining rate
○ to ◎: film remaining rate 95% to less than 100% ○: film remaining rate 90% to less than 95% Δ: film remaining rate 70% to less than 90% ×: film remaining rate less than 70%

(6) Tape peeling resistance after alkali degreasing The test steel sheet was immersed for 2 minutes in a degreasing solution adjusted to 20 g / L, 60 ° C. with an alkaline degreasing agent (manufactured by Nippon Parkerizing Co., Ltd .: CL-N364S), pulled up, After washing with water and drying, a cellophane tape (manufactured by Nichiban Co., Ltd.) was applied to the surface of the test steel sheet, peeled after 24 hours and 48 hours, and evaluated by the area ratio where the top coat resin film remained.
(Evaluation criteria)
◎: 100% film remaining rate
○ to ◎: film residual rate 95% or more to 100%
○: Residual rate of film 90% to less than 95% Δ: Residual rate of film 70% to less than 90% ×: Residual rate of film less than 70%

(7) Calculation of absorption strength of organic resin by FT-IR measurement The FT-IR measurement and analysis conditions for investigating the resin content in the surface modified layer of the formed resin-coated metal sheet (steel plate) are as follows: It is as follows.
Measurement method: High-sensitivity reflection method (incident angle 75 °, parallel polarized light irradiated with infrared light)
Comparative material: Gold vapor deposition mirror Resolution: 4 cm ^-1
Integration number: 500 times Device: JEOL Ltd .: JIR-5500 type Fourier transform infrared spectrophotometer IR-RSC110 reflection measurement unit (variable angle type)
IR-SEM100 sample switching stage From the peak area of 1496 cm ^{−1 to} 1776 cm ⁻¹ , the surface modification layer is obtained by subtracting the absorption strength of the steel plate not added with the organic resin from the absorption strength of the steel plate added with the organic resin. The absorption intensity derived from the structure of the organic resin inside was calculated.

[Preparation of aqueous polyurethane resin dispersion]
Production Example 1
60 g of polytetramethylene ether glycol (average molecular weight 1000) manufactured by Hodogaya Chemical Co., Ltd. as a polyol component in a 0.8 L internal synthesizer equipped with a stirrer, thermometer and temperature controller, 1,4-cyclohexanedimethanol 14 g and 20 g of dimethylolpropionic acid were charged, and 30.0 g of N-methylpyrrolidone was added as a reaction solvent. 104 g of tolylene diisocyanate (hereinafter sometimes simply referred to as “TDI”) was added as an isocyanate component, and the temperature was raised from 80 to 85 ° C. and reacted for 5 hours. The obtained prepolymer had an NCO content of 8.9%. Further, 16 g of triethylamine was added for neutralization, a mixed aqueous solution of 16 g of ethylenediamine and 480 g of water was added, emulsified at 50 ° C. for 4 hours, and chain extended to obtain an aqueous polyurethane resin dispersion 1 (solid content 29.1). %, Acid value 41.4).

Production Example 2
67 g of polytetramethylene ether glycol (average molecular weight 1500) manufactured by Hodogaya Chemical Co., Ltd. as a polyol component, 1,4-cyclohexanedimethanol as a polyol component in a 0.8 L internal synthesizer equipped with a stirrer, thermometer and temperature controller 30 g and 14 g of dimethylolpropionic acid were charged, and 120.0 g of N-methylpyrrolidone was added as a reaction solvent. As the isocyanate component, 78 g of tolylene diisocyanate (TDI) was charged, heated to 80 to 85 ° C., and reacted for 5 hours. The obtained prepolymer had an NCO content of 2.3%. Further, 11 g of triethylamine was added for neutralization, a mixed aqueous solution of 5 g of hydrazine monohydrate and 330 g of water was added, emulsified at 50 ° C. for 5 hours, and subjected to chain extension reaction to obtain an aqueous polyurethane resin dispersion 2 (Solid content 30.5%, acid value 29.8).

Production Example 3
60 g of polytetramethylene ether glycol (average molecular weight 1500) manufactured by Hodogaya Chemical Co., Ltd. as a polyol component and 1,4-cyclohexanedimethanol as a polyol component in a 0.8 L internal synthesizer equipped with a stirrer, thermometer and temperature controller 14 g and 6 g of dimethylolpropionic acid were charged, and 90.0 g of N-methylpyrrolidone was added as a reaction solvent. As an isocyanate component, 100 g of diphenylmethane diisocyanate (hereinafter sometimes simply referred to as “MDI”) was charged, and the temperature was raised to 80 to 85 ° C. and reacted for 10 hours. The obtained prepolymer had an NCO content of 6%. Further, 5 g of triethylamine was added for neutralization, a mixed aqueous solution of 6 g of hydrazine monohydrate and 350 g of water was added, and a chain extension reaction was carried out at 50 ° C. for 5 hours to obtain an aqueous polyurethane resin dispersion 3 (solid content) 30.2%, acid value 15.2).

Production Example 4
60 g of polytetramethylene ether glycol (average molecular weight 1500) manufactured by Hodogaya Chemical Co., Ltd. as a polyol component and 1,4-cyclohexanedimethanol as a polyol component in a 0.8 L internal synthesizer equipped with a stirrer, thermometer and temperature controller 14 g and 13 g of dimethylolpropionic acid were charged, and 90.0 g of N-methylpyrrolidone was added as a reaction solvent. As an isocyanate component, 34 g of TDI and 50 g of MDI were charged, heated to 80 to 85 ° C., and reacted for 9 hours. The NCO content of the obtained prepolymer was 5%. Further, neutralization was performed by adding 11 g of triethylamine, a mixed aqueous solution of 8 g of hydrazine monohydrate and 325 g of water was added, emulsified at 50 ° C. for 3 hours, and chain extension reaction was carried out to obtain an aqueous polyurethane resin dispersion 4 (Solid content 31.3%, acid value 31.0).

Production Example 5
50 g of polytetramethylene ether glycol (average molecular weight 1000) manufactured by Hodogaya Chemical Co., Ltd. as a polyol component in a 0.8 L internal synthesizer equipped with a stirrer, thermometer and temperature controller, 1,4-cyclohexanedimethanol 14 g and 6 g of dimethylolpropionic acid were charged, and 90.0 g of N-methylpyrrolidone was added as a reaction solvent. 104 g of dicyclohexylmethane diisocyanate (hereinafter sometimes simply referred to as “hydrogenated MDI”) was added as an isocyanate component, and 6 drops of organotin catalyst manufactured by Tokyo Fine Chemical Co., Ltd .: L-101 was added, and the temperature was raised to 90 to 95 ° C. Warmed and allowed to react for 9 hours. The obtained prepolymer had an NCO content of 6.3%. Further, 5 g of triethylamine was added for neutralization, a mixed aqueous solution of 6 g of hydrazine monohydrate and 325 g of water was added, and the mixture was emulsified at 50 ° C. for 5 hours to cause chain extension reaction. Obtained (solid content 29.9%, acid value 16.3).

Production Example 6
As a polyol component, 50 g of polyoxypropylene glycol (P-1000: average molecular weight 1000) manufactured by Asahi Denka Kogyo Co., Ltd. as a polyol component was added to a 0.8 L internal synthesizer equipped with a stirrer, a thermometer, and a temperature controller. 2.9 g of cyclohexanedimethanol and 6 g of dimethylolpropionic acid were charged, and 60.0 g of N-methylpyrrolidone was further added as a reaction solvent. 79 g of dicyclohexylmethane diisocyanate (hereinafter sometimes simply referred to as “hydrogenated MDI”) is added as an isocyanate component, and 3 drops of organotin catalyst manufactured by Tokyo Fine Chemical Co., Ltd .: L-101 is added, and the temperature is raised to 90 to 95 ° C. Allowed to react for 8 hours. The NCO content of the obtained prepolymer was 7.6%. Further, 5 g of triethylamine was added for neutralization, and a mixed aqueous solution of 13 g of hydrazine monohydrate and 280 g of water was added, emulsified at 50 ° C. for 5 hours, and subjected to chain extension reaction to obtain an aqueous polyurethane resin dispersion 6 Obtained (solid content 29.8%, acid value 18.0).

Production Example 7
40 g of polyoxypropylene glycol (PP-400: average molecular weight 400) manufactured by Sanyo Kogyo Co., Ltd. as a polyol component in a 0.8 L internal synthesizer equipped with a stirrer, thermometer and temperature controller, 1,4-cyclohexane 7.2 g of dimethanol and 25 g of dimethylolpropionic acid were charged, and 80.0 g of N-methylpyrrolidone was further added as a reaction solvent. 105 g of dicyclohexylmethane diisocyanate (hereinafter sometimes simply referred to as “hydrogenated MDI”) was added as an isocyanate component, and 2 drops of an organotin catalyst manufactured by Tokyo Fine Chemical Co., Ltd .: L-101 was added, and the temperature was raised to 90 to 95 ° C. Allowed to react for 8 hours. The obtained prepolymer had an NCO content of 2.2%. Further, 21 g of triethylamine was added for neutralization, a mixed aqueous solution of 4.5 g of hydrazine monohydrate and 330 g of water was added, emulsified at 50 ° C. for 5 hours, and subjected to chain extension reaction, to obtain an aqueous polyurethane resin dispersion 7 (solid content 29.7%, acid value 58.0).

Production Example 8
200 g of ethylene acrylic acid copolymer with an acid value of 160 mgKOH / g, 4 g of 48% sodium hydroxide aqueous solution, 22 g of 25% aqueous ammonia in an autoclave with an emulsification equipment of 0.8 L with an agitator, thermometer and temperature controller Then, 581 g of soft water was added and sealed, followed by high-speed stirring at 150 ° C. and 4 atm for 3 hours, and cooling to 40 ° C. An aqueous dispersion of the copolymer (resin content: 25%, acid value: 160 mgKOH / g) was obtained. Next, 500 g of the polyurethane resin aqueous dispersion 1 obtained in Production Example 1 is being stirred at room temperature in a stirring vessel having an internal volume of 0.8 L equipped with a stirrer, a thermometer, and a temperature controller. 175 g of an aqueous dispersion of ethylene acrylic acid copolymer resin was added, heated and stirred, and after raising the temperature to 70 ° C., 20 g of 25% aqueous 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane and 58 g of soft water were added. Was added, and the mixture was stirred at 80 to 85 ° C. for 2 hours, cooled to 40 ° C., and filtered through a 150-mesh filter cloth to obtain a modified polyurethane resin aqueous dispersion 8.

Production Example 9
In an autoclave of an emulsification facility having an internal capacity of 0.8 L equipped with a stirrer, a thermometer, and a temperature controller, 200 g of oxidized polyethylene wax: AC-629 having an acid value of 16 mgKOH / g manufactured by Honeywell, 48% sodium hydroxide 5 g of aqueous solution, manufactured by Toho Chemical Industry Co., Ltd .: 25 g of Peganol L-12 and 420 g of soft water were added and sealed, and the mixture was stirred at 150 ° C. and 5 atm for 3 hours, cooled to 40 ° C., and polyethylene oxide An aqueous dispersion of wax (resin content: 35.1%, acid value: 16 mgKOH / g) was obtained. Next, 500 g of the polyurethane resin aqueous dispersion 4 obtained in Production Example 4 is stirred at room temperature in a stirring vessel having an internal volume of 0.8 L equipped with a stirrer, a thermometer, and a temperature controller. 100 g of an aqueous dispersion of oxidized polyethylene wax was added and stirred uniformly. Further, 1.8 g of CaCO ₃ was added, and the mixture was heated to 80 ° C. and cooled to carry out a crosslinking reaction. Got.

Production Example 10
An emulsion polymerization facility having an internal capacity of 1 L equipped with a stirrer, a thermometer, and a temperature controller was charged with 180 g of water and 5 g of Peganol L-12 manufactured by Toho Chemical Industry Co., Ltd., and heated to 85 ° C. In another monomer mixing facility, a monomer composed of 160 g of 2-ethylhexyl acrylate, 200 g of methyl methacrylate, and 40 g of methacrylic acid was prepared by mixing 15 g of PEGNOL L-30P and 350 g of water, manufactured by Toho Chemical Industry Co., Ltd. The monomer emulsified liquid was added dropwise over 6 hours while maintaining the temperature of the emulsion polymerization equipment at 80 to 85 ° C. After completion of dropping, the mixture was aged at 85 to 90 ° C. for 30 minutes and cooled to obtain an acrylic resin emulsion (resin content: 38.8%, acid value: 36). Next, 500 g of the polyurethane resin aqueous dispersion 5 obtained in Production Example 5 is being stirred at room temperature in a 0.8 L stirring tank equipped with a stirrer, a thermometer, and a temperature controller. Add 138 g of acrylic resin emulsion and stir, and then add 5 g of 25% 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane aqueous solution, 0.5 g of MgCO ₃ and 20 g of soft water, and add 2 at 80 to 85 ° C. After stirring for a period of time, the mixture was cooled to 40 ° C. and filtered through a 150 mesh filter cloth to obtain a modified polyurethane resin aqueous dispersion 10.

Production Example 11
An emulsion polymerization facility having an internal capacity of 1 L equipped with a stirrer, a thermometer, and a temperature controller was charged with 180 g of water and 5 g of Peganol L-12 manufactured by Toho Chemical Industry Co., Ltd., and heated to 85 ° C. In another monomer mixing facility, a monomer composed of 160 g of 2-ethylhexyl acrylate, 200 g of methyl methacrylate, and 40 g of methacrylic acid was prepared by mixing 15 g of PEGNOL L-30P and 350 g of water, manufactured by Toho Chemical Industry Co., Ltd. The monomer emulsified liquid was added dropwise over 6 hours while maintaining the temperature of the emulsion polymerization equipment at 80 to 85 ° C. After completion of dropping, the mixture was aged at 85 to 90 ° C. for 30 minutes and cooled to obtain an acrylic resin emulsion (resin content: 38.8%, acid value: 36 mgKOH / g). Next, 500 g of the polyurethane resin aqueous dispersion 7 obtained in Production Example 7 was stirred at room temperature in a stirring vessel having an internal volume of 0.8 L equipped with a stirrer, a thermometer, and a temperature controller. Add 138 g of acrylic resin emulsion and stir, and then add 15 g of 25% 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane aqueous solution, 1.5 g of MgCO ₃ and 20 g of soft water, and add 2 at 80 to 85 ° C. After stirring for a period of time, the mixture was cooled to 40 ° C. and filtered through a 150 mesh filter cloth to obtain a modified polyurethane resin aqueous dispersion 11.

Production Example 12
80 g of polytetramethylene ether glycol (average molecular weight 1000) manufactured by Hodogaya Chemical Co., Ltd. and 20 g of dimethylolpropionic acid are charged as polyol components in a 0.8 L internal synthesizer equipped with a stirrer, thermometer and temperature controller. Further, 30.0 g of N-methylpyrrolidone was added as a reaction solvent. 104 g of tolylene diisocyanate was added as an isocyanate component, and the temperature was raised from 80 to 85 ° C. and reacted for 5 hours. The obtained prepolymer had an NCO content of 8.9%. Further, 16 g of triethylamine was added for neutralization, a mixed aqueous solution of 16 g of ethylenediamine and 480 g of water was added, and emulsified at 50 ° C. for 4 hours to obtain a polyurethane resin aqueous dispersion 12 which was subjected to crosslinking reaction to extend the chain (solid). 30.1% min, acid value 41.4).

Production Example 13
A synthesis device having an internal volume of 0.8 L equipped with a stirrer, a thermometer, and a temperature controller was charged with 50 g of 1,4-cyclohexanedimethanol and 20 g of dimethylolpropionic acid as polyol components, and further with 30 g of N-methylpyrrolidone as a reaction solvent. 0 g was added. 104 g of tolylene diisocyanate was added as an isocyanate component, and the temperature was raised from 80 to 85 ° C. and reacted for 5 hours. The obtained prepolymer had an NCO content of 8.9%. Further, 16 g of triethylamine was added for neutralization, a mixed aqueous solution of 16 g of ethylenediamine and 480 g of water was added, emulsified at 50 ° C. for 4 hours, and subjected to a crosslinking reaction to obtain an aqueous polyurethane resin dispersion 13 (solid content 29.6). %, Acid value 47.3).

[Production and evaluation results of resin-coated metal sheet (steel sheet)]
Example 1
Colloidal silica (manufactured by Nissan Chemical Industries, Ltd .: ST-40), epoxy-based crosslinking agent (manufactured by Dainippon Ink & Chemicals, Inc .: Epicron CR75), polyethylene wax particles (manufactured by Mitsui Chemicals, Inc.) Chemipearl W-700, average particle diameter 1 μm, softening point 132 ° C.) was added to prepare a film forming composition. The blending ratio of each component was blended so as to be 83 parts by weight of a carboxyl group-containing polyurethane resin, 10 parts by weight of colloidal silica, 2 parts by weight of an epoxy-based crosslinking agent, and 5 parts by weight of polyethylene wax particles in terms of solid content. Further, Cylest P (DTPA · 5Na) was added so that the chelating agent content was 3 parts by mass in 100 parts by mass of the solid content of the film-forming composition. This film-forming composition was applied to the surface of an electrogalvanized steel sheet (Zn deposition amount 20 g / m ² , plate thickness 0.8 mm) with a squeeze roll, and heated and dried for 1 minute at a plate temperature of 90 ° C. A resin-coated metal plate (steel plate) on which a resin film having an amount of 1.0 g / m ² was formed was obtained. The obtained resin-coated metal plate (steel plate) was evaluated for corrosion resistance, lubricity, workability, and paintability. The results are shown in Table 1.

(Example 2)
An aqueous polyurethane resin dispersion 1, colloidal silica (ST-40), an epoxy-based crosslinking agent, and polyethylene wax particles (W-700, an average particle diameter of 1 μm, a softening point of 132 ° C.) were added to prepare a film forming composition. The blending ratio of each component was blended so as to be 83 parts by weight of a carboxyl group-containing polyurethane resin, 10 parts by weight of colloidal silica, 2 parts by weight of an epoxy-based crosslinking agent, and 5 parts by weight of polyethylene wax particles in terms of solid content. Further, various chelating agents shown in Table 2 were added. Using this film-forming composition, a resin-coated steel sheet was obtained in the same manner as in Example 1. The obtained resin-coated metal plate (steel plate) was evaluated for corrosion resistance, lubricity, workability, and paintability. The results are shown in Table 2.

(Example 3)
Colloidal silica (ST-40), an epoxy-based crosslinking agent, and polyethylene wax particles (W-700: average particle diameter 1 μm, softening point 132 ° C.) were added to the aqueous polyurethane resin dispersion 1 to prepare a film-forming composition. . The blending ratio of each component is 43 to 93 parts by mass of a carboxyl group-containing polyurethane resin, 0 to 45 parts by mass of colloidal silica, 2 parts by mass of an epoxy-based crosslinking agent, and 5 parts by mass of polyethylene wax particles in terms of solid content. It mix | blended (however, it shall be 100 mass parts in total). Further, Cylest P (DTPA · 5Na) was added so that the chelating agent content was 3 parts by mass in 100 parts by mass of the solid content of the film-forming composition. Using this film-forming composition, a resin-coated metal plate (steel plate) was obtained in the same manner as in Example 1. The obtained resin-coated metal plate (steel plate) was evaluated for corrosion resistance, lubricity, workability, and paintability. The results are shown in Table 3.

Example 4
Colloidal silica (ST-40), an epoxy-based crosslinking agent, and polyethylene wax particles (W-700: average particle diameter 1 μm, softening point 132 ° C.) were added to the aqueous polyurethane resin dispersion 1 to prepare a film-forming composition. . The compounding ratio of each component is 70 to 85 parts by mass of a carboxyl group-containing polyurethane resin, 10 parts by mass of colloidal silica, 0 to 25 parts by mass of an epoxy-based crosslinking agent, and 5 parts by mass of polyethylene wax particles in terms of solid content. It mix | blended (however, it shall be 100 mass parts in total). Further, Cylest P (DTPA · 5Na) was added so that the chelating agent content was 3 parts by mass in 100 parts by mass of the solid content of the film-forming composition. Using this film-forming composition, a resin-coated metal plate (steel plate) was obtained in the same manner as in Example 1. The obtained resin-coated metal plate (steel plate) was evaluated for corrosion resistance, lubricity, workability, and paintability. The results are shown in Table 4.

(Example 5)
Colloidal silica (ST-40), an epoxy-based crosslinking agent, and polyethylene wax particles (W-700: average particle diameter 1 μm, softening point 132 ° C.) were added to the aqueous polyurethane resin dispersion 1 to prepare a film-forming composition. . The blending ratio of each component is 78 to 88 parts by mass of a carboxyl group-containing polyurethane resin, 10 parts by mass of colloidal silica, 2 parts by mass of an epoxy-based crosslinking agent, and 0 to 10 parts by mass of polyethylene wax particles in terms of solid content. It mix | blended (however, it shall be 100 mass parts in total). Further, Cylest P (DTPA · 5Na) was added so that the chelating agent content was 3 parts by mass in 100 parts by mass of the solid content of the film-forming composition. Using this film-forming composition, a resin-coated metal plate (steel plate) was obtained in the same manner as in Example 1. The obtained resin-coated metal plate (steel plate) was evaluated for corrosion resistance, lubricity, workability, and paintability. The results are shown in Table 5.

(Example 6)
Colloidal silica (ST-40), an epoxy-based crosslinking agent, and polyethylene wax particles having an average particle diameter of 7 μm or less (softening point: 132 ° C.) were added to the polyurethane resin aqueous dispersion 1 to prepare a film-forming composition. The blending ratio of each component was blended so as to be 83 parts by weight of a carboxyl group-containing polyurethane resin, 10 parts by weight of colloidal silica, 2 parts by weight of an epoxy-based crosslinking agent, and 5 parts by weight of polyethylene wax particles in terms of solid content. Further, Cylest P (DTPA · 5Na) was added so that the chelating agent content was 3 parts by mass in 100 parts by mass of the solid content of the film-forming composition. Using this film forming composition, a resin-coated metal plate (steel plate) was obtained in the same manner as in Example 8. The obtained resin-coated metal plate (steel plate) was evaluated for corrosion resistance, lubricity, workability, and paintability. The results are shown in Table 6.

(Example 7)
Colloidal silica (ST-40), an epoxy-based crosslinking agent, and polyethylene wax particles having a softening point of 75 to 150 ° C. (average particle diameter of 1 μm) were added to the aqueous polyurethane resin dispersion 1 to prepare a film forming composition. The blending ratio of each component was blended so as to be 83 parts by weight of a carboxyl group-containing polyurethane resin, 10 parts by weight of colloidal silica, 2 parts by weight of an epoxy-based crosslinking agent, and 5 parts by weight of polyethylene wax particles in terms of solid content. Further, Cylest P (DTPA · 5Na) was added so that the chelating agent content was 3 parts by mass in 100 parts by mass of the solid content of the film-forming composition. Using this film-forming composition, a resin-coated metal plate (steel plate) was obtained in the same manner as in Example 1. The lubricity and workability of the obtained resin-coated metal plate (steel plate) were evaluated. The results are shown in Table 7.

(Example 8)
Colloidal silica (ST-40), an epoxy-based crosslinking agent, and polyethylene wax particles (W-700, an average particle diameter of 1 μm, a softening point of 132 ° C.) were added to the polyurethane resin aqueous dispersion 1 to prepare a film forming composition. . The blending ratio of each component is 63 to 88 parts by mass of a carboxyl group-containing polyurethane resin, 5 to 30 parts by mass of colloidal silica, 2 parts by mass of an epoxy-based crosslinking agent, and 5 parts by mass of polyethylene wax particles in terms of solid content. It mix | blended (however, it shall be 100 mass parts in total). Further, Cylest P (DTPA · 5Na) was added so that the chelating agent content was 3 parts by mass in 100 parts by mass of the solid content of the film-forming composition. This film-forming composition was applied with a squeeze roll onto a galvanized layer of an electrogalvanized steel sheet (Zn adhesion amount 20 g / m ² , plate thickness 0.8 mm) provided with a surface modification layer as described below. Then, it was heated and dried at a plate temperature of 90 ° C. to obtain a resin-coated metal plate (steel plate) on which a resin film having an adhesion amount of 1.0 g / m ² was formed. The lubricity and workability of the obtained resin-coated metal plate (steel plate) were evaluated. The results are shown in Table 8.

As an undercoat surface treatment agent, an acidic aqueous liquid (solid content) in which aluminum biphosphate (manufactured by Nippon Chemical Industry Co., Ltd.), colloidal silica (manufactured by Nissan Chemical Industries, Ltd .: ST-O), and polyacrylic acid (reagent, molecular weight 25000) are mixed. 50% by weight) was used. The surface treatment agent for the base is sprayed onto an alkaline degreased electrogalvanized steel sheet by spraying, the excess solution is removed with a ringer roll, washed with water at a spray pressure of 100 kPa for 5 seconds, and dried at 40 ° C. A surface modification layer was provided on the galvanized layer of the plated steel sheet. As a result of measuring the contents of Si, P and Al in the surface modified layer with a fluorescent X-ray apparatus (Shimadzu Corporation: MIF2100), SiO ₂ was 5 mg / m ² in terms of Si, and P: 2.6 mg / m. ² and Al: 1.8 mg / m ² .

Example 9
As an undercoat surface treatment agent, an acidic solution obtained by mixing aluminum biphosphate (manufactured by Nippon Chemical Industry Co., Ltd., solid content 50 mass%) and colloidal silica (manufactured by Nissan Chemical Co., Ltd .: ST-O) into a composition as shown in Table 9 An aqueous liquid was used. The surface treatment agent for the base is sprayed onto an alkaline degreased electrogalvanized steel sheet by spraying, the excess solution is removed with a ringer roll, washed with water at a spray pressure of 100 kPa for 5 seconds, and dried at 40 ° C. A surface modification layer was provided on the galvanized layer of the plated steel sheet. In addition, a test steel plate was also prepared in which washing with water was omitted. The Si, P, and Al concentrations in the base surface treatment agent were measured with an ICP emission analyzer (manufactured by Seiko Advance). Further, the contents of Si, P, and Al in the surface modified layer were measured with a fluorescent X-ray apparatus (Shimadzu Corporation: MIF2100).

Colloidal silica (ST-40), an epoxy-based crosslinking agent, and polyethylene wax particles having a softening point of 132 ° C. (average particle diameter of 1 μm) were added to the aqueous polyurethane resin dispersion 1 to prepare a film forming composition. The blending ratio of each component was blended so as to be 83 parts by weight of a carboxyl group-containing polyurethane resin, 10 parts by weight of colloidal silica, 2 parts by weight of an epoxy-based crosslinking agent, and 5 parts by weight of polyethylene wax particles in terms of solid content. Further, Cylest P (DTPA · 5Na) was added so that the chelating agent content was 3 parts by mass in 100 parts by mass of the solid content of the film-forming composition. This film-forming composition was applied to the surface modified layer of the electrogalvanized steel sheet (Zn deposition amount 20 g / m ² , sheet thickness 0.8 mm) provided with the surface modified layer as described above by a drawing roll. It was applied and dried at a plate temperature of 90 ° C. to obtain a resin-coated metal plate (steel plate) on which a resin film having an adhesion amount of 1.0 g / m ² was formed. The obtained resin-coated metal plate (steel plate) was evaluated for tape peel resistance and tape peel resistance after alkali degreasing. The results are shown in Table 10.

(Example 10)
Compositions as shown in Table 10 are polyacrylic acid, aluminum biphosphate (manufactured by Nippon Kagaku Kogyo Co., Ltd., solid content: 50% by mass) and colloidal silica (manufactured by Nissan Chemical Co., Ltd .: ST-O). An acidic aqueous solution mixed with was used. The surface treatment agent for the base is sprayed onto an alkaline degreased electrogalvanized steel sheet by spraying, the excess solution is removed with a ringer roll, washed with water at a spray pressure of 100 kPa for 5 seconds, and dried at 40 ° C. A surface modification layer was provided on the galvanized layer of the plated steel sheet. The Si, P, and Al concentrations in the base surface treatment agent were measured with an ICP emission analyzer (manufactured by Seiko Advance). Further, the contents of Si, P, and Al in the surface modified layer were measured with a fluorescent X-ray apparatus (Shimadzu Corporation: MIF2100).

  In the same manner as in Example 9, a resin-coated metal plate (steel plate) in which a resin film was formed on the surface modified layer of the electrogalvanized steel plate provided with the surface modified layer as described above was obtained. The obtained resin-coated galvanized steel sheet was evaluated for tape peel resistance and tape peel resistance after alkali degreasing. The results are shown in Table 12.

[FT-IR measurement of organic resin in surface modified layer]
FT-IR measurement was performed on the organic resin in the surface modified layer of the formed surface-treated steel sheet. Infrared absorption spectra (absorbance display) of S9 shown in Table 9 (without addition of polyacrylic acid) and S23 shown in Table 11 (with addition of polyacrylic acid) are shown in FIGS. 1 and 2, respectively. Moreover, the standard spectrum (transmittance display) of sodium polyacrylate was shown in FIG. Polyacrylic acid in the spectrum of Figure 2 was added 0.50 g / L during the treatment agent, 1346Cm in the spectrum of Figure 1 without the addition of the polyacrylic acid was observed ^{-1, 1421cm -1, 1457cm - 1} , 1592 cm ⁻¹ absorption is observed. These coincide with the absorption of sodium polyacrylate shown in FIG. 3, and the added polyacrylic acid is considered to be in the form of polyacrylate.

The FT-IR spectrum of the surface treating agent which does not contain polyacrylic acid. The FT-IR spectrum of the surface treating agent containing polyacrylic acid. FT-IR spectrum of sodium polyacrylate.

Claims (21)

A resin-coated metal plate provided with a resin film obtained from a film-forming composition containing a carboxyl group-containing polyurethane resin, the film-forming composition comprising ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) , Hydroxyethylidene diphosphonic acid (HEDP), N, N, N ′, N′-tetrakis (phosphonomethyl) ethylenediamine (EDTMP), nitrilotriacetic acid (NTA) and hydroxyethylethylenediaminetetraacetic acid (HEDTA), and salts thereof 0.5 to 10 parts by mass of one or more chelating agents selected from the group consisting of 0.5 to 10 parts by mass in the solid content of 100 parts by mass of the film-forming composition ,
The carboxyl group-containing polyurethane resin is obtained by chain extension reaction of a urethane prepolymer with a chain extender, and 1,4-cyclohexanedimethanol, polyether polyol is used as a polyol component constituting the urethane prepolymer. And a resin-coated metal sheet characterized by essentially using all the polyols having a carboxyl group .   The film-forming composition contains one or more chelating agents selected from the group consisting of an EDTA salt, a DTPA salt, a HEDP salt, an EDTMP salt, an NTA salt and a HETDA salt containing Na ions. Item 2. A resin-coated metal plate according to Item 1.   The film-forming composition contains EDTA salt, DTPA salt, HEDP salt, EDTMP salt, NTA containing Na ions and containing at least one metal ion selected from Mg, Ca, Co, Zn, Mn and Fe ions. The resin-coated metal sheet according to claim 1, which contains one or more chelating agents selected from the group consisting of a salt and a HEDTA salt.   The film-forming composition contains one or more chelating agents selected from the group consisting of EDTA salts, DTPA salts, HEDP salts, EDTMP salts, NTA salts and HETDAs containing amine ions or ammonium ions. The resin-coated metal plate according to claim 1, which is a metal plate.   The film-forming composition includes an EDTA salt, a DTPA salt, a HEDP containing an amine ion or an ammonium ion and containing at least one metal ion selected from Na, Mg, Ca, Co, Zn, Mn, and Fe ions. The resin-coated metal sheet according to claim 1, which contains one or more chelating agents selected from the group consisting of a salt, an EDTMP salt, an NTA salt, and a HEDTA salt. The film-forming composition is
The carboxyl group-containing polyurethane resin: 30 to 93.5 parts by mass;
Silica particles: 5 to 40 parts by mass;
Polyethylene wax particles: 0.5-15 parts by mass; and epoxy-based crosslinking agent: 1-15 parts by mass ,
As the polyisocyanate component of the urethane prepolymer, tolylene diisocyanate, to any one of claims 1 to 5 is obtained by using at least one in essentially selected from the group consisting of diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate The resin-coated metal plate described.   The resin-coated metal sheet according to any one of claims 1 to 6, wherein the chain extender is ethylenediamine or hydrazine.   The resin according to any one of claims 1 to 7, wherein a mass ratio of the 1,4-cyclohexanedimethanol and the polyether polyol is 1,4-cyclohexanedimethanol: polyether polyol = 1: 1 to 1:19. Painted metal plate.   The resin-coated metal plate according to claim 1, wherein the polyether polyol is polyoxypropylene glycol or polytetramethylene ether glycol.   The resin-coated metal sheet according to any one of claims 1 to 9, wherein the carboxyl group-containing polyurethane resin has an acid value of 10 to 60 mgKOH / g.   The resin-coated metal plate according to claim 1, wherein the polyethylene wax particles have a spherical shape and an average particle diameter of 0.1 to 3 μm.   The resin-coated metal sheet according to any one of claims 1 to 11, wherein the polyethylene wax particles have a softening point of 100 to 140 ° C.   The resin-coated metal according to any one of claims 1 to 12, wherein a film-forming temperature of the resin film is lower than a softening point of the polyethylene wax particles, and the shape of the polyethylene wax particles is held in a spherical shape in the resin film. Board.   The film-forming composition further contains a second carboxyl group-containing resin having an acid value of 5 mgKOH / g or more, which is not more than half the mass of the carboxyl group-containing polyurethane resin, and the second resin and the carboxyl The resin-coated metal plate according to any one of claims 1 to 13, wherein a resin film is formed by crosslinking a group-containing polyurethane resin with a second crosslinking agent.   The resin-coated metal sheet according to claim 14, wherein the second crosslinking agent is an epoxy-based crosslinking agent, a divalent metal-based crosslinking agent, or an aziridine-based crosslinking agent. The metal plate is a zinc-based plated steel plate, a surface-modified layer is formed on a zinc-based plated layer, and the resin coating is formed on the surface-modified layer, the resin-coated metal plate having the surface The modified layer contains 1-30 mg / m ² SiO ₂ in terms of Si, P: 0.5-15 mg / m ² , Al: 0.5-10 mg / m ^2. The resin-coated metal plate according to any one of the above. The resin-coated metal sheet according to claim 16, wherein the contents of Si, P, and Al contained in the surface modification layer satisfy the following relational expressions (1) and (2).
0.5 ≦ Si / P ≦ 20 ··· Formula (1)
0.7 ≦ P / Al ≦ 4.5 ・ ・ ・ ・ ・ ・ Formula (2)   The resin-coated metal plate according to claim 16 or 17, wherein the surface-modified layer further contains an organic resin.   The resin-coated metal sheet according to claim 18, wherein the absorption intensity (peak area) of FT-IR derived from the structure of the organic resin contained in the surface modified layer is 0.1 to 15. A silica-containing phosphoric acid-based surface treatment agent for forming a surface-modified layer of a resin-coated metal sheet according to any one of claims 16 to 19, wherein the treatment agent has a solid content concentration of 0.01 to 15 % (Meaning mass%, the same applies hereinafter), and the content and composition ratio (mass ratio) of Si, P, and Al contained in the treatment agent satisfy the following requirements: Surface treatment agent.
Si: 0.002 to 4.5%
P: 0.0005 to 1.5%
Al: 0.0001 to 0.5%
4.5 ≦ Si / Al ≦ 230, 1.5 ≦ Si / P ≦ 60. The surface treatment agent according to claim 20, wherein the surface treatment agent further contains an organic resin, and the addition concentration of the organic resin is 0.01 to 3 g / L.

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