CN107109111B - Coating material for hot-dip galvanized steel sheet, method for treating steel sheet, method for producing surface-treated steel sheet, and surface-treated steel sheet - Google Patents

Coating material for hot-dip galvanized steel sheet, method for treating steel sheet, method for producing surface-treated steel sheet, and surface-treated steel sheet Download PDF

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CN107109111B
CN107109111B CN201480084464.3A CN201480084464A CN107109111B CN 107109111 B CN107109111 B CN 107109111B CN 201480084464 A CN201480084464 A CN 201480084464A CN 107109111 B CN107109111 B CN 107109111B
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hot
steel sheet
galvanized steel
dip galvanized
mass
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CN107109111A (en
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田中雅能
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating With Molten Metal (AREA)

Abstract

The invention provides a coating for hot-dip galvanized steel sheets, which is used for endowing the hot-dip galvanized steel sheets with excellent appearance characteristics, excellent friction resistance and excellent corrosion resistance. The coating material for hot dip galvanized steel sheet of the present invention contains a cationic polyurethane resin (A) having at least one cationic functional group selected from a primary to tertiary amino group and a quaternary ammonium salt group, the cationic polyurethane resin (A) having a polycarbonate structural unit and a bisphenol structural unit, a temperature (Tg1) at which a maximum peak of a loss modulus E ' of the cationic polyurethane resin (A) is exhibited is in a range of-60 ℃ to-5 ℃, and a loss tangent tan, which is a ratio of the loss modulus E ' to a storage modulus E ' of the cationic polyurethane resin (A)δConsisting of one peak.

Description

Coating material for hot-dip galvanized steel sheet, method for treating steel sheet, method for producing surface-treated steel sheet, and surface-treated steel sheet
Technical Field
The present invention relates to a coating material for hot-dip galvanized steel sheet, a method for treating hot-dip galvanized steel sheet, a method for producing surface-treated hot-dip galvanized steel sheet, and surface-treated hot-dip galvanized steel sheet.
Background
Conventionally, zinc-based plated steel sheets including a hot-dip zinc-plated steel sheet, a hot-dip zinc-5% aluminum alloy-plated steel sheet, a hot-dip zinc alloy-plated steel sheet, and the like have been widely used in household electric products, building materials, and the like. Examples of the method for producing a zinc-based plated steel sheet include: a method of immersing a steel sheet as an object to be processed in a hot-dip galvanizing bath and applying plating (so-called "hot-dip galvanizing") to the entire surface thereof by an immersion method, and the resulting steel sheet is also called a hot-dip galvanized steel sheet. In the immersion method by hot dip plating (hereinafter, also referred to as hot dip plating method), the control of the zinc adhesion by an air knife or the like performed in CGL (Continuous hot dip Galvanizing Line) is not performed.
For zinc-based plated steel sheets, steel sheets subjected to chromate treatment with a treatment solution containing chromic acid, dichromic acid, or salts thereof as a main component are widely used for the purpose of improving corrosion resistance.
However, since chromate treatment films generally contain 6-valent chromium, which is highly environmentally responsible, there has been an increasing demand for 6-valent chromium-free treatment films, and various techniques have been proposed in recent years.
For example, patent document 1 discloses a method for preventing corrosion of a surface of a zinc-plated steel material by bringing an aqueous solution containing a vanadate and a water-soluble acrylic resin into contact with the surface.
Documents of the prior art
Patent document
Patent document 1: japanese patent application laid-open No. 2002-146554.
Disclosure of Invention
Problems to be solved by the invention
On the other hand, in recent years, zinc-based plated steel sheets have been expanded to various uses, and not only further improvement in corrosion resistance but also improvement in other properties have been desired. Examples thereof include: improvement in appearance characteristics of zinc-based plated steel sheet; or the resistance of the coating film (the coating film disposed on the zinc-based plated steel sheet) to peeling off of a marking ink (magic ink) marked as a mark during wiping assembly work with a cloth or the like soaked in alcohol, i.e., the resistance of the coating film (hereinafter referred to as "rubbing resistance") is improved. In particular, improvement of the above properties (corrosion resistance, appearance properties, and friction resistance) is strongly required for hot-dip galvanized steel sheets.
The present inventors have evaluated the above-described various properties of a steel sheet obtained by applying the method described in patent document 1 to a hot-dip galvanized steel sheet, and as a result, have found that: the appearance characteristics, the abrasion resistance and the corrosion resistance cannot be simultaneously satisfied at the recent level of the requirements, and further improvement is required.
In view of the above circumstances, an object of the present invention is to provide a coating material for hot-dip galvanized steel sheets (or hot-dip galvanized steel sheets or zinc-plated steel sheets) for imparting excellent appearance characteristics, excellent friction resistance, and excellent corrosion resistance to hot-dip galvanized steel sheets (or hot-dip galvanized steel sheets or zinc-plated steel sheets).
Means for solving the problems
The present inventors have conducted intensive studies on the above problems, and as a result, have found that: by using a coating material containing a cationic urethane resin exhibiting predetermined characteristics, a desired effect can be obtained.
More specifically, it was found that: the above object can be achieved by the following constitution.
(1) A coating material for hot dip galvanized steel sheet, which comprises a cationic polyurethane resin (A) having at least one cationic functional group selected from primary to tertiary amino groups and quaternary ammonium salt groups, wherein the cationic polyurethane resin (A) has a polycarbonate structural unit and a bisphenol structural unit, the temperature (Tg1) at which the maximum peak of the loss modulus E ' of the cationic polyurethane resin (A) is exhibited is in the range of-60 ℃ to-5 ℃, and the loss tangent tan, which is the ratio of the loss modulus E ' to the storage modulus E ' of the cationic polyurethane resin (A)δConsisting of one peak.
(2) The coating material for hot-dip galvanized steel sheet according to (1), wherein the loss tangent tanδHas a peak temperature (Tg2) in the range of-50 ℃ to-2 ℃.
(3) The coating material for hot-dip galvanized steel sheet according to (1) or (2), further comprising a phosphoric acid compound (B).
(4) The coating material for hot-dip galvanized steel sheet according to (3), wherein the phosphoric acid compound (B) contains at least one selected from orthophosphoric acid, condensed phosphoric acid and salts thereof.
(5) The coating material for hot-dip galvanized steel sheet according to any one of (1) to (4), wherein the Amine Value (AV) of the cationic polyurethane resin (A) is 2.0 to 5.0 mgKOH/g.
(6) The coating material for hot-dip galvanized steel sheet, wherein the ratio ((BV)/(AV)) of the content ratio (BV) of the phosphoric acid compound (B) to the solid content (mass%) of the cationic polyurethane resin to the amine value is 0.1 to 9.5.
(7) The coating material for hot-dip galvanized steel sheet according to any one of (1) to (6), further comprising a trivalent chromium compound (C).
(8) A method for treating a hot-dip galvanized steel sheet, which comprises treating the hot-dip galvanized steel sheet with the coating material for a hot-dip galvanized steel sheet described in any one of (1) to (7).
(9) A method for producing a surface-treated hot-dip galvanized steel sheet, which comprises bringing the coating material for a hot-dip galvanized steel sheet described in any one of (1) to (7) into contact with the hot-dip galvanized steel sheet to produce a surface-treated hot-dip galvanized steel sheet having the hot-dip hot-galvanized steel sheet and a film disposed on the surface of the hot-dip hot.
(10) A surface-treated molten zinc-plated steel sheet obtained by the production method according to (9).
Effects of the invention
According to the present invention, there can be provided a coating material for hot-dip galvanized steel sheets (or hot-dip galvanized steel sheets or zinc-plated steel sheets) for imparting excellent appearance characteristics, excellent friction resistance, and excellent corrosion resistance to hot-dip hot-galvanized steel sheets (or hot-dip galvanized steel sheets or zinc-plated steel sheets).
Also, there may be provided: a method for treating a hot-dip galvanized steel sheet (or a hot-dip galvanized steel sheet or a zinc-based plated steel sheet) by treating a hot-dip galvanized steel sheet (or a hot-dip zinc-based plated steel sheet or a zinc-based plated steel sheet) with the use of the coating material; and a method for producing a surface-treated hot-dip galvanized steel sheet (or a hot-dip galvanized steel sheet or a zinc-plated steel sheet) having a hot-dip galvanized steel sheet (or a hot-dip galvanized steel sheet or a zinc-plated steel sheet) and a film disposed on the surface thereof by bringing the coating material into contact with the hot-dip galvanized steel sheet (or a hot-dip galvanized steel sheet or a zinc-plated steel sheet); and a steel sheet thereof.
The coating material for hot-dip galvanized steel sheet according to the present invention is a technique that does not contain 6-valent chromium, but the performance is greatly improved by containing trivalent chromium. Further, the system containing no trivalent chromium exhibits a desired effect.
Detailed Description
Hereinafter, the coating material for hot-dip galvanized steel sheet (hereinafter, also simply referred to as "coating material") of the present invention will be described in detail. The reason why the desired effect is obtained by using the coating material of the present invention is presumed as follows.
First, the reasons for improving the appearance characteristics include: the temperature (Tg1) at which the maximum peak of the loss modulus E '' of the cationic polyurethane resin is exhibited is in the range of-60 ℃ to-5 ℃. The present inventors have found that the temperature (Tg1) is correlated with the appearance characteristics and the abrasion resistance of the coating film. That is, the loss modulus E ″ is an index indicating the viscosity of the object, and when the temperature at which the maximum peak of the loss modulus E ″ is exhibited is too low, the resin exhibits good fluidity, and the flatness of the film is improved, thereby obtaining excellent appearance characteristics, but the hardness of the formed film is poor, causing a decrease in the friction resistance. On the other hand, when the temperature is too high, the hardness of the formed film is excellent and the abrasion resistance is excellent, but the fluidity of the resin is lowered and the appearance characteristics are poor. The invention discovers that: when the temperature (Tg1) of the cationic urethane resin is within the above range, both the appearance characteristics and the abrasion resistance can be satisfied. The rubbing resistance means resistance of the coating film to an operation of applying a marking ink (magic ink) as a mark during a wiping assembly operation with a cloth or the like impregnated with alcohol.
The reason why the corrosion resistance is improved is as follows: loss tangent tan of cationic polyurethane resinδAn aspect consisting of one peak. In general, a polyurethane resin easily forms a sea-island structure having two or more regions of a soft segment and a hard segment in a film form due to its resin skeleton. Therefore, when the dynamic viscoelasticity measurement is performed, the loss tangent tan is obtainedδMore than two peaks are observed. On the other hand, it is presumed that the cationic urethane resin used in the present invention has a loss tangent tanδThe sea-island structure is not easily formed in the film due to the single peak, and a uniform film is formed, resulting in an improvement in corrosion resistance.
Further, in order to ensure good surface coating adhesion and impact resistance, it is preferable that the cationic polyurethane resin has a loss tangent tanδHas a peak temperature (Tg2) in the range of-50 ℃ to-2 ℃. Depending on the environment in which the product coated with the coating material of the present invention is used, the processing may be performed in a cold region. If used in surface treatment, the surface treatment may contain loss tangent tanδThe coating material containing the component having a high peak temperature of (3) is hard, and therefore, particularly when the coating material is processed at a low temperature in winter, the coating adhesion of the surface coating layer is insufficient, and the coating film is likely to peel off. Further, the surface treatment may be carried out by using a composition containing tanδThe coating material of (3) is a component having a low peak temperature, and therefore, the impact resistance is insufficient and the coating film is likely to be peeled off particularly when the coating material is processed at a high temperature in summer. On the other hand, it is presumed that the loss tangent tanδWhen the peak temperature (Tg2) of (B) is in the range of-50 ℃ to-2 ℃, the coating film has sufficient flexibility and hardness at both low temperatures and high temperatures, and exhibits sufficient surface coating adhesion and impact resistance.
Further, in order to ensure good storage stability, it is preferable that the amine value of the cationic polyurethane resin is in the range of 2.0 to 5.0 mgKOH/g. The cationic functional group in the cationic polyurethane resin contributes to making the cationic polyurethane resin water-soluble or water-dispersible. Therefore, if the cationic functional group is small, in other words, if the amine value is low, the stability of the cationic polyurethane resin is insufficient, and the resin may be redispersed in a coating material, but precipitation of the resin is likely to occur. Therefore, in order to improve the stability of the cationic urethane resin, it is desirable to increase the amount of cationic functional groups, that is, to increase the amine value, but if the hydrophilic group in the resin is excessively increased, that is, if the amine value is excessively increased, the cationic urethane resin is conversely water-dissolved, and therefore the viscosity is increased, the coating material is thickened, and the redispersibility of the coating material is affected in some cases. Further, thickening may also affect coating workability. Therefore, it is presumed that good storage stability を can be obtained by controlling the amine value of the cationic polyurethane resin to be in the range of 2.0 to 5.0 mgKOH/g.
In addition, as another effect of the coating material of the present invention, phosphate treatability is excellent. The reason why the phosphate treatability is excellent is that a cationic urethane resin having a predetermined functional group is used. It is presumed that the cationic functional group in the cationic urethane resin in the coating film formed on the hot-dip galvanized steel sheet interacts with phosphoric acid present in the phosphoric acid compound, and becomes a starting point of a phosphate generation reaction such as zinc phosphate in the phosphate treatment, and the phosphatability is improved. The ratio (BV)/(AV) of the content ratio (BV) of the phosphoric acid compound to the solid content (mass%) of the cationic urethane resin and the amine value is not particularly limited, and is 0.05 to 20, preferably 0.1 to 9.5, more preferably 0.5 to 9.0, and still more preferably 0.5 to 6.0. It is presumed that by setting (BV)/(AV) within the above range (0.1 to 9.5), the starting point of the phosphate formation reaction is more favorably generated on the coating film, and more excellent phosphate treatability can be obtained. In this case, it is assumed that when the amount of the phosphate compound is relatively large, that is, (BV)/(AV) is large, a relatively large amount of the phosphate compound is eluted from the phosphate treatment liquid, and therefore, in many cases, the formation of the phosphate film is easily delayed, and conversely, when the amount of the phosphate compound is relatively small, that is, (BV)/(AV) is small, the interaction between the phosphate compound and the cationic functional group of the cationic urethane resin is relatively reduced, and therefore, the swelling or dissolution of the cationic urethane resin by the phosphate treatment liquid is reduced, and the formation of the phosphate film is easily delayed.
The phosphate treatment is a treatment using a phosphate treatment solution containing zinc phosphate, manganese phosphate, magnesium phosphate, or the like as a main component, which is suitable for a primer coating or the like. The coating type phosphate treatment is one mode of phosphate treatment. The coating type phosphate treatment is a treatment in which a coating type phosphate treatment liquid is applied to the surface of an object to be treated (for example, a zinc plated steel sheet such as a hot-dip galvanized steel sheet) to form fine and dense crystals of zinc phosphate, thereby improving the sliding resistance of a frictional joint surface with a strong bolt.
The coating material of the present invention can be suitably applied to hot-dip galvanized steel sheets, and also to zinc-based plated steel sheets including hot-dip galvanized steel sheets produced by CGL (continuous hot-dip galvanized steel sheet production line) or the like, hot-dip zinc-5% aluminum alloy plated steel sheets, hot-dip zinc-55% aluminum alloy plated steel sheets, alloyed hot-dip zinc plated steel sheets, electrogalvanized steel sheets produced by EGL (electrogalvanizing line) or the like, and can improve the above-described various properties (appearance, friction resistance, corrosion resistance, surface coating adhesion, impact resistance, phosphatability, and the like). In other words, the coating material of the present invention can be suitably applied to a zinc-based plated steel sheet, and can also be used as a coating material for a zinc-based plated steel sheet. In particular, the coating composition can be suitably applied to hot-dip galvanized steel sheets, hot-dip galvanized steel sheets produced by CGL (continuous hot-dip galvanized steel sheet production line) or the like, hot-dip zinc-5% aluminum alloy plated steel sheets, hot-dip zinc-55% aluminum alloy plated steel sheets, alloyed hot-dip galvanized steel sheets, and other hot-dip galvanized steel sheets obtained by plating with hot zinc, and can also be used as a coating material for hot-dip galvanized steel sheets.
The coating material of the present invention contains at least a cationic urethane resin (a).
Hereinafter, each component contained in the coating material will be described in detail, and thereafter, a method of treating a hot-dip galvanized steel sheet using the coating material (in other words, a method of producing a surface-treated hot-dip galvanized steel sheet having a hot-dip galvanized steel sheet and a coating film disposed on the surface thereof, and a method of producing a surface-treated hot-dip galvanized steel sheet) will be described in detail.
< cationic polyurethane resin (A) >
The coating material of the present invention contains a cationic polyurethane resin (a) having at least one cationic functional group selected from primary to tertiary amino groups and quaternary ammonium salt groups.
Anionic resins used in the prior art generally tend to have poor alkali resistance and excellent acid resistance. If the alkali resistance is poor, the coating film is easily dissolved and peeled off in an alkali degreasing step or the like after the formation of the coating film, and thus the corrosion resistance is reduced. In addition, since the acid resistance is excellent, it is difficult to perform the phosphate treatment in many cases. On the other hand, the cationic urethane resin (a) is excellent in alkali resistance, and therefore also excellent in corrosion resistance after the alkali degreasing step. Further, the polyurethane resin is tough with a film due to hydrogen bonds derived from urethane bonds in the molecule, and corrosion resistance is improved. In addition, in some cases, the resin has a cationic functional group, and therefore, the resin is easily phosphate-treated because of its low acid resistance.
(cationic functional group)
Examples of the cationic functional group contained in the cationic urethane resin (a) include: amino, methylamino, ethylamino, dimethylamino, diethylamino, trimethylamino, triethylamino, and the like, but there is no particular limitation as long as the amino group is a primary to tertiary amino group or a quaternary ammonium salt group.
The cationic functional group in the cationic polyurethane resin (a) contributes to making the cationic polyurethane resin (a) water-soluble or water-dispersible. The cationic urethane resin (a) can be dissolved or dispersed in water based on the self-solubility or self-dispersibility of the cationic urethane resin (a) in water, and can be dissolved or dispersed by a cationic surfactant (e.g., an alkyl quaternary ammonium salt) and/or a nonionic surfactant (e.g., an alkyl phenyl ether).
(temperature showing the maximum peak of loss modulus E' (Tg1))
The temperature (Tg1) at which the maximum peak of the loss modulus E ″ of the cationic polyurethane resin (A) is exhibited is in the range of-60 ℃ to-5 ℃, and is preferably-55 ℃ to-10 ℃, more preferably-50 ℃ to-15 ℃ in terms of more excellent at least one of appearance, abrasion resistance, corrosion resistance, phosphatability, surface coating adhesion, impact resistance and storage stability (hereinafter, also referred to simply as "more excellent aspect of the present invention").
When the temperature (Tg1) is less than-60 ℃, the abrasion resistance is poor, and when the temperature exceeds-5 ℃, the appearance of the coating film is poor.
The maximum peak is a maximum peak among peaks observed in a loss modulus curve (a temperature dependence curve of loss modulus in a graph in which the abscissa represents temperature and the ordinate represents loss modulus) obtained by the dynamic viscoelasticity measurement described later. The peak may also be called maximum.
(loss tangent tan)δ)
The ratio of the loss modulus E 'to the storage modulus E' (loss modulus E '/storage modulus E') of the cationic urethane resin (A) is the loss tangent tanδConsisting of one peak (with only one peak). Namely, loss tangent tan obtained by the dynamic viscoelasticity measurement described laterδCurve (temperature on the horizontal axis and loss tangent tan on the vertical axis)δLoss tangent tan in the graph of (1)δTemperature dependence curve) of (a), is composed of one peak (has only one peak). In other words, it means that two or more peaks are not present. When two or more peaks are observed as described above, the formed coating film is microscopically uneven and poor in corrosion resistance.
(loss tangent tan)δPeak temperature (Tg2)
Tan of loss tangentδThe peak temperature (Tg2) of (C) is not particularly limited, but is preferably from-50 ℃ to-2 ℃, more preferably from-48 ℃ to-5 ℃, and still more preferably from-45 ℃ to-10 ℃ in terms of further excellent effects of the present invention (particularly, surface coating adhesion and impact resistance).
As a method for measuring dynamic viscoelasticity, a dynamic viscoelasticity measuring apparatus "RSAG 2" manufactured by TA instruments was used, and a Transverse Direction (TD) of a film (sample area: nip length. times. width: 20 mm. times.5 mm) of the cationic urethane resin (A) was measured at a vibration frequency of 10Hz and a strain of 0.1% at a temperature rise rate of 5 ℃/min from-100 ℃ to 200 ℃ to calculate a storage modulus E', a loss modulus E ″ and a loss tangent tanδ。
The above-mentioned properties (loss modulus E '', loss) of the cationic polyurethane resin (A) contained in the coating material of the present inventionTan of loss tangentδ) Can be adjusted appropriately by controlling the structure or synthesis method thereof.
For example, the temperature (Tg1) can be controlled by the amount and molecular weight of the polyol which becomes the soft segment constituting the cationic urethane resin (a), or the temperature at the time of polymerization. When the amount of the polyol is large, the temperature (Tg1) tends to be low, and when the amount is small, the temperature (Tg1) tends to be high.
In addition, in order not to observe more than two loss tangents tanδThe peak of (2) is, for example, a method of controlling the molecular weight of the polyol which is a soft segment constituting the cationic urethane resin (A) or the temperature at the time of polymerization.
(Structure of urethane resin)
The cationic urethane resin (a) has a polycarbonate structural unit and a bisphenol structural unit. In other words, the cationic urethane resin (a) has a repeating unit of a polycarbonate structure and a repeating unit of a bisphenol structure as repeating units constituting the resin.
The carbonate structural unit has excellent flexibility and adhesion, but tends to have poor hydrolysis resistance when the film is wetted with water or the like. Bisphenol structural units, although excellent in hydrolysis resistance, tend to be hard and poor in flexibility and are easily damaged by friction or the like.
That is, if the polycarbonate structural unit and the bisphenol structural unit are not contained, the corrosion resistance and the abrasion resistance are inferior to those of the case where the polycarbonate structural unit and the bisphenol structural unit are contained.
In the present invention, by combining both, and controlling the temperature (Tg1) at which the maximum peak of the loss modulus E '' is exhibited to be in the range of-60 ℃ to-5 ℃, excellent corrosion resistance, abrasion resistance and appearance characteristics can be obtained at the same time.
The polycarbonate structural unit is a repeating unit having a plurality of carbonate bonds (-O-C (= O) -O-) in its structure. Generally, a polyurethane resin is produced by reacting a polyol with a polyisocyanate. Therefore, examples of the method for introducing a carbonate structural unit into the cationic urethane resin (a) include: a method for producing a cationic polyurethane resin (A) using a polycarbonate polyol.
As the polycarbonate polyol, there can be exemplified: and polycarbonate polyols having a hydroxyl group at the terminal obtained by reacting a polyhydric alcohol such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 1, 9-nonanediol, 1, 8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, bisphenol a, or hydrogenated bisphenol a with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, or the like.
Examples of the bisphenol structural unit include: structural units derived from bisphenol A, bisphenol F, or bisphenol S. Examples of the method for introducing a bisphenol structural unit into the cationic urethane resin (a) include: a method for producing a cationic polyurethane resin (A) by using a polyol having a bisphenol structure.
Examples of the polyol having a bisphenol structure include: polyhydric alcohols obtained by adding alkylene oxides (alkylene oxides) to bisphenol a, bisphenol F, bisphenol E, and bisphenol a; a polyol obtained by adding an alkylene oxide to bisphenol F; a polyol obtained by adding an alkylene oxide to bisphenol E; polyols obtained by adding alkylene oxides to hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol A; polyhydric alcohols obtained by adding alkylene oxides to hydrogenated bisphenol F; a polyol obtained by adding an alkylene oxide to hydrogenated bisphenol E.
The cationic urethane resin (a) may have a structural unit other than the above-described polycarbonate structural unit and bisphenol structural unit.
For example, in the production of the cationic polyurethane resin (a), polyols other than polycarbonate polyols such as polyether polyol and polyester polyol may be used in combination.
In addition, when the cationic polyurethane resin (a) is produced, a desired cationic functional group can be introduced into the polyurethane resin by using an alcohol compound having a cationic functional group such as a (substituted) amino group (preferably a polyol compound having a cationic functional group such as a (substituted) amino group) (for example, N-methyldiethanolamine, N-dimethylaminodimethylolpropane, etc.) or an amine compound having a predetermined cationic functional group.
In addition, the cationic urethane resin (a) is obtained by reacting the above polyol with a polyisocyanate (for example, an aliphatic, alicyclic or aromatic polyisocyanate) as described above.
As the polyether polyol, there can be exemplified: polyethylene glycols such as diethylene glycol and triethylene glycol, polyethylene/propylene glycol, and the like.
As the polyester polyol, there can be exemplified: and polyester polyols having a hydroxyl group at the terminal, which are obtained by polycondensation of a polyhydric alcohol such as an alkylene (e.g., a1 to 6 carbon-atom) diol (e.g., ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, or hexylene glycol), a polyether polyol, bisphenol a, hydrogenated bisphenol a, trimethylolpropane, or glycerin, and a polybasic acid such as succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid.
As the aliphatic, alicyclic or aromatic polyisocyanate, there can be exemplified: toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and the like.
(amine number)
The amine value of the cationic polyurethane resin (A) is not particularly limited, but is preferably 2.0 to 5.0mgKOH/g, more preferably 2.3 to 4.5mgKOH/g, and further preferably 2.5 to 4.0mgKOH/g, from the viewpoint of further improving the storage stability of the coating material.
The amine value is a value measured by the following measurement method and is defined as a total amine value.
The cationic polyurethane resin (A) was collected in an amount of about 3g in terms of solid content and accurately weighed. Thereafter, dimethylformamide was added thereto to dissolve it. Next, several drops of bromocresol green indicator were added, titration was performed by 0.1mol/L hydrochloric acid titration solution, and the amount of the titration solution was read with the point of change from blue to yellow as an end point. The total amine value (mgKOH/g) was calculated according to the following equation.
Total amine value = [ (F1-F2) × F × 5.611/S ]
In the formula:
f1: the amount of 0.1mol/L hydrochloric acid solution (mL) required for titration in this test;
f2: the amount of 0.1mol/L hydrochloric acid solution for titration (mL) required for the blank test;
f: the titer of the solution for titration with 0.1mol/L hydrochloric acid;
s: sample collection amount (g).
The blank test described above is a test in which the measurement is performed using deionized water instead of the cationic urethane resin.
< other optional ingredients >
The coating material of the present invention may contain other components than the cationic urethane resin (a). Hereinafter, the optional components will be described in detail.
(phosphoric acid Compound (B))
The coating material of the present invention may contain a phosphoric acid compound (B). By containing the phosphoric acid compound (B), the corrosion resistance is further improved.
Examples of the phosphoric acid compound (B) include: at least one selected from the group consisting of inorganic phosphoric acid, inorganic phosphate, organic phosphoric acid and organic phosphate.
Examples of the inorganic phosphoric acid and salts thereof include: monophosphates such as phosphoric acid (orthophosphoric acid), phosphorous acid, triphosphoric acid, hypophosphorous acid, and derivatives and salts of monophosphoric acid, condensed phosphoric acids such as metaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, and hexaphosphoric acid, derivatives and salts of condensed phosphoric acids, and the like.
Examples of the organic phosphoric acid and its salt include: phosphoric monoesters (e.g., monododecyl dihydrogen phosphate, monotridecyl dihydrogen phosphate, etc.) and salts thereof, phosphoric diesters (e.g., ditridecyl hydrogen phosphate, etc.) and salts thereof, and the like. Specific examples of the organic phosphoric acid include: r10O-P(=O)(OR11)(OR12) The compounds represented. In addition, R is10Represents an organic radical, R11And R12Each independently represents a hydrogen atom or an organic group. Examples of the organic group include: hydrocarbyl radical(for example, an alkyl group, an aryl group, or a combination thereof).
The salts such as inorganic phosphate (salts of inorganic phosphoric acid) and organic phosphate (salts of organic phosphoric acid) are not particularly limited, and examples thereof include: alkali metal salts, ammonium salts, amine salts.
Among them, in terms of more excellent effects of the present invention, it is preferable that the phosphoric acid compound (B) contains at least one selected from orthophosphoric acid, condensed phosphoric acid and salts thereof.
(trivalent chromium Compound (C))
The coating material of the present invention may contain a trivalent chromium compound (C). By containing the trivalent chromium compound (C), the corrosion resistance is further improved.
The trivalent chromium compound (C) is a compound capable of supplying trivalent chromium ions, and examples thereof include: a trivalent chromium salt. Examples of the kind of salt include: inorganic acid salts such as nitrate, sulfate and hydrochloride, and organic acid salts such as acetate, oxalate and succinate.
Specific examples of the trivalent chromium compound (C) include: chromium (III) fluoride, chromium (III) chloride, chromium (III) nitrate, chromium (III) sulfate, chromium (III) acetate, and the like.
(solvent)
Solvents may be included in the coatings of the present invention. Examples of the solvent include: water or an organic solvent (e.g., an alcohol).
(other additives)
The coating material of the present invention may contain a thickener, a leveling agent, a wettability improver, an antifoaming agent, a surfactant, a water-soluble alcohol, a cellosolve-based solvent, and the like for the purpose of adjusting coatability.
In addition, preservatives, antibacterial agents, coloring agents, anti-marring agents, lubricants and the like may be contained.
Further, benzotriazole, guanidine compounds, hindered amines, and the like may be contained.
< coating for hot-dip galvanized steel sheet >
The coating material of the present invention contains the above-mentioned various components.
The content of the cationic polyurethane resin (a) in the coating material is not particularly limited, but is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, based on the total mass of the coating material, from the viewpoint of further improving the effect of the present invention and from the viewpoint of handling properties.
When the phosphoric acid compound (B) is contained in the coating material, the content of the phosphoric acid compound (B) is not particularly limited, and is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 25 parts by mass, and further preferably 1 to 10 parts by mass, based on 100 parts by mass of the cationic urethane resin (a), from the viewpoint of further excellent effects of the present invention.
When the coating material contains the trivalent chromium compound (C), the content of the trivalent chromium compound (C) is not particularly limited, and is preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the cationic urethane resin (a), in terms of the more excellent effects of the present invention.
The method for preparing the coating material is not particularly limited, and for example, the coating material can be prepared by adding the cationic urethane resin (a) and other optional components to a solvent such as water and mixing them.
< method for producing surface-treated hot-dip galvanized steel sheet >
The coating material of the present invention can be suitably applied to a hot-dip galvanized steel sheet, and a surface-treated hot-dip galvanized steel sheet having a hot-dip galvanized steel sheet and a coating film disposed on the surface thereof can be produced by bringing the coating material of the present invention into contact with the hot-dip galvanized steel sheet.
As described above, the coating material of the present invention can be suitably applied to a zinc-plated steel sheet (or a molten zinc-plated steel sheet) including a hot-dip galvanized steel sheet.
Hereinafter, a typical example of using a hot-dip galvanized steel sheet as a treatment object will be described, but a surface-treated zinc-based plated steel sheet having excellent properties can be produced by forming a predetermined coating film on a zinc-based plated steel sheet other than the hot-dip galvanized steel sheet under the conditions described later. When the above-described molten zinc-plated steel sheet is used, a surface-treated molten zinc-plated steel sheet having a molten zinc-plated steel sheet and a coating film disposed thereon can also be produced.
The method for producing a surface-treated hot-dip galvanized steel sheet using the above-described coating composition is not particularly limited, but generally includes the following steps: the surface-treated hot-dip galvanized steel sheet is obtained by bringing the above-described coating material into contact with a hot-dip galvanized steel sheet, and heating and drying the coating material as necessary to form a coating film on the hot-dip galvanized steel sheet.
Hereinafter, first, a hot-dip galvanized steel sheet as a treatment object will be described in detail, and thereafter, the sequence of steps will be described in detail.
(Hot-dip hot-dip galvanized steel plate)
A hot-dip galvanized steel sheet refers to a steel sheet obtained by a dipping method in which a steel sheet as an object to be treated is dipped in a molten zinc bath, and the object to be treated is directly and slowly pulled from the plating bath, thereby performing plating. As described above, in the hot dip plating method, the object to be treated is pulled from the plating tank and left as it is (cooled) without performing the zinc adhesion amount control by the air knife or the like performed in CGL.
The type of the steel sheet subjected to hot-dip galvanizing plating is not particularly limited, and examples thereof include: the zinc-plated steel plate is used for all construction materials subjected to zinc plating processing, such as H-shaped steel, guard rails, corrugated pipes, columns or beams of buildings, sound insulation wall pillars, identification pillars, lighting columns, large-scale bridge girders, bridges such as overpasses, iron bars, stringing metal appliances such as power towers, bolts, seeds, nuts and other small parts, seat frames of solar cells or small wind power generation devices, outdoor exposed iron frames and the like, and can also be cut plate-shaped steel or coiled steel.
It is preferable that the surface of the hot-dip galvanized steel sheet is cleaned with an alkali degreasing agent, a neutral degreasing agent, an acid degreasing agent, or the like, and then hot water washing or water washing is performed to clean the surface.
(method of contacting coating Material)
The method of contacting the coating material with the hot-dip galvanized steel sheet is not particularly limited, and examples thereof include: immersion treatment, spray treatment, brush coating treatment, electrostatic coating treatment, and the like, which are performed in the cooling step after the plating process. When the hot-dip galvanized steel sheet is in the form of a coil, conventionally used methods can be applied, and examples thereof include: roll coating, shower roller (shower roller), spray treatment, dip treatment, curtain coating, flow coating, spin coating, and the like.
(method of drying coating Material)
The most economical method for drying the coating material is a method using preheating after the plating process, and the hot-dip galvanized steel sheet can be dried by immersing the steel sheet in the coating material and leaving the steel sheet as it is. In addition, during the drying, wind may be blown to efficiently blow off the moisture adhering to the surface of the hot-dip galvanized steel sheet.
In the treatment step, when it is difficult to use preheating after zinc plating, it is preferable to use drying equipment capable of evaporating moisture contained in the coating material. In this case, the type of the drying equipment is not particularly limited, and examples thereof include: hot air drying equipment, induction heating type drying equipment, infrared heating drying equipment, near infrared heating drying equipment and the like. The drying temperature when using these drying facilities is not particularly limited, and the limit temperature of the surface of the hot-dip galvanized steel sheet is preferably 60 to 200 ℃, and more preferably 80 to 180 ℃.
(coating film adhesion amount)
By performing the above treatment, a surface-treated hot-dip galvanized steel sheet having a hot-dip galvanized steel sheet and a coating film disposed on the surface thereof is produced.
The amount of the coating is not particularly limited, but is preferably 0.3 to 5.0g/m in terms of more excellent effects of the present invention2More preferably 0.5 to 3.0g/m2。
The produced surface-treated hot-dip galvanized steel sheet can be suitably used for various applications, and examples thereof include: parts for home appliances and building materials, and the like.
The surface-treated hot-dip galvanized steel sheet of the present invention may be coated. In this case, some kind of processing may be further performed on the coated sheet.
Examples
The present invention will be specifically described below by referring to examples of the present invention and comparative examples, but the present invention is not limited to these examples.
1. Test materials
The test materials (raw materials) used are described below. In general, the hot-dip galvanized plated product is a shaped product in many cases, but a plate is used as a raw material in this test. It should be noted that even if the shape of the raw material is changed, the effect exhibited by the present invention is not affected at all.
The hot-dip galvanized steel sheet denoted by M1 below corresponds to the hot-dip galvanized steel sheet produced by hot-dip coating described above. M1 to M3 correspond to molten zinc-plated steel sheets (note that M2 and M3 do not correspond to hot-dip galvanized steel sheets).
M1: hot-dip galvanized steel sheet (according to JIS H8641 HDZ35), spangle (spangle) is small and sized: 700mm × 150mm × 1.6mm (plate thickness), double-sided plating adhesion amount: 360g/m2
M2: hot-dip galvanized steel sheet (according to JIS G3302 SGCC Z06), dimensions: 700mm × 150mm × 0.8mm (plate thickness), double-sided plating adhesion amount: 60g/m2
M3: molten zinc-5% aluminum alloy plated steel sheet (according to JIS G3317 SZACCY08), size: 700mm × 150mm × 0.8mm (plate thickness), double-sided plating adhesion amount: 80g/m2
2. Pretreatment (degreasing treatment)
The test material was subjected to spray treatment for 10 seconds under conditions of a concentration of 20g/L and a temperature of 60 ℃ using Fine Cleaner E6406 (manufactured by Parkerizing, Japan), which is a silicate-based alkaline degreasing agent, and further washed with pure water for 30 seconds, followed by drying, and the obtained dried product was used in the following test.
3. Coating material
Table 1 shows details of the cationic urethane resin (a) used. The manufacturing method is described in detail in the subsequent section.
Loss modulus E '' and loss tangent tan of cationic urethane resin (A)δThe measurement was performed in the following procedure. First, a film (thickness: 300 to 500 μm) of the cationic polyurethane resin (A) was left at room temperature for 15 hours, and then dried at 80 ℃ for 6 hours and further at 120 ℃ for 20 minutes.
Then, the Transverse Direction (TD) of the obtained film (sample area: holding length. times. width: 20 mm. times.5 mm) was measured at a vibration frequency of 10Hz and a strain of 0.1% at a temperature increase rate of 5 ℃/min from-100 ℃ to 200 ℃ using a dynamic viscoelasticity measuring apparatus "RSAG 2" manufactured by TA instruments, and the storage modulus E', the loss modulus E ″ and the loss tangent tan were calculatedδ. The distance between the jigs (chucks) was set to 10 mm.
The amine number was determined as follows.
In Table 1, Tg1 represents the temperature of the maximum peak of the loss modulus E ″ obtained by the above measurement, and Tg2 represents the loss tangent tan obtained by the above measurementδPeak temperature of (c).
The number of peaks is a loss tangent tan which is a ratio of a loss modulus E' to a storage modulus EδThe number of peaks in the temperature dependence curve of (a).
[ Table 1]
Figure 304612DEST_PATH_IMAGE001
Production example 1 cationic urethane resin (A1)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1000 parts by mass of a polycarbonate polyol (Nippollan981R, manufactured by Tosoh corporation, Mw 2,000), bisphenol A-bis (hydroxyethyl ether) (BPE20T, manufactured by Sanyo chemical Co., Ltd., hydroxyl value 346mg/g)100 parts by mass, N-methyldiethanolamine 100 parts by mass, hexamethylene diisocyanate 400 parts by mass and methyl ethyl ketone 800 parts by mass were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0 mass% relative to the non-volatile component. The solution was cooled to 40 ℃, 103 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was subjected to desolventization under reduced pressure at 50 ℃ to obtain an aqueous polyurethane dispersion 1 containing a cationic polyurethane resin (a1) having a nonvolatile content of about 35% by mass.
Production example 2 cationic urethane resin (A2)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1500 parts by mass of polycarbonate polyol (Nippollan981R, manufactured by tokyo corporation, Mw 2,000), 50 parts by mass of bisphenol a-bis (hydroxyethyl ether) (BPE20T, manufactured by mitsunobu corporation, hydroxyl value 346mg/g), 50 parts by mass of N-methyldiethanolamine, 325 parts by mass of hexamethylene diisocyanate, and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to the nonvolatile content. The solution was cooled to 40 ℃, 47 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 2 containing a cationic polyurethane resin (A2) having a nonvolatile content of about 35% by mass.
Production example 3 cationic urethane resin (A3)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube were charged 1000 parts by mass of a polycarbonate polyol (Nippollan980, manufactured by Tosoh Co., Ltd., Mw 1,000), bisphenol A-bis (hydroxyethyl ether) (BPE20T, manufactured by Sanyo chemical Co., Ltd., hydroxyl value 346mg/g)300 parts by mass, N-methyldiethanolamine 100 parts by mass, hexamethylene diisocyanate 535 parts by mass, dicyclohexylmethane diisocyanate 250 parts by mass and methyl ethyl ketone 800 parts by mass, and the mixture was reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0 mass% with respect to the nonvolatile content. The solution was cooled to 40 ℃, 95 parts by mass of dimethyl sulfate was added thereto, and then 2700 parts by mass of deionized water was slowly added thereto to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 3 containing a cationic polyurethane resin (A3) having a nonvolatile content of about 35% by mass.
Production example 4 cationic urethane resin (A4)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1000 parts by mass of a polycarbonate polyol (Nippollan981R, manufactured by tokyo corporation, Mw 2,000), 200 parts by mass of bisphenol a-bis (hydroxyethyl ether) (BPE20T, manufactured by sanyo chemical corporation, hydroxyl value 346mg/g), 100 parts by mass of N-methyldiethanolamine, 480 parts by mass of hexamethylene diisocyanate, and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to a nonvolatile component. The solution was cooled to 40 ℃, and after adding 101 parts by mass of dimethyl sulfate, 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 4 containing a cationic polyurethane resin (A4) having a nonvolatile content of about 35% by mass.
Production example 5 cationic urethane resin (A5)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1500 parts by mass of polycarbonate polyol (Nippollan981R, manufactured by tokyo corporation, Mw 2,000), bisphenol a-bis (hydroxyethyl ether) (BPE20T, manufactured by sanyo corporation, hydroxyl value 346mg/g)100 parts by mass, 50 parts by mass of N-methyldiethanolamine, 370 parts by mass of hexamethylene diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to the non-volatile component. The solution was cooled to 40 ℃, 48 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 5 containing a cationic polyurethane resin (a5) having a nonvolatile content of about 35 mass%.
Production example 6 cationic urethane resin (A6)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1000 parts by mass of a polycarbonate polyol (Nippollan980, manufactured by Tosoh Co., Ltd., Mw 1,000), 200 parts by mass of bisphenol A-bis (hydroxyethyl ether) (BPE20T, manufactured by Sanyo chemical Co., Ltd., hydroxyl value 346mg/g), 100 parts by mass of N-methyldiethanolamine, 450 parts by mass of hexamethylene diisocyanate, 220 parts by mass of dicyclohexylmethane diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to the nonvolatile content. The solution was cooled to 40 ℃, 87 parts by mass of dimethyl sulfate was added thereto, and then 2700 parts by mass of deionized water was slowly added thereto to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 6 containing a cationic polyurethane resin (A6) having a nonvolatile content of about 35% by mass.
Production example 7 cationic urethane resin (A7)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1500 parts by mass of polycarbonate polyol (Nippollan981R, manufactured by tokyo corporation, Mw 2,000), bisphenol a-bis (hydroxyethyl ether) (BPE20T, manufactured by sanyo chemical corporation, hydroxyl value 346mg/g)100 parts by mass, 50 parts by mass of N-methyldiethanolamine, 260 parts by mass of hexamethylene diisocyanate, 150 parts by mass of dicyclohexylmethane diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to a non-volatile component. The solution was cooled to 40 ℃, 49 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was subjected to desolventization under reduced pressure at 50 ℃ to obtain an aqueous polyurethane dispersion 7 containing a cationic polyurethane resin (a7) having a nonvolatile content of about 35% by mass.
Production example 8 cationic urethane resin (A8)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1500 parts by mass of polycarbonate polyol (Nippollan981R, manufactured by tokyo corporation, Mw 2,000), bisphenol a-bis (hydroxyethyl ether) (BPE20T, manufactured by sanyo chemical corporation, hydroxyl value 346mg/g)100 parts by mass, 50 parts by mass of N-methyldiethanolamine, 315 parts by mass of hexamethylene diisocyanate, 80 parts by mass of dicyclohexylmethane diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to a non-volatile component. The solution was cooled to 40 ℃, 49 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 8 containing a cationic polyurethane resin (A8) having a nonvolatile content of about 35% by mass.
Production example 9 cationic urethane resin (A9)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1500 parts by mass of polycarbonate polyol (Nippollan981R, manufactured by tokyo corporation, Mw 2,000), 50 parts by mass of bisphenol a-bis (hydroxyethyl ether) (BPE20T, manufactured by sanyo chemical corporation, hydroxyl value 346mg/g), 50 parts by mass of N-methyldiethanolamine, 310 parts by mass of hexamethylene diisocyanate, 35 parts by mass of dicyclohexylmethane diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0 mass% with respect to the nonvolatile content. The solution was cooled to 40 ℃, 49 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 9 containing a cationic polyurethane resin (a9) having a nonvolatile content of about 35 mass%.
Production example 10 cationic urethane resin (A10)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube were charged 750 parts by mass of a polycarbonate polyol (Nippollan981R, manufactured by Tosoh Corp., Ltd., Mw 2,000), 125 parts by mass of bisphenol A-bis (hydroxyethyl ether) (BPE20T, manufactured by Sanyo Kabushiki Kaisha, hydroxyl value 346mg/g), 50 parts by mass of N-methyldiethanolamine, 290 parts by mass of hexamethylene diisocyanate, 35 parts by mass of dicyclohexylmethane diisocyanate and 800 parts by mass of methyl ethyl ketone, and the mixture was reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to a non-volatile component. The solution was cooled to 40 ℃, 51 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 10 containing a cationic polyurethane resin (a10) having a nonvolatile content of about 35 mass%.
Production example 11 cationic urethane resin (A11)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube were charged 750 parts by mass of a polycarbonate polyol (Nippollan981R, manufactured by Tosoh Corp., Ltd., Mw 2,000), 125 parts by mass of bisphenol A-bis (hydroxyethyl ether) (BPE20T, manufactured by Sanyo Kabushiki Kaisha, hydroxyl value 346mg/g), 50 parts by mass of N-methyldiethanolamine, 220 parts by mass of hexamethylene diisocyanate, 110 parts by mass of dicyclohexylmethane diisocyanate and 800 parts by mass of methyl ethyl ketone, and the mixture was reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to a non-volatile component. The solution was cooled to 40 ℃, 50 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 11 containing a cationic polyurethane resin (A11) having a nonvolatile content of about 35% by mass.
Production example 12 cationic urethane resin (A12)
Into a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 500 parts by mass of a polycarbonate polyol (Nippollan980, manufactured by tokyo corporation, Mw 1,000), 150 parts by mass of a polycarbonate polyol (Nippollan981R, manufactured by tokyo corporation, Mw 2,000), 250 parts by mass of bisphenol a-bis (hydroxyethyl ether) (BPE20T, manufactured by mitsui chemical corporation, hydroxyl value 346mg/g), 50 parts by mass of N-methyldiethanolamine, 275 parts by mass of hexamethylene diisocyanate, 150 parts by mass of dicyclohexylmethane diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0 mass% with respect to the nonvolatile content. The solution was cooled to 40 ℃, 44 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 12 containing a cationic polyurethane resin (A12) having a nonvolatile content of about 35% by mass.
Production example 13 cationic urethane resin (A13)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1500 parts by mass of polycarbonate polyol (Nippollan980, manufactured by Tosoh Co., Ltd., Mw 1,000), 25 parts by mass of bisphenol A-bis (hydroxyethyl ether) (BPE20T, manufactured by Sanyo chemical Co., Ltd., hydroxyl value 346mg/g), 50 parts by mass of N-methyldiethanolamine, 500 parts by mass of hexamethylene diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to the nonvolatile content. The solution was cooled to 40 ℃, 49 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was subjected to desolventization under reduced pressure at 50 ℃ to obtain an aqueous polyurethane dispersion 13 containing a cationic polyurethane resin (a13) having a nonvolatile content of about 35% by mass.
Production example 14 cationic urethane resin (A14)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1500 parts by mass of polycarbonate polyol (Nippollan980, manufactured by Tosoh Co., Ltd., Mw 1,000), 25 parts by mass of bisphenol A-bis (hydroxyethyl ether) (BPE20T, manufactured by Sanyo chemical Co., Ltd., hydroxyl value 346mg/g), 50 parts by mass of N-methyldiethanolamine, 500 parts by mass of hexamethylene diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to the nonvolatile content. The solution was cooled to 40 ℃, 25 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 14 containing a cationic polyurethane resin (A14) having a nonvolatile content of about 35% by mass.
Production example 15 cationic urethane resin (A15)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 1600 parts by mass of a polycarbonate polyol (Nippollan981R, manufactured by Tosoh Corp., Ltd., Mw 2,000), 150 parts by mass of bisphenol A-bis (hydroxyethyl ether) (BPE20T, manufactured by Sanyo Kabushiki Kaisha, having a hydroxyl value of 346mg/g), 50 parts by mass of N-methyldiethanolamine, 245 parts by mass of hexamethylene diisocyanate, 275 parts by mass of dicyclohexylmethane diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to a non-volatile component. The solution was cooled to 40 ℃, 48 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 15 containing a cationic polyurethane resin (a15) having a nonvolatile content of about 35 mass%.
Production example 16 cationic urethane resin (A16)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 600 parts by mass of a polycarbonate polyol (Nippollan981R, manufactured by Tosoh Co., Ltd., Mw 2,000), 50 parts by mass of bisphenol A-bis (hydroxyethyl ether) (BPE20T, manufactured by Sanyo chemical Co., Ltd., hydroxyl value 346mg/g), 175 parts by mass of N-methyldiethanolamine, 550 parts by mass of hexamethylene diisocyanate and 800 parts by mass of methyl ethyl ketone were charged, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0% by mass relative to the nonvolatile content. The solution was cooled to 40 ℃, 179 parts by mass of dimethyl sulfate was added, and then 2700 parts by mass of deionized water was slowly added to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was subjected to desolventization under reduced pressure at 50 ℃ to obtain an aqueous polyurethane dispersion 16 containing a cationic polyurethane resin (a16) having a nonvolatile content of about 35% by mass.
Production example 17 cationic urethane resin (A17)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube were charged 1000 parts by mass of polycarbonate Polyol (Kuraray Polyol C-3090, manufactured by Kuraray, inc., Mw 3, 000), bisphenol a-bis (hydroxyethyl ether) (BPE20T, manufactured by sanyo chemical corporation, hydroxyl value 346mg/g)20 parts by mass, N-methyldiethanolamine 30 parts by mass, hexamethylene diisocyanate 160 parts by mass and methyl ethyl ketone 800 parts by mass, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0 mass% relative to the non-volatile component. The solution was cooled to 40 ℃, and 30 parts by mass of dimethyl sulfate was added, followed by slowly adding 2700 parts by mass of deionized water to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 17 containing a cationic polyurethane resin (a17) having a nonvolatile content of about 35 mass%.
Production example 18 cationic urethane resin (A18)
600 parts by mass of polyethylene glycol (PEG2000, manufactured by Sanyo chemical Co., Ltd., Mw of 2,000), 30 parts by mass of N-methyldiethanolamine, 80 parts by mass of hexamethylene diisocyanate, and 800 parts by mass of methyl ethyl ketone were charged into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas blowing tube, and reacted at 75 ℃ for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.0 mass% with respect to the nonvolatile component. The solution was cooled to 40 ℃, and 30.2 parts by mass of dimethyl sulfate was added, followed by slowly adding 2700 parts by mass of deionized water to carry out emulsification dispersion. Thereafter, an aqueous solution prepared by dissolving 45 parts by mass of ethylenediamine in 100g of water was added thereto, and the mixture was stirred for 1 hour. This was desolventized at 50 ℃ under reduced pressure to obtain an aqueous polyurethane dispersion 18 containing a cationic polyurethane resin (A18) having a nonvolatile content of about 35% by mass.
The phosphoric acid compound (B) used is shown in table 2, and the trivalent chromium compound (C) used is shown in table 3.
[ Table 2]
TABLE 2
Reference numerals Composition (I)
B1 Phosphoric acid
B2 Metaphosphoric acid
[ Table 3]
TABLE 3
Reference numerals Composition (I)
C1 Chromium fluoride
4. Preparation of coating Material
A cationic urethane resin (a), a phosphoric acid compound (B), and a trivalent chromium compound (C) were mixed in the combination and ratio shown in table 4 in this order, and the solid content concentration was adjusted to 20 mass% with deionized water to prepare a coating material. The content ratio of the phosphoric acid compound (B) and the trivalent chromium compound (C) is based on the mass% of the solid content of the cationic urethane resin (a) (in other words, the content (mass part) of each component based on 100 mass parts of the cationic urethane resin (a)).
In table 4, "BV/AV" represents the ratio of the content ratio (% by mass) (BV) of the phosphoric acid compound (B) to the solid content (mass%) of the cationic urethane resin (a) to the amine value.
[ Table 4]
Figure 48577DEST_PATH_IMAGE002
5. Method for manufacturing test board
Test pieces were produced by applying the coating material of the present invention to each test piece with a bar coater and subjecting the resultant to heat treatment at a limiting plate temperature shown in table 5 to form a coating film on each test piece. The coating amounts in the examples are shown in table 5, and the adjustment of the coating amounts was performed by adjusting the concentration of the coating material (deionized water dilution) and the number of the bar coater.
[ Table 5]
Figure 692048DEST_PATH_IMAGE003
[ Table 6]
Figure 27215DEST_PATH_IMAGE004
[ Table 7]
Figure 756136DEST_PATH_IMAGE005
[ Table 8]
Figure 553060DEST_PATH_IMAGE006
6. Evaluation method
(1) Appearance Property (skin appearance)
The appearance of the resulting test panel was visually evaluated, and the level of ○ or more was a practical level.
◎ + (ii) has substantially the same appearance as plated film, and hardly changes after film treatment;
◎, the plating appearance is almost the same as that of plating, but there is little color variation depending on the visual angle;
○, which has almost the same appearance as plating but has little color variation;
△, a part having a slightly white or yellow color different from the appearance of the plating;
x: the plating appearance was clearly seen in white or yellow in many portions.
(2) Rub resistance (solvent resistance)
The surface of the skin of the test plate obtained by immersing ethanol in gauze was subjected to a rubbing test of 20 times to and fro, and the surface was observed to be at a level of not less than △.
◎ + (iii) no change in appearance;
◎, no appearance change (no change from front view) and slight change from oblique view;
○ slight variation from frontal view;
△ slight variation from front view (half left or right peel);
x: there was a variation (substantially whole area peeling).
(3) Corrosion resistance
The test panels thus obtained were subjected to a salt water spray test in accordance with JIS-Z-2371 to determine the white rust area ratio after 24 hours, and the white rust area ratio was evaluated in accordance with the following criteria. △ or more is a practical level.
◎ + less than 5%;
◎, more than 5% and less than 10%;
○ + more than 10% and less than 20%;
○, more than 20% and less than 30%;
△ + more than 30% and less than 40%;
△, more than 40% and less than 50%;
x: more than 50 percent.
(4) Phosphate treatability (coating type phosphate treatability)
The test plate thus obtained was treated with a chemical synthesis chemical Palbond L15C for phosphate treatment (A agent 250g/L + B agent 250g/L, 25 ℃ C., brush coating) manufactured by Parkerizing, Japan, and then left to stand for 5 minutes, and the surface shape of the brush coated portion was observed to determine the area ratio of the gray color change of the brush coated portion, and the evaluation was made according to the following criteria.
◎+：100％；
◎, more than 95% and less than 100%;
○, more than 85% and less than 95%;
△, more than 70% and less than 85%;
x: less than 70 percent.
(5) Adhesion of surface coating
Next, 100 grids having a width of 1mm were applied to the coating film by a dicing machine, left to stand in a constant temperature storage at-20 ℃ for 5 hours or more, immediately after being taken out from the constant temperature storage, and then subjected to an Erichsen (Erichsen) processing by 7mm extrusion, and a tape peeling test of the processed portion was performed, and the number of peeled grids was evaluated as follows, and the number of peeled grids was △ or more, which is a practical level.
◎ + without peeling;
◎, the number of peeled pieces is more than 1 and less than 5;
○, the number of peeled pieces is more than 6 and less than 10;
△, the number of peeled pieces is more than 11 and less than 20;
x: the number of the peeled pieces is more than 20.
(6) Impact resistance
Next, the test plate having the coating film was left to stand in a constant temperature storage at 40 ℃ for 5 hours or more, and immediately after the test plate was taken out, a DuPont impact tester was used to drop a lead weight (hanging ) having a diameter of 1/2 inches and 1kg from a height of 50cm against the coating film, and then the impact portion was subjected to tape peeling, and it was judged that the residual area ratio of the coating film was determined to be at least △, which is a practical level.
◎+：100％；
◎, more than 95% and less than 100%;
○, more than 80% and less than 95%;
△, more than 50% and less than 80%;
x: less than 50 percent.
(7) Storage stability of the coating
When the coating materials used in the examples and comparative examples were allowed to stand at 40 ℃ for a period until gelation and precipitation occurred, the storage stability was evaluated as follows, and the storage stability was at least △.
◎ + for more than 3 months;
◎, more than 2 months and less than 3 months;
○, more than 1 month and less than 2 months;
△, more than 2 weeks and less than 1 month;
x: less than 2 weeks.
[ Table 9]
Figure 51037DEST_PATH_IMAGE007
[ Table 10]
Figure 822684DEST_PATH_IMAGE008
[ Table 11]
Figure 242164DEST_PATH_IMAGE009
[ Table 12]
Figure 593511DEST_PATH_IMAGE010
As shown in Table 6, it was confirmed that the desired effects can be obtained by using the coating material of the present invention.
Among them, according to the comparison of examples 2, 5, 12 and 21 with other examples, it was confirmed that: when a phosphoric acid compound is used, the effect is more excellent (particularly, the phosphate treatability is excellent).
In addition, from comparison of example 26 with other examples (e.g., example 25, etc.), it was confirmed that: loss tangent tanδWhen the peak temperature (Tg2) is in a predetermined range (-50 ℃ to-2 ℃), the coating adhesion of the surface coating layer is more excellent.
Further, comparison between examples 7 to 8 and examples 12 to 19 confirmed that: the ratio ((BV)/(AV)) is in a predetermined range (0.1 to 9.5), and the effect is further excellent.
Further, comparison between example 20 and examples 27 to 29 confirmed that: when the Amine Value (AV) is within a predetermined range (2 to 5mgKOH/g), the effect is more excellent (particularly, the storage stability is excellent).
Further, comparison between example 25 and examples 30 to 32 confirmed that: by further using the trivalent chromium compound (C), the effect is more excellent (particularly, the corrosion resistance is excellent).

Claims (20)

1. A coating material for hot dip galvanized steel sheet, which contains a cationic polyurethane resin (A) having at least one cationic functional group selected from primary to tertiary amino groups and quaternary ammonium salt groups,
the cationic urethane resin (A) has a polycarbonate structural unit and a bisphenol structural unit,
the temperature (Tg1) at which the maximum peak of the loss modulus E' of the cationic polyurethane resin (A) appears is in the range of-60 ℃ to-5 ℃,
the loss tangent tan δ, which is the ratio of the loss modulus E ″ to the storage modulus E' of the cationic urethane resin (a), is composed of one peak.
2. The coating material for hot-dip galvanized steel sheet according to claim 1, wherein the peak temperature (Tg2) of the loss tangent tan δ is in the range of-50 ℃ to-2 ℃.
3. The coating material for hot dip galvanized steel sheet according to claim 1, further comprising a phosphoric acid compound (B).
4. The coating material for hot dip galvanized steel sheet according to claim 2, further comprising a phosphoric acid compound (B).
5. The coating material for hot dip galvanized steel sheet according to claim 3, wherein the phosphoric acid compound (B) contains at least one selected from the group consisting of orthophosphoric acid, condensed phosphoric acid and salts thereof.
6. The coating material for hot dip galvanized steel sheet according to claim 4, wherein the phosphoric acid compound (B) contains at least one selected from the group consisting of orthophosphoric acid, condensed phosphoric acid and salts thereof.
7. The coating material for hot-dip galvanized steel sheet according to claim 1, wherein the Amine Value (AV) of the cationic polyurethane resin (A) is 2.0 to 5.0 mgKOH/g.
8. The coating material for hot-dip galvanized steel sheet according to claim 2, wherein the Amine Value (AV) of the cationic polyurethane resin (A) is 2.0 to 5.0 mgKOH/g.
9. The coating material for hot-dip galvanized steel sheet according to claim 3, wherein the Amine Value (AV) of the cationic polyurethane resin (A) is 2.0 to 5.0 mgKOH/g.
10. The coating material for hot-dip galvanized steel sheet according to claim 4, wherein the Amine Value (AV) of the cationic polyurethane resin (A) is 2.0 to 5.0 mgKOH/g.
11. The coating material for hot-dip galvanized steel sheet according to claim 5, wherein the Amine Value (AV) of the cationic polyurethane resin (A) is 2.0 to 5.0 mgKOH/g.
12. The coating material for hot-dip galvanized steel sheet according to claim 6, wherein the Amine Value (AV) of the cationic polyurethane resin (A) is 2.0 to 5.0 mgKOH/g.
13. The coating material for hot-dip galvanized steel sheet according to claim 9, wherein the ratio ((BV)/(AV)) of the content ratio (BV) of the phosphoric acid compound (B) to the solid content (mass%) of the cationic polyurethane resin to the amine value is 0.1 to 9.5.
14. The coating material for hot-dip galvanized steel sheet according to claim 10, wherein the ratio ((BV)/(AV)) of the content ratio (BV) of the phosphoric acid compound (B) to the solid content (mass%) of the cationic polyurethane resin to the amine value is 0.1 to 9.5.
15. The coating material for hot-dip galvanized steel sheet according to claim 11, wherein the ratio ((BV)/(AV)) of the content ratio (BV) of the phosphoric acid compound (B) to the solid content (mass%) of the cationic polyurethane resin to the amine value is 0.1 to 9.5.
16. The coating material for hot-dip galvanized steel sheet according to claim 12, wherein the ratio ((BV)/(AV)) of the content ratio (BV) of the phosphoric acid compound (B) to the solid content (mass%) of the cationic polyurethane resin to the amine value is 0.1 to 9.5.
17. The coating material for hot dip galvanized steel sheet as set forth in any one of claims 1 to 16, further comprising a trivalent chromium compound (C).
18. A method for treating a hot-dip galvanized steel sheet, which comprises treating the hot-dip galvanized steel sheet with the coating material for a hot-dip galvanized steel sheet according to any one of claims 1 to 17.
19. A method for producing a surface-treated hot-dip galvanized steel sheet, which comprises bringing the coating material for a hot-dip galvanized steel sheet described in any one of claims 1 to 17 into contact with a hot-dip galvanized steel sheet to produce a surface-treated hot-dip galvanized steel sheet having the hot-dip hot-galvanized steel sheet and a film disposed on the surface of the hot-dip hot-.
20. A surface-treated hot-dip galvanized steel sheet obtained by the production method according to claim 19.
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